REGATEC 2015

Bringing technology and industry together

Conference Proceedings
2nd International Conference on
Renewable Energy Gas Technology
7-8 May 2015, Barcelona, Spain

Editors: Jörgen Held and Frank Scholwin

22nd International Conference on Renewable Energy Gas Technology

nd International Technology
7-8
7-8May
May2015,
2015, Barcelona, Spain
Barcelona, Spain
Conference proceedings - 2nd International Conference on Renewable Energy Gas
Technology
7th – 8th of May 2015, Barcelona, Spain
Editors: Dr. Jörgen Held, Renewable Energy Technology International AB
Prof. Frank Scholwin, Institute for Biogas, Waste Management & Energy

Publisher
Renewable Energy Technology International AB
Skarpskyttevägen 10 D
SE-226 42 Lund
SWEDEN
info@renewtec.se

Renewable Energy Technology International AB is a private company promoting the

transfer to a sustainable and environmentally friendly energy system.

© Renewable Energy Technology International AB. All rights reserved.

Printed by Serviceförvaltningen/Tryckeriet Lunds kommun, Lund, SWEDEN, 2015

ISBN 978-91-981149-1-1
PREFACE

Oil remains the world’s leading fuel, with 32.9% of the global energy consumption (2013).
However, it continued to lose market share for the 14th consecutive year. Natural gas is at
23.7% of the global energy consumption and being a clean and versatile fuel with excellent
emission data it´s expected to surpass oil as the dominating fuel during this century. Natural
gas as transport fuel is growing and in Europe there is a new directive forcing the member
states to offer filling stations for CNG/CBG every 150 km.

The growing market for natural gas provides excellent opportunities for renewable methane
since it’s miscible in any proportion with natural gas and can be distributed in an efficient
and environmentally friendly way through the existing natural gas grid. The fact that
renewable methane is sustainable, in principle has a zero carbon footprint, and can be
produced by conversion of different types of waste and by-products or from stranded
electricity makes it an attractive fuel. The rapid growth of biogas upgrading capacity in
Europe and the increasing trade within the EU member countries as well as cross border
trading reflect this fact.

The thermo-chemical conversion path related to gasification and methanation of lingo-

cellulose feedstock is not as developed as the anaerobic digestion sector but there has been
good progress in the last decade. Last year the world’s first industrial scale biomethane
plant, GoBiGas, was taken into operation.

A third sector under development is related to the Power-to-gas concept where intermittent
or stranded electricity is used to produce hydrogen, which in turn is reacted with carbon
dioxide and/or carbon monoxide to form methane. Here the Audi e-gas project and the
BioCat project demonstrate catalytical and biological methanation in the MW scale.

There are several synergies between these three sectors that haven’t been exploited yet.
The most obvious ones are to apply carbon dioxide removal technology from the biogas
sector to the thermo-chemical conversion path and use carbon dioxide from biogas and
gasification plants in the Power-to-gas concept. Other synergies are related to innovative
heat integration, better utilization of the feedstock, increased security of methane supply,
and cost sharing for the upgrading, distribution and utilization of renewable methane.

We started the REGATEC conference series primarily to create a platform for the renewable
methane community to meet and exchange ideas, information and experiences and to
highlight the latest advances and progress as well as showcase unique industrial projects.
The conference is also an important meeting point for academia, technology developers,
industry and decision makers.

It’s our hope that the conference will spark new ideas and insights and that your
expectations will be fulfilled. Please enjoy two days of exciting oral presentations, the poster
session, the exhibition, the display of NGVs, and the possibility to make new contacts.

Dr. Jörgen Held and Prof. Frank Scholwin

2nd International Conference on Renewable Energy Gas Technology, REGATEC 2015
7th-8th of May 2015
Barcelona, Spain

THANKS TO THE SPONSORS

We are very pleased that leading biogas, gasification, gas distribution, and energy companies
as well as research institutes from Bulgaria (1), France (1), Germany (2), Spain (1), Sweden
(2) and the Netherlands (1) have chosen to support REGATEC 2015, reflecting the
multifaceted and international character ofthe conference. This conference would not have
been possible withoutthe financial support ofthe REGATEC 2015 sponsors. Thank you!

GOLD SPONSORS

SILVER SPONSORS

ORGANIZERS
The 2nd International Conference on Renewable Energy Gas Technology is organized by
Renewable Energy Technology International AB, Sweden and Institute for Biogas, Waste
Management & Energy, Germany.
CONTENT
Plenary session I

The role of biogas in the global energy transition

Presen ng author: Dr. Shunichi Nakada, Interna onal Renewable Energy Associa on 1

Renewable methane for mobility and EBA’s perspe ve on the biomethane market
Presen ng author: Dr. Jan Stambasky, European Biogas Associa on 5

Parallel session Ia. Biogas cleaning R&D and experiences

Next genera on technology to reduce biogas up-grada on cost by 46%

Presen ng author: Mr. Aniruddha Sharma, Carbon Clean Solu ons Ltd 9

Development of next ge n biogas cleaning & upgrading technology

– Demonstration of terpene removal
Presen ng author: Dr. Marco Linders, TNO 13

Towards a measurement infrastructure for the conformity assessment of

biomethane and upgraded biogas
Presen ng author: Dr. Adriaan van der Veen, VSL 15

Parallel session Ib. Gasifica on R&D including CHP

M ves for biomass based bio-SNG produc on and perspe ves on the
Heatpipe Reformer technology
Presen ng author: Prof. Jürgen Karl, University of Erlangen-Nuremberg 19

Challenges in biomass gasifica on

Presen ng author: Dr. Bram van der Dri , Energy Research Centre o he Netherlands 23

Bioenergy Sustaining the Future – a pan-European funding mechanism for

bioenergy demonstrators
Presen ng author: Dr. Megan Cooper, Department of Energy & Climate Change 27

Parallel session IIa. Advances in biogas upgrading

Small scale upgrading of biogas with in-situ methane enrichment and wood ash filter
Presen ng author: MSc. Johan Andersson, Swedish Ins ute of Agricultural and Environmental
Engineering 31

Hydrogenotrophic methanogenesis: Performance and robustness of a self

regenera ve biocatalyst
Presen ng author: Dr. Sandra Esteves, University of South Wales 35

Parallel session IIb. Product gas cleaning R&D

Cleaning biomass derived syngas with fluid bed reforming catalysts

Presen ng author: Dr. Kim Magrini, Na onal Renewable Energy Laboratory 39
TÜBITAK gas cleaning R&D ac vi es
Presen ng author: Dr. Ersin Üresin, TÜBITAK 43

Parallel session IIIa. Biological methana on and P2G

Innova ve bioelectrochemical-anaerobic-diges on coupled system for ammonia

recovery and biomethane produc on from ammonia-rich residues
Presen ng author: Dr. Yifeng Zhang, Technical University of Denmark 47

BioCat project – Taking biological methana on to market readiness

Presen ng author: Mr. Dominic Hofste r, Electrochaea 51

Experiences with one year opera on of power-to-gas in Rozenburg, NL

Prese g author: BSc. Johan Holstein, DNV GL – Oil & Gas 55

Parallel session IIIb. Cataly cal/biological methana n incl. P2G

Experiences of cataly c methana on: contexts of P2G concept and biomass-based

processes
Presen ng author: Prof. Anne-Cécile Roger, University of Strasbourg 59

Methana on technology and planned ac v es within the SYNFERON project

Presen ng author: Dr. Niels Bjarne Rasmussen, Danish Gas Technology Centre 63

Cataly c methana n – the Audi e-gas project as an example of industrialized

technology for power to gas
Presen ng author: Mr. Gregor Waldstein, ETOGAS GmbH 67

Parallel session IVa. Industrial biogas/landfill gas projects

Developing the biomethane market in Brazil: The Dois Arcos case and the
regulatory challenges
Presen g author: Mr. Márcio Schi , Ecometano 69

Feasibility of renewable natural gas (RNG) projects, an interna onal overview

Presen ng author: Mr. Eberhart Wusterhaus Gomez, Schmack Carbotech GmbH 72

Experiences from Sweden’s largest biogas plant, Jordberga

Presen ng author: Ms. Pia Ekelund, Swedish Biogas Interna onal 74

Parallel session IVb. Industrial gasifica on projects

Pres g authors: Dr. Friedrich Kirnbauer, Bioenergy 2020+ GmbH 76

Industrial scale gasifica on of agricultural and forest residues using EQTEC gasifier
technology coupled to IC engines
Presen ng author: Mr. Luis Sanchez Angrill, EQTEC Iberia S.L. 80

Presen ng author: MSc. Malin Hedenskog, Gothenburg Energy 82

Plenary session II

Biomethane in Sweden – statistics and perspectives

Presenting author: Dr. Jörgen Held, Renewable Energy Technology International AB 84

Renewable methane in France and Europe – an industrial perspective

Presenting author: Dr. Olivier Guerrini, GDF Suez 88

Poster session

Syngas production in sewage treatment plants: development of a single catalyst

for tar conversion and direct biogas reforming
Presenting author: Manuel Jesús Benito González, CIEMAT 89

Energy production during wastewater treatment through combination of biogas

production and microalgae culture
Presenting author: Ignacio de Godos Crespo, FCC Aqualia S.A. 91

Thermo-economic and experimental investigation of small to medium-scale

integrated biomass gasification solid oxide fuel cell systems
Presenting author: Stephan Herrmann, Technische Universität München 93

Room temperature synthesis of synthetic natural gas using a catalytic-dielectric

barrier discharge (DBD) plasma reactor
Presenting author: Teresa Andreu, IREC 95

BIOGAS+. Enhancing anaerobic conversion of biomass and biogas production by

controlled dosing of iron to Archea bacteria via designed iron oxide nanoparticles
Presenting author: Victor Puntes, Applied Nanoparticles S.L. 97

Biomass gasification using pure oxygen instead of air

Presenting author: Alexandre Bacq, Xylowatt SA 99

Green gas by gasification of wet biomass in supercritical water

Presenting author: Angela Justina Kumalaputri, Rijksuniversiteit Groningen 101

Application of a modular and interdisciplinary approach to the development of

a biological methane production (BMP) process
Presenting author: Sébastien Bernacchi, Vienna University of Technology 103

Effects of influent methane concentration on biogas upgrading and biogas

slurry purification under various LED light wavelengths by using of Chlorella sp.
Presenting author: Cheng Yan, China University of Geosciences 105

Biolimp-Siloxa. Technology for biogas cleaning for its use as biofuel

Presenting author: Joaquin Reina Hernández, Energy & Waste S.L. 107

Operation window for advanced SOFC system operated with natural gas or
biogas
Presenting author: Noora Kaisalo, VTT Technical Research Institute of Finland 109
Challenges in the design and autom c opera on of an anaerobic diges on
machine – experiences from the ORION project
Presen ng author: Belén Fernández, IRTA 111

Air-steam biomass gasifica on in a fluidised bed reactor in presence of

ceramic filters
Presen ng author: Giacomo Spinelli, University of Teramo 113

Autothermal biomass gasifica on system for clean and efficient power gener n
Presen ng author: Janina Ilmurzynska, Ins tute of Power Engineering 115

High-pressure anaerobic diges on up to 100 bar: the effects on biogas

produc on and upgrading
Presen ng author: Wolfgang Merkle, University of Hohenheim 117

Pneum c conveying of biocolal from hydrothermal carboniza on: An approach

for small scale entrained-flow gasifica on
Pres g author: Ludwig Briesemeister, Technische Universität München 119

Establishment and analysis of a two-stage process for simultaneous produ on

of biohydrogen and biomethane
Presen ng author: Robert Manig, DBI Gastechnologisches Ins tut 121

Medium-temperature cataly c tar reforming of biogenous synthesis gas

– modelling and sensi vity analysis
Presen ng author: Michaela Fraubaum, Vienna University of Technology 123

Process for cost-effec ve removal of sulphur and oxygen from biomethane

on iron oxide sorbents
Presen ng author: Toni Raabe, DBI Gastechnologisches In ut 125

High temperature biomass gasifica on in an entrained flow reactor

– commissioning and first trials of a 100 kW test facility
Presen g author: Michael Kremling, Technische Universität München 127

Biogas upgrading by electromethanogenesis using microbial electrolysis cell

Presen ng author: August Bonma Blasi, GIRO Joint Research Unit IRTA-UPC 129

RENOVAGAS project – ge ng synthe c natural gas from renewable energy

sources (RES)
Presen ng author: Susana Pérez Gil, Tecnalia 131

The effect of heat buffering on the performance of concentra on swing

adsorption for the purpose of biogas upgrading
Presen ng author: Carole Harrivelle, Universität Stu gart 133

Syngas cleaning and upgrading for SNG produc on – experimental results on tars,
hydrocarbons and other impuri es
Presen ng author: Sebas an Fendt, Technische Universität München 135
Advanced concepts for integrated SNG production at pulp mills
Presenting author: Katja Kuparinen, Lappeenranta University of Technology 137

Off-grid biomethane mobile solution – investigation on upgrading & storage

mobile units and centralized injection facility
Presenting author: Laura Gil Carrera, Gas Networks Ireland 139

Offshore biomethane production: the new frontier of anaerobic digestion in

aquaculture and maritime operations
Presenting author: Mario A. Rosato, Sustainable Technologies SL 141

Analysis of power-to-gas technology with oxyfuel combustion integration

Presenting author: Manuel Bailera, Fundación CIRCE 143

Scrubber oil recovery in biomass gasification plants

Presenting author: Laura Malek, Lund University 145

Energy balance, mass balance analysis and econometric modelling of a

biological-fermentative power-to-gas process
Presenting author: Katharina Edelmann, Wissenschaftszentrum Straubing 147

Catalytic decomposition of biogas: a novel approach for biogas valorisation into

syngas and bio-carbon nanofibers
Presenting author: Saul de Llobet, Instituto de Carboquímica (CSIC) 149

Towards energy self-sufficiency at Murcia Este WWTP

Presenting author: Francisco J. Navarro Sánchez, Aguas de Murcia 151

Potential candidates for improvement of anaerobic degradation of lignocellulosic

biomass
Presenting author: Orsolya Strang, University of Szeged 153

Leachate recirculation and its effect on enhancing LFG production, and site
stabilization, a modelling study
Presenting author: Belkacem Adouane, University of Batna 155

Digesters upflow anaerobic sludge blanket treating brewery effluent

Presenting author: Ederaldo Godoy Junior, University of Taubaté 157

Experience of Aguas de Murcia on biogas valorization R&D projects

Presenting author: Teresa Reyes Serna, Aguas de Murcia 159

Enzymatic upgrading of biogas and how renewable resources can be integrated

into the natural gas grid
Presenting author: Thomas Hernø, HMN Gashandel A/S 161

Biogas as a component for dual fuel system of vehicle´s internal combustion engines
Presenting author: Jamshid Inoyatkhodjaev, General Motors Powertrain Uzbekistan 163
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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

The role of biogas in the global energy transition

Shunichi NAKADA1
1 International Renewable Energy Agency (IRENA), Bonn, Germany

1. Current application also produced in small, domestic-scale

Today, use of biomass currently makes up digesters, mainly in developing countries
75% of total renewable energy consump- —including China, India, Nepal, and
tion, with traditional use of biomass Rwanda—and is combusted directly to
accounting for more than half of all provide heat for cooking [1].
renewables. High share derived from its
versatile capacity as an energy source, Power application
which can generate not only power, but Use of biogas for power generation also is
also heat and transport fuel. Diversity in rising rapidly in Europe. By the end of
feedstock (energy crop, crop residue, 2012, more than 13,800 biogas power
agro-processing residue, animal waste, plants (up roughly 1,400 over the year),
MSW, wood resource, etc.) and associated with a total installed capacity of 7.5 GW,
conversion technology also support wide were in operation. In China, bio-power
range of energy application globally. capacity rose very rapidly for several
Biogas also inherit this characteristics and years, but growth has slowed recently due
currently applied for power generation for to limited availability of suitable biomass.
mini grid through CHP, district heating By the end of 2013, bio-power capacity
through gas grid, small scale digester to reached 6.2 GW (excluding 2.3 GW of
replace traditional biomass for cooking/ waste-to-energy combustion). Most of this
heating, and biomethane for transporta- was direct combustion of agricultural and
tion and heat application, etc. forestry biomass, including 1.7 GW of
bagasse, 1.2 GW from gasification of
Heat application sludge and biomass, 0.3 GW of large-scale
Biogas heat application can be classified biogas, and other sources [1].
into three categories, industry application,
district heating, and small digester for Transport fuel application
home cooking/heating. In developed The use of biomethane as a transport fuel
countries, it is used primarily in CHP is increasing as well, mainly in Norway and
plants, which produce 110 TJ of heat and Sweden.
44.5 GWh of electricity. The small remain-
der used by the transport sector was first 2. Advantage of Biogas
upgraded to biomethane, with limited There are two main processes converting
volumes now being traded among EU biomass feedstock into biogas, bio-
member states by injection into the chemical conversion and thermochemical
natural gas grid. A number of large-scale conversion. There are some similarity and
plants that run on biogas are also difference between these two pathways.
operating across Asia and Africa, including Thermochemical gasification has several
many for industrial process heat. Biogas is advantages over biomass combustion or

1
conventional fossil fuel. Fuel flexibility is by 2030 if all its potential beyond the
even higher than biomass combustion business as usual is implemented.
since it can use wet biomass feedstock
directly. Wide range of feedstock is appli-
cable especially waste and residue. Bio-
chemical gasification also has higher fuel
flexibility, however it cannot efficiently
digest cellulose rich feedstock and most of
biochemical gasification in practice, use
animal waste or MSW as main feedstock.
End use flexibility is also important
characteristics of biogas. Generated bio-
gas can be directly combusted in boilers,
or can be converted to a variety of fuels
(H2, Fischer-Tropsch (FT) diesels, synthetic
gasoline) and chemicals (methanol, urea)
as substitutes for petroleum-based chemi-
cals. Gaseous form is easier to handle,
store and transport compared to solid
biomass fuel.
From the health and environmental
perspective, it is cleaner than biomass
combustion. During combined cycles for
combined heat and power generation,
contaminants in the syngas such as
sulphur and nitrogen species and trace
elements are removed efficiently resulting
in much lower emissions.
Liquefied petroleum gas (LPG) cooking fuel
is an oil refinery and gas processing by-
product, and its supply prospects are
uncertain in the long term. Instead, Figure 1. Global renewable energy use by
modern renewable energy can replace technology and sector, 2010 and in REmap
traditional use of biomass for cooking, 2030 [2]
which has significant health impact.
Worldwide, there are about 50 million Nearly a third of this total would be
biogas installations for cooking, notably in consumed to produce power and district
China and India. [2] heat generation. About 30% would be
There are also other advantages such as utilised in biofuels production for the
higher thermal efficiency compared to transport sector. The remainder would be
direct combustion, reduced cost of waste halved between heating applications in
treatment by producing valuable substan- the manufacturing industry and building
ce from waste, creation of job opportunity. sectors. Biomass use in combined heat
and power (CHP) generation will be key to
3. Potential and Barriers raise its share in the manufacturing
Based on REmap analysis by IRENA, Global industry and power sectors. [2]
biomass demand could double to 108 EJ

2
Substitution of traditional biomass is Based on the IRENA costing analysis, one
another key issue to increase share of of the difficulties in biogas deployment is
modern biomass in building sector. For relatively higher supply cost largely due to
both applications, biogas plays a key role. higher capital cost. However, biogas can
still be a good option for decentralized
power supply. Renewable solutions tend
to be significantly cheaper than diesel- or
kerosene-based energy supply systems.
They are also cheaper than grid extension
in situations with low population density
and low per capita demand. IRENA
analysis for the Pacific has shown that
retrofit of diesel mini-grids with renew-
ables is technically and economically
feasible in all cases. IRENA analysis
suggests that full access would raise global
electricity demand by only 1%. More than
Figure 2. Breakdown of biomass supply by half of this demand would be met with
regions, 2030 [3] renewables through decentralised solu-
tions.
By looking at the regional distribution of
different type of biomass potential, it can 4. Policy options for further promotion
be seen that residue/waste is dominant in IRENA REmap assessment showed that
Asia, woody biomass is concentrated in bioenergy will play a key role in doubling
Europe and North America. This implies renewable energy supply and access. It
that residue/waste based technology is showed there is enough biomass potential
important in Asia and wood based to meet the increasing demand. However,
technology is important in Europe and N. the issue is how to accelerate actual
America. Biogas can be an important investment/deployment of these resou-
technology option for these biomasses. rces. Currently over 140 countries
introduce renewable energy target. Feed
in Tariff is introduced in over 60 countries.
Blending mandate for transport fuel is also
introduced in over 60 countries. Heating
obligation is not as common as FIT and
blending mandate but introduced in less
than 20 countries. Key issue is how to set
volume and price level to support
technology cost reductions while prov-
iding economic incentives to bioenergy
developers. Other important policy is
environmental policy such as indirect Land
Use Change, which EU member countries
and United States have recently taken into
account. As biomass has to enhance
Figure 3. Breakdown of biomass supply by biomass’ multi-dimensional role while
regions, 2030 [3] mitigating the possible trade-offs associat-

3
ed with bio-energy deployment, an
effective policy mix is needed rather than
a single stand-alone policy or individual
policy measures.

5. References
[1] REN21, “RENEWABLES 2014, GLOBAL
STATUS REPORT” (2014)
[2] IRENA, “REmap2030, A Renewable Energy
Roadmap” (2014)
[3] IRENA, “Global Bioenergy, Supply and
demand projections” (2014)

4
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Renewable methane for mobility and EBA’s perspective on the

biomethane market
Jan Stambasky1
1 President, European Biogas Association, Renewable Energy House, Rue d’Arlon 63-65, B – 1040 Brussels,
BELGIUM

1. Introduction The distribution of production among the

Biomethane is usually defined as non- three major pathways of anaerobic
fossil methane produced from various digestion shows that 69% of methane was
sources of biomass with properties close generated in plants processing raw
to natural gas. In a broader sense the materials derived from the agriculture and
word biomethane can be applied in all from waste streams of the food and other
cases when either the source is biogenic industries (Table 1):
(biomass) or the technological process is
biological. Table 1. Biogas production
Production 2013 toe %
The production of biomethane opens new
dimensions for the biogas industry, while Landfill gas 2,881 21.49
x biomethane can be used not only Sewage gas 1,254 9.35
for generating electricity and heat Biogas from agri- 9,272 69.16
(as raw biogas) but also as a culture + industrial
waste stream
biofuel for transportation,
Total 13,407 100.00
x biomethane can be forwarded
everywhere (including cross-
Only 2% of the anaerobic digestion plants
border) through the natural gas (282 units) were equipped with biogas
distribution system. upgrading installations at the end of 2013.
The European biomethane production
The presentation provides an overall view capacity has been on a rise in the last five
on the present status, future prospects, years and achieved 9.4 TWh by the end of
challenges and opportunities of the 2013. (EBA Biogas Report 2014).
biogas/biomethane industry as seen by
the European Biogas Association. Biomethane is being produced in 15
European countries. In 12 countries (AT,
2. Biogas and biomethane statistics CH, DE, DK, ES, FR, FI, LX, NL, NO, SE, UK)
According to the EBA Biogas Report 2014 the product is injected into the natural gas
there were about 14,572 biogas producing pipeline system, while biomethane is used
plants in operation in Europe at the end of as vehicle fuel in 12 (AT, CH, DE, DK, ES,
2013. The total primary energy production FR, FI, HU, IS, IT, NL, SE, UK) countries.
by the industry reached 13.4 million tons
of oil equivalent in 2013 (EurObserv’ER The other European governments have
Biogas Barometer 2014). not yet acknowledged that biomethane

5
offers significant advantages (over raw The intrinsic “bio” (here stands for
biogas) in every fields of application, such renewable, sustainable) biomethane
as: needs to be monetised otherwise the
x „Green” electricity generation: investments into new producing
biomethane can be utilised in installations cannot be financed. It is up to
existing natural gas fuelled power the national governments to decide to
which extent they wish to promote this
stations and CHP units enabling the
form of renewable energy. In any case, the
highest level of energy utilisation. biomethane industry needs realistic,
x Heating: biomethane brought to stable, transparent and reliable incentive
city homes through the existing schemes for strong development.
natural gas distribution network is
by far the best way of supplying As far as the transportation fuel market is
concerned EBA expects and supports the
renewable energy for domestic
very dynamic growth of the gaseous
heating.
motor fuel consumption in Europe. The
x Transportation: natural gas and biogas/biomethane industry is fully
biomethane are complementary capable to keep pace with the expansion
fuels, they should grow together of the CNG/LNG. EBA believes that natural
on account of liquid vehicle fuel gas and biomethane are complementary
consumption. fuels and the close cooperation of the
natural gas and biomethane industries
corresponds to the interests of both
3. Potential
partners while the natural gas-biomethane
The potential for biological methane
blend (either compressed or liquefied) is a
production is substantial but not
clean vehicle fuel with the best GHG
unlimited. EBA estimates that the overall
emission characteristics. EBA prefers
potential for realistic biological methane
supplying NG/biomethane blends through
production from anaerobic digestion in
a widely developed refuelling station
2030 will be in the magnitude of 30 billion
network (instead of selling pure
m3/year (in methane equivalent). Thermal
biomethane on a few, scattered sites).
biomass gasification is expected - with the
EBA is working on assessing the future
further development of the technology –
development in this field. The preliminary
to take a very important share in the total
findings of this work are shown in Table 2:
biomethane production. With the
inclusion of biomethane from thermal
Table 2. Natural gas and biomethane in
biomass gasification, the total European
billion m3.
biological methane production could
reach 50 billion m3/year (in methane equi- 2014 2020 2030
valent). Thus, by 2030 and with the right Natural gas 3.0 8-12 20-24
policies in place, the industry could Biomethane 0.3 2-3 5-6
produce renewable energy corresponding
Total 3.3 10-15 25-30
to about 8 10% of the EU’s methane
(natural gas + biomethane) consumption. Share bio- 9.1 20 20
methane [%]
4. Conclusions
Feasibility (substantially influenced by the Biomethane is one of very few products,
support schemes) remains a major issue. which cannot be freely transported from

6
one EU member state to another keeping 5. References
the ‘bio’ value along the contractual chain. EBA 2014, Biogas Report 2014, European
Together with other stakeholders EBA is Biogas Association (EBA), <http://europ-
ean-biogas.eu/wp-content/uploads/2015/
working on solutions enabling the cross- 01/EBA-Biogas-Report-2014.pdf>.
border biomethane trade. In principle EurObserv’ER 2014, Biogas Barometer,
there are three ways of monetizing the <http://www.energies-renouvelables.org/
“bio” value of biomethane on the inter- observer/stat_baro/observ/baro224_
national market (Table 3.) Biogas_en. pdf>.

In addition to the establishment and

harmonisation of the documentation/
registration and certification schemes it is
essentially important that the European
natural gas system is recognised as an
integrated, closed network with regard to
biomethane mass-balancing.

Table 3. Different ways of monetizing the “bio” value of biomethane

Art of trade Market Source of bonus payment Documentation
Physical product Regulated by EU and State aid: financial support/ Mass-balancing
national governments incentives
Product Certificate Free market Willing biomethane cons- “Book and claim”
umers
Emission Emission Trading Environment polluters Certification
Certificate System

7
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esiŐŶ͕WcoŶstƌƵcƟoŶĂŶĚKΘDoĨ/ŶteŐƌĂteĚiomĂssΘtĂste
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'ĂsiĮeƌdecŚŶoůoŐLJ

Expertise in power plants between 1 to 20 MWe

www.ebioss.com iŶĨoΛeqtec.com www.eqtec.com

2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Next generation technology to reduce biogas up-gradation cost by 46%

Aniruddha Sharma1 and Prateek Bumb2
1 CEO, Carbon Clean Solutions Limited, UK
2 CTO, Carbon Clean Solutions Limited, UK

1. Introduction 2. Technology description

Carbon Clean Solutions Limited (CCSL) is In MethPureTM upgrading process the raw
an innovative leader in carbon dioxide biogas is fed through bottom of absorbing
(CO2) separation technology for industrial section of the system. The process
and gas treating application. CCSL’s carbon recovers more than 99.9% of the methane
capture technology comprises of a from the raw biogas, by scrubbing CO2
proprietary regenerable solvent and a using APBS solvent. Methane is then made
unique heat integrated mechanism. This available for vehicle fuel or can be fed to
enables the removal of carbon dioxide natural gas grid. The stripped off CO2 using
from any mixture of gases. thermal energy has >99% purity, that can
Biogas is an important source of be used in green houses, as a cooling
renewable energy. It is produced by the agent or generally for industrial use – a
anaerobic digestion (or fermentation) of valuable by-product of the biogas up-
bio-degradable materials such as manure, grading process. The biogas upgrading unit
plant materials, green waste, energy is designed in modules allowing cost
crops, household and industry wastes, effective variations in plant size and
sewage sludge and municipal waste. capacity. Fig. 1 shows process flow
Biogas contains methane, hydrogen diagram of MethpureTM .
sulfide and carbon dioxide as its major
components.
Up-gradation of biogas is separation of
hydrogen sulfide and carbon dioxide from
methane to increase its energy content.
This up-graded biogas can be used for
electricity generation or vehicular
purposes. CCSL’s technology for up-
gradation of biogas involves a solvent
named APBS and a technology called Figure 1: MethPureTM process flow
MethPureTM which involves an advanced diagram
heat integration. MethPure works on
atmospheric pressure to recover methane 3. Case Study
from biogas up-to levels of more than MT-Biomethane operates a biogas plant of
99.9%. APBS has been commercialized at 6,000 Nm3/day at Zeven, Germany. The
biogas up-grading plant at Zeven, biogas is produced from agricultural waste
Germany operated by MT-Biomethane. and the up-graded biogas i.e. bio-methane
The biogas is produced from agricultural is fed to electricity grid.
waste with a capacity of 6,000 m3/day.

9
aMDEA was the solvent used for up-
gradation in the plant which was swapped
with APBS. Daily operational problems
cited by operators were foaming and high
make-up of chemicals. It was also
observed that the plant has higher
thermal energy. The biogas & bio-
methane composition is shown in Table 1
& Table 2 respectively.

Table 1: Biogas composition

CH4 (%vol) 50 Figure 2: Net loading capacity
CO2 (%vol) 50
3.1.2. Recovery of Methane from biogas
H2S (ppm) 0
Methane recovery using APBS solvent has
Flow rate (Nm3/hr) 200-250 been shown in Fig 3. As APBS is inert to
methane the recovery from biogas is >
Table 2: Bio-methane composition 99.9%
CH4 (%vol) 97-99
CO2 (%vol) 1-3

The plant at Zeven has been operating

with APBS solvent since July 2014 and has
completed 5,712 hours of run till April
2015. Corrosion test had been performed
on APBS solvent to evaluate its
performance on material of construction
used in the plant. To study life of APBS,
accelerated testing on laboratory scale Figure 3: Recovery of methane
had been performed.
3.1.3. Foaming
3.1. Results One of the major operational problems
3.1.1. Net loading capacity encountered by aMDEA had been foaming
It has been observed that APBS has net once a week. This leads to undue stoppage
loading capacity for CO2 1.5 times higher of plant and loss of processing of biogas
than aMDEA. Figure 2 shows the results of hence revenue. On swapping of aMDEA
capacity comparison of aMDEA and APBS. with APBS it had been observed that since
Higher capacity of solvent for CO2 leads to the start of run there has been no foaming
decrease in circulation rate of solvent and in the absorber. Figure 4 shows foaming in
hence reduction in size of equipments. absorber due to aMDEA and no foaming
due to APBS.

10
 for the current plant operation period. Fig.
6 shows the comparison of aMDEA with
APBS of makeup chemicals for on-going
operations.

aMDEA APBS
Figure 4: Foaming

3.1.4. Energy
Thermal energy is needed for regenerating
the solvent while electrical energy is
measured as power required by pumps to
circulate the solvent in the system. APBS
has shown consistent performance in
terms of energy on just solvent swap. It Figure 6: Make up chemicals
must be noted that no process change was
made as a part of solvent change. Figure 5 3.1.6. Corrosion Rate
shows thermal and electrical energy SS316L, Ethylene propylene diene ter-
performance of APBS. The average polymer (EPDM) & polyethylene (PE) are
thermal energy for APBS is ~0.55 used as material of construction of plant.
3
kWh/Nm3 of raw biogas. The electrical Corrosion rate trials were conducted on
energy has been 0.1 kWh/Nm3 of raw these materials at severe conditions with
biogas. Biogas up-grading systems APBS. The tests were conducted for 7 days
designed with MethPureTM’s advanced in presence of gas composition having CO2
heat integration can have further 20% & N2, 40 & 60 % vol. respectively. The
reduction in thermal energy demand. temperatures were kept 140 & 150 °C for
EPDM & SS316L while for PE temperature
was kept 70 °C. The test showed a
corrosion rate of 0.035 mpy4 for SS316L
and no significant % change in dimensions
for EPDM & PE which suggests the
longevity of materials used in construction
of plant. For corrosion analysis, APBS with
two types of carbon steel coupons were
used and were attached to PTFE coupon.
Through analytical techniques it was
found that APBS solvent developed
Figure 5: APBS’s Energy crystalline passivation layer growth. The
chemical composition of these passivation
3.1.5. Make-up chemicals layers suggests an 1:3 ratio of C to oxygen.
Over a period of time due to vapour Detailed analysis of the corrosion coupons
pressure and degradation, performance of results shows (-ve) corrosion rates for
aMDEA starts to diminish. Hence a regular APBS. Detailed Scanning Electron
make up of chemicals are needed to Microscope (SEM) images show evidence
achieve the required performance. In case of passive layer formation with APBS
of APBS it has been observed that there solvent reducing the corrosion. This
has been no need for make-up chemicals formation of passive layer plays an

11
important role in reducing corrosion 5. Observations
through APBS. Through solvent run conducted at Zeven
following can be observed about Meth-
3.1.7. Degradation PureTM in comparison to aMDEA:
Due to high temperature operation 1. Through CCSL advanced heat integrated
involved in the plant aMDEA tends to MethPureTM process a) Thermal energy
degrade over a period of time and can be decreased to 0.44 kWh/Nm3 of
degraded product leaves the system raw biogas. Through waste heat further
through various methane and CO2 gas reduction in usage can be achieved. b)
streams leaving the system. It has been Electrical energy can be reduced to 0.06
observed that there are no emissions of kWh/Nm3 of raw biogas as the capacity
APBS solvent through the above of APBS solvent is higher than aMDEA
mentioned streams. 5An accelerated 2. Using APBS solvent cause no foaming
degrading test to understand the life of hence processing efficiency of raw
solvent was performed at 160 °C for 3 biogas and uptime increases.
weeks saturated with CO2 and was 3. No use of make-up chemicals
observed that APBS’ degradation is 66 % 4. Higher solvent life leads to up to four
lesser than aMDEA. times reduced frequency of fresh
solvent charge and disposal cost over
4. Comparison with other technologies plant life.
In technologies such as Pressurized water 5. Lower corrosion rate leads to lower
scrubbing (PWS), Pressure swing wear and tear of system components
adsorption (PSA) and Membranes the and less maintenance.
recovery of methane is limited to < 98%.
The un-recovered methane goes through 6. Conclusions
CO2 stream and hence has to be treated It can be concluded that due to
since methane is a more potent green- MethPureTM savings in thermal & electrical
house gas than CO2. For these energy can be up-to 20% and 40%
technologies regenerative thermal respectively. No occurrence of foaming
oxidizer (RTO) is needed for combustion of can increase productivity of biogas
methane present in CO2 stream. processing. Due to higher solvent life and
MethPureTM can recover >99.9% of very low corrosion rate the overall
methane in biogas so none/negligible investment over the plant life can be
methane goes in CO2 stream and hence no decreased. MethPureTM process with
RTO is needed. The capital investment for innovative APBS solvent will result up-to
MethPureTM is 25-33% less as compared to 30% savings in operating cost compared to
PWS, PSA & membranes. The electrical aMDEA and 16% reduction in capital cost.
energy for PWS, PSA & Membranes is in In comparison with PWS, PSA &
the range of 0.2-0.35 kWh/Nm3 of raw Membranes the capital expenditure in
biogas while MethPureTM has electrical MethPureTM is lower by 25-33% while opex
energy < 0.1 kWh/Nm3 of raw biogas. The reduction can range upto 8-27%.
overall operational savings of MethPureTM
compared to these technologies is in the References
3
range of 8-27%. On heat recovery from Corrosion rate test conducted at Subodh
MethPureTM and integration with digester Technologies Pvt. Ltd., India
4
further savings in operating cost can be mpy – milli-inches per year
5
realized. Degradation test conducted at TNO,
Netherlands

12
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Development of next generation biogas cleaning & upgrading

technology. Demonstration of terpene removal
Marco J.G. Linders1, Leen V. van der Ham1, Leon C. Stille1, Henk C. Trap1, Lars Huigen2,
Jacco Mooijer3, and Earl L.V. Goetheer1
1 TNO, Process and Instrument Development, Leeghwaterstraat 46, 2628 CA, Delft, the Netherlands.
2 Attero, Vloeiveldweg 8, 5048 TD, Tilburg, the Netherlands.
3 Frames, Raoul Wallenbergplein 29, 2404 ND, Alphen aan den Rijn, the Netherlands.

1. Introduction
Terpenes are a problem for biogas
producers, as grid owners will refuse entry
to the natural gas grid when more than a
few ppm terpenes are detected in the Regeneration
renewable natural gas injected. The High Temperature

problems are related to the integrity of

pipelines, safety at the upgrading plant
and the fact that terpenes mask the odour Absorption
Terpene Low Temperature
of the standard added tetrahydro- (guest)
thiophene (THT) odorant in natural gas, Host molecule
which is unacceptable for grid owners, as
it may lead to safety risks. Moreover, the Figure 1. Host-guest chemistry –
technology currently used by most biogas regenerative selective chemical absorption
producers is removal of terpenes with using an affinity based extractant.
activated carbon, which is a costly process.
The degree of remaining adsorbent
capacity is hard to monitor, which leads to 3. Experimental approach
an increased risk of an occasional slip of Experiments were performed with several
terpenes. model terpene compounds and host
molecules. A constant amount of terpene
2. Technology description was injected into a vaporizer and mixed
The TNO concept for terpene removal [1] with nitrogen, resulting in a constant
is using affinity based extractants, or host- concentration of the terpene (4.0 g/m3 in
guest chemistry. The terpene removal the result shown here). The terpene
system aims at a broad-spectrum solution, containing gas flow of 100 ml/min was
removing various of terpenes with one or, added to a glass bottle containing 100 ml
if necessary, a mixture of extractants. At of solvent, consisting of water with the
low temperature the terpene (or the dissolved host compound. The outlet
guest) is captured by the extractant (or terpene concentration in the gas was
the host). By raising the temperature the measured at several time intervals using
terpene is released again, and the solvent gas chromatography.
is returned for the next absorption step.

13
4. Results process design of the terpene removal
Figure 2 shows a typical test result. At the system will be made. In combination with
start of the experiment the concentration a techno-economic evaluation this serves
is practically immediately reduced to zero. as input for a system validation via small
As time progressed, the outlet terpene scale piloting. A pilot scale installation is
concentration was increasing, slowly being designed and will be built, that is
approaching the inlet terpene going to be used to demonstrate terpene
concentration. Negligible foaming was removal from biogas at a biogas
observed during the entire experiment. As production location.
a reference, an experiment was
performed with pure water as solvent, so 5. Conclusions
without the presence of the host Based on the preliminary results it is
compound. In this case, the terpene is concluded that a proof of principle of a
hardly removed from the gas: the outlet terpene removal system based on host-
terpene concentration does not decrease guest interaction has been demonstrated.
to zero and it returns to the inlet Currently, the solvent composition as well
concentration very rapidly. These results as the operational conditions are further
demonstrate the ability of the host optimized and will be followed by
containing solvent to remove terpene designing and building a demonstration
contaminants from a gas stream. pilot scale installation to be applied for
biogas cleaning in practice. The obtained
results so far as well as the latest
developments will be presented in more
detail.

6. Acknowledgement
The Netherlands Enterprise Agency is
thanked for its financial support for
project TEG0414003.

7. References
[1] Goetheer, E.L.V., Linders, M.J.G., Stille,
L.C.; Biogas purification. EP14176550, 10
Figure 2. Absorption of terpene in a host July 2014. [Filed]
containing solvent compared with pure
water.

In the next phase the solvent composition

as well as the operational conditions will
be optimized. Specific aspects that are
being addressed to reach a proof of
concept are the required extractants to
capture the range of terpenes that can be
present, the capacity and stability of the
solvent, and the operating temperatures.
Based on these results a conceptual

14
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Towards a measurement infrastructure for the conformity assessment

of biomethane and upgraded biogas
Adriaan M.H. van der Veen1 and Jianrong Li1
1 Chemistry Group, Van Swinden Laboratorium, Thijsseweg 11, 2629 JA, Delft, the Netherlands

1. Introduction 2. Specifications
The Renewable Energy Directive The feed stocks used for producing biogas
2009/28/EC [1] establishes a framework differ substantially, as do the processes for
for the promotion of energy from producing the biogas and upgrading it to
renewable sources, thus reducing CO2 biomethane. The diversity of the feed
emissions and securing the supply of stocks used to produce biogas means that
energy in the European Union. In its clause a larger number of parameters than for
(2) [1], the use of renewable energy in the natural gas need to be specified, in
transport sector is referred to as a means particular with respect to critical
to reduce the EU's dependence on fossil impurities. Draft specifications for
fuels. Furthermore, in clause (57) [1] the biomethane for injection into natural gas
need to integrate renewable energy into grids [5] and as automotive fuel [6] are
existing transmission and distribution grids underway. Meeting these specifications is
is stated. The use of agricultural material crucial for the integrity of piping networks,
[1, clause (12)] is identified as having a metering equipment, and of the end-
high potential for greenhouse gas users’ appliances.
emission reduction and for having
significant environmental advantages at Once finalised, these specifications need
the same time. to be implemented. The producers of
biomethane and upgraded biogas are
To promote the use of biomethane as responsible for demonstrating that their
required by 2003/55/EC [4], the properties product meets the specifications. On the
of biomethane / biogas need to be other hand, the natural gas grid owners as
specified. Through mandate M/475 [3], well as the operators of refuelling stations
the European Commission has mandated should accept this green gas.
CEN, the European Organisation for
Standardisation, to draw up such 3. Measurement methods and reference
specifications for biomethane for injection materials
into the natural gas transport and Demonstrating that biomethane and
distribution grids and for use as transport upgraded biogas meets the specifications
fuels. Access to the natural gas grids is [5,6] requires, among others, reliable
essential for the promotion of biomethane measurement and test methods of known
and shall not be discriminatory [1, article performance. As a first step towards
16]. In this respect, the Renewable Energy developing these methods, reference
Directive supplements the requirements in methods are developed in the project
directive 2003/55/EC [4]. “Metrology for Biogas” in the European

15
Metrology Research Programme (EMRP). 3 years’ time frame. The project started on
These methods are in turn used to 1 June 2014.
develop measurement standards which
enable the production and dissemination 4. Conformity assessment
of calibration gas mixtures (CGMs) and For conformity assessment, some steps
certified reference materials (CRMs) for beyond the scope of the aforementioned
calibrating instruments used in monitoring project are needed. One of these is to
the biogas specifications. develop and draft harmonised methods
that enable onsite or offsite measurement
The objectives of the project are aims to of relevant properties. The frequency with
develop and validate methods for which such measurements need to take
determining key impurities, moisture, place is subject to agreement between the
particulates, calorific value, and density: biogas producer and receiver.
௅ novel traceable methods for the
measurement of the contents of In the conformity assessment, the
key trace-level impurities in biogas measurement uncertainty plays an
and biomethane namely: total important role. Measurement uncertainty
silicon and siloxanes, sulphur- is a parameter that informs about the
containing compounds, aromatic accuracy (quality) of a measurement
hydrocarbons, halogenated result. It is closely related to the
hydrocarbons, ammonia, hydrogen reproducibility of a method. Measurement
cyanide, hydrogen chloride and uncertainty is evaluated in accordance
carbon monoxide. with the GUM [7]. It is, together with the
௅ robust analytical capabilities for specification limit and the measured
the measurement of the value, an input necessary to do the
particulate content and water conformity assessment [8].
content / dew point of biogas and
biomethane. Another important aspect concerns the
௅ methods for the measurement of use of appropriate CRMs and CGMs to
the calorific value, heat capacity, ensure that the equipment is duly
and density of biogas and calibrated and periodically checked. In
biomethane. doing so, the equipment provides results
௅ a traceable method for that are free from significant biases, thus
determining the concentration of ensuring that the results are
biomethane in samples of blended metrologically traceable. In the natural gas
biomethane and natural gas. area, all results used for custody transfer
௅ robust methods for sampling and conformity assessment are
biogas and biomethane in the field, metrologically traceable to ensure that
and to enable the biogas industry they are fit for purpose.
to perform robust and traceable
quality assessment measurements. A further issue concerns the sampling of
biogas, in particular for the determination
The project consortium is formed by 12 of the contents of impurities. Many of
European National Metrology Institutes these impurities have a tendency to react
and 3 European Universities. It covers vast or adsorb on surfaces of samplers,
array of expertise and competences, sampling lines, and sample collection
necessary for carrying out the work in a vessels. The activities in the above

16
mentioned project focus on assessing the in transport and injection in natural gas
compatibility and suitability of widely used pipelines, Brussels, 8 November 2010
means for biogas sampling, such as
sampling bags and adsorption tubes. [4] Directive 2003/55/EC of the European
Effects such as losses, and the Parliament and of the Council concerning
repeatability and reproducibility of results the common rules for the internal market
as a function of the storage time are in natural gas, Brussels, 26 June 2003
studied and a good practice guide will be
developed in due course. [5] European Organization for Standard-
ization, prEN 16723-1 -- Natural gas and
5. Concluding remarks biomethane for use in transport and
The project “Metrology for Biogas” is one biomethane for injection in the natural gas
of the key steps in implementing the network — Part 1: Specifications for
specifications EN 16723 for biogas and biomethane for injection in the natural gas
biomethane. It broadens the array of network, 2014
measurement methods used in natural gas
custody transfer to address the specific [6] European Organization for Standardi-
issues related to the injection of zation, prEN 16723-2 -- Natural gas and
biomethane and upgraded biogas into biomethane for use in transport and
natural gas grids and for use as transport biomethane for injection in the natural gas
fuel. network — Part 2: Automotive fuel
specifications, 2014
The project serves as a step-up towards
the development of European harmonised [7] BIPM, IEC, IFCC, ILAC, ISO, IUPAC,
standard test methods for the parameters IUPAP, OIML, ``Guide to the Expression of
in biogas, not covered so far. In this Uncertainty in Measurement, JCGM
development, other parties need to have 100:2008, GUM 1995 with minor
their say, as the methods developed in the corrections'', JCGM 100:2008
project “Metrology for Biogas” are
developed for a different purpose and are [8] BIPM, IEC, IFCC, ILAC, ISO, IUPAC,
optimised for accuracy rather than for IUPAP, OIML, ``Evaluation of
routine conformity assessment of measurement data -- The role of
biomethane and upgraded biogas. measurement uncertainty in conformity
assessment'', JCGM 106:2012
6. References
[1] Directive 2009/28/EC of the European
Parliament and of the Council on the
promotion of the use of energy from
renewable sources, Brussels, 23 April 2009

[2] COM (2010) 639, Energy 2020, A

strategy for competitive, sustainable and
secure energy

[3] European Commission, Directorate-

general for energy, M/475 EN, Mandate to
CEN for standards for biomethane for use

17
18
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Motives for biomass based bio-SNG production and perspectives of the

Heatpipe Reformer technology
Jürgen Karl1
1 Chair of Energy Process Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany

wind and photovoltaics during the next

1. Introduction
decades. As shown in Figure 2 typical load
The production of synthetic natural gas profiles indicate that these back-up capac-
(SNG = Substitute Natural Gas) from bio- ities have to be most flexible in order to
mass is a promising option to reduce up- provide load peaks with highest capacities
coming bottlenecks and to substitute fossil and transients. Gas turbines in combina-
fuels with renewable energy. The current tion with existing gas storage capacities
reserves-to-production ratio of European are the most suitable technologies to
natural gas reserves is 14.8 years only [1]. meet these challenges. Consequently, Eu-
Thus, Europe will mainly depend on Rus- rope will continue to require gaseous
sian Natural Gas reserves within few fuels.
years:

Figure 2. Typical load profile of Germany’s

electricity production (spring 2013)

A quite promising alternative to Russian

Figure 1. Perspectives of Europe’s Natural natural gas supplies is the conversion of
Gas supply Dual fluidised bed woody biomass into so-called ‘Substitute
Natural Gas’ (SNG). This methanation of
In spite of the huge success of the transi- biomass consists of two process steps. The
tion to renewable energies in many Euro- first step converts biomass into syngas
pean countries Europeans dependencies heat
on Natural Gas supplies will not change CHn O m  (1  m) H2 O o

significantly. Power from conventional §n ·
¨  1  m ¸ H2  CO
power plants will still have to back-up ©2 ¹

19
that resembles finally to methane: All these technologies apply fluidized
beds. Most of the currently proposed con-
3 H2  CO 
o CH 4  H2 O
cepts combine fluidized bed combustion
The water gas shift reaction adjusts the with fluidized bed gasification – compris-
H2/CO-ratio and releases CO2: ing so-called Dual Fluidized Bed (DFB) gasi-
CO  H2 O 
o CO 2  H2 fiers [5]. The term “Dual Fluidized Bed”
usually applies to interconnected fluidized
The theoretical overall reaction equation bed gasification systems. However, indi-
for the methanation of typical wooden rectly heated gasifier systems such as the
biomass (n=1.37, m = 0.61) for oxygen- Heatpipe Reformer, also consist of two
blown gasification fluidized beds as indicated in Figure 3:
CH1,37O0,61  0,35 O2 
o 0,34CH4  0,66 CO2

and steam-blown gasification

CH1,37 O 0 ,61  0 ,35 H2 O o 0 ,52 CH4  0 ,48 CO 2

indicate that CO2 removal is a third im-

portant process step in case that the gas
shall substitute fossile gas in existing natu-
ral gas infrastructures.

2. Gasification technologies for bio-SNG

Oxygen-blown autothermal gasification is Figure 3. Interconnected and indirectly
still state-of-the-art for large-scale heated dual fluidized bed gasification sys-
methanation of coal and lignite [2]. How- tems
ever, small- and medium-scale systems are
particularly feasible with steam-blown or The most successful gasification concept
allothermal gasification. Steam gasifica- so far is Hofbauers ‘Fast Internal Circulat-
tion of biomass provides exceptionally ing Fluidized Bed’ – the Güssing gasifier. It
high gas qualities. Hydrogen contents up has been demonstrated most successfully
to 50% or even more make the technology in the Austrian town of Güssing with wood
particularly interesting for the conversion chips since 2001 [6]. Several similar plants
of biomass into second generation fuels are in operation in Oberwart, Villach, Aus-
such as Fischer-Tropsch diesel, methanol, tria, Senden, Germany and Gothenburg,
dimethyl ether (DME) or Substitute Natu- Sweden [7].
ral Gas (SNG) [3,4]. The key challenge is The alternative concept - to provide the
the necessity to provide the heat-of- heat for the gasification process into the
reaction for the fuel drying, heating, and gasification reactor by means of heat ex-
the endothermic gasification reactions at changers - has been proposed by the
highest temperatures above 700-800°C. Bergbauforschung [8] and MTCI [9] al-
Three solutions are known for a sufficient- ready 30 years ago. Both concepts suf-
ly effective heating of such gasifiers: fered from the huge number of heat ex-
changer tubes that have to be installed in
1. Discontinuous intermittent operation the fluidized beds due to the poor heat
of a single fluidized bed transfer between heat carrier gases inside
2. Circulation of particles between two the tubes and the heat exchanger tubes. A
interconnected fluidized beds significant reduction of heat exchanger
3. Indirectly heated fluidized beds

20
tubes in the gasifier was achieved by the reformer. An inner insulation (4) keeps the
application of so-called heat pipes. Heat upper flanges close to ambient tempera-
pipes are closed tubes with a liquid inside. tures. The main advantage of this inte-
Evaporation and condensation inside the grated concept is that there are no moving
tube guarantee highest heat transfer coef- parts facing high temperatures and the
ficients and reduce the required heat heat losses are kept low. Pressurized
transfer area in the reactor by a factor of steam is fed into the gasifier through a
10 to 20. The concept was first proposed steam inlet (5). The solid fuel falls through
in 1999. Two first prototypes of the a lock-hopper system and a stand-pipe (6)
Heatpipe Reformer have been developed into the gasifier. The syngas leaves the
and successfully tested during the Europe- gasifier through an upper outlet (8) to an
an FP5 project “Biomass Heatpipe Re- external candle filter which removes dust
former”. A first pilot plant of the Biomass and char particles. An integrated air pre-
Heatpipe Reformer with a thermal input of heater (7) reduces exhaust losses and im-
500 kW has been developed by agnion proves the cold gas efficiency.
energy Inc. and operated successfully in
Pfaffenhofen, Germany [10]. Agnion er- 3. Mass and energy balances
rected further plants in Grassau, Germany
and Auer, Italy. The methanisation converts 50-60% of the
Figure 4 shows the conceptual design of biomass energy into SNG. But total effi-
the Biomass Heatpipe Reformer. The re- ciencies of 60% require an extraordinary
former pressure vessel (1) is completely high cold gas efficiency of the gasifier (see
integrated into the combustion chamber Figure 5). The Heatpipe Reformer pilot in
(2). Pfaffenhofen reached cold gas efficiencies
above 70% [11]. Key for such high efficien-
cies are an efficient air preheating and
conversion of char inside of the gasifier
[10]. The SNG production offers significant
economic and commercial advantages in
case that the SNG is produced in small-
scale decentralized plants. In particular,
the option to use the waste heat of the
process for domestic heating or heating
grids increases the total efficiency. Analo-
gously to combined heat and power pro-
duction (CHP) this so-called ‘polygenera-
tion’ provides additional revenues for the
plant operator. A ‘double income’ situa-
tion allows for higher specific investment
Figure 4. Concept of the Heatpipe costs and offers an interesting market for
Reformer [10] small-scale methanation sites.
Heat pipes (3) transfer the heat-of-
combustion form the combustor into the

21
Figure 5. Energy balance of bio-SNG systems
[5] Pfeifer C, Puchner B, Hofbauer H.
4. Conclusions Comparison of dual fluidized bed steam
Despite of the most successful implemen- gasification of biomass with and without
tation of renewables Europe’s energy selective transport of CO2. Chem Eng Sci
2009;64:5073–83.
economy will continue to largely depend
doi:10.1016/j.ces.2009.08.014.
on natural gas for the next decades. Sub- [6] Reichhold A, Hofbauer H. Internally
stitute Natural Gas is the most suitable circulating fluidized bed for continuous
solution for transportation, storage and adsorption and desorption. Chem Eng
most flexible use of bioenergy in order to Process Process Intensif 1995;34:521–7.
back-up wind and PV and. It also offers the doi:10.1016/0255-2701(95)00623-0.
opportunity to substitute Russian gas de- [7] Kern S, Pfeifer C, Hofbauer H. Synergetic
Utilization of Renewable and Fossil Fuels:
liveries to Europe using world-wide bio-
Dual Fluidized Bed Steam Co-gasification of
mass resources in the medium and long- Coal and Wood. APCBEE Procedia
term. 2012;1:136–40.
doi:10.1016/j.apcbee.2012.03.022.
[8] Jüntgen H, van Heek KH. Gasification of
5. References
Coal with steam using heat from HTRs. Nucl
[1] Bundesanstalt für Geowissenschaften und Eng Des 1985;34:59–63.
Rohstoffe (BGR). Reserven, Ressourcen und [9] Williams RH, Larson ED, Katofsky RE, Chen
Verfügbarkeit von Energierohstoffen 2013 J. Methanol and hydrogen from biomass for
2013:112. transportation. Energy Sustain Dev
[2] Karellas S, Panopoulos KD, Panousis G, 1995;1:18–34. doi:10.1016/S0973-
Rigas A, Karl J, Kakaras E. An evaluation of 0826(08)60083-6.
Substitute natural gas production from [10] Karl J. Biomass heat pipe reformer—design
different coal gasification processes based and performance of an indirectly heated
on modeling. Energy 2012;45:183–94. steam gasifier. Biomass Convers Biorefinery
[3] Hamelinck CN, Faaij AP. Future prospects 2014;4:1–14.
for production of methanol and hydrogen [11] Gallmetzer G, Ackermann P, Schweiger A,
from biomass. J Power Sources Kienberger T, Gröbl T, Walter H, et al. The
2002;111:1–22. doi:10.1016/S0378- agnion Heatpipe-Reformer—operating
7753(02)00220-3. experiences and evaluation of fuel
[4] Kopyscinski J, Schildhauer TJ, Biollaz SMA. conversion and syngas composition.
Production of synthetic natural gas (SNG) Biomass Convers Biorefinery 2012;2:207–
from coal and dry biomass – A technology 15.
review from 1950 to 2009. Fuel
2010;89:1763–83.

22
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Challenges in biomass gasification

Bram van der Drift1
1 ECN, Petten, The Netherlands, vanderdrift@ecn.nl

1. Introduction financing, permitting, etc., this paper deals

In gasification processes, the solid with some specific technical challenges
feedstock’s energy merely ends up in only.
gaseous molecules. Only a small part is
converted into (high-temperature) heat. 2. Gasification
This gives gasification several attractive Most unplanned downtime in biomass
benefits over combustion, where the plants in general is caused by feeding
energy ends up in heat only. The benefits issues. Simply getting the fuel into the
are various. conversion unit is not as easy as it seems.
Most existing gasification capacity Reasons are various, but often have to do
worldwide (mainly coal gasification in with the quality of the biomass. Biomass is
China) is used to synthesize chemicals like heterogeneous and its quality changes
methanol (www.gasification.org). For over time scales of minutes, days and
biomass, power production through seasons. Biomass gasification certainly
gasification has been popular because of suffers from this issue. Especially if the
its relatively high efficiency. Especially at gasifier is pressurized and feeding systems
smaller scales, see Figure 1. Additionally, contain much more critical parts. Some
engine-based gasification power plants plant owners choose expensive wood
can supply heat without compromising the pellets to limit the feeding issues.
power output, which enables very high Gasification technologies that have
overall efficiencies. relatively little feeding issues are fixed bed
processes. Here, batches of fuel are fed on
gasifier/engine/ORC top of a slowly moving bed. Because of the
gasifier/engine
60% gasifier/gas turbine/steam turbine (IGCC) large biomass inventory, interruptions in
50% combustion/steam turbine
feeding are less of a problem. Entrained
Electric Efficiency

40%
flow processes are on the other side of the
30%
20%
scale. Residence times are small and short
10% interruptions cause big problems.
0% Once the feedstock is in the gasifier, there
0.01 0.1 1 10 100 1000
Power Output [MWe] is a risk of melting. In case of fluidized bed
processes, this causes de-fluidization.
Figure 1. Biomass-to-power efficiency for
Particles will stick together (agglo-
combustion and gasification processes.
meration) and good mixing and uniform
Undoubtedly, gasification gets a lot of temperature no longer is guaranteed. This
attention for many reasons. Biomass results in hot spots and an acceleration of
gasification however, has its issues and the de-fluidization process. Figure 2 shows
challenges. Although many challenges are temperatures and pressures measured in
non-technical, like feedstock contracts, a fluidized bed gasifier from 20 minutes

23
 before to 10 minutes after de-fluidization up to coronene, which has a molecular
occurs. The problem announces itself, but mass of 300 g/mol. There seems to be a
it already is too late to avoid de- relation between the size and the content
fluidization. of hydrocarbons: the larger the molecules,
the lower the concentration. The Figure
60 below shows some examples of
850
bed temperatures
50
hydrocarbons in gas from wood and waste
750 40
gasification in two types of fluidized bed

pressure drop over bed [mbar]

.

30
650
gasifiers at ~820°C. It clearly shows the
temperature [°C]

20

550 pressure drop

agglomeration
(end of test) 10 relation between size and content.
0
450
temperature under first signs of 1 000 000
air distributor agglomeration -10 waste - indirect gasifier - 804C
350 wood - indirect gasifier - 820C

hydrocarbon concentration [mg/Nm3]

-20
waste - CFB - 820C
250 -30
-20 -15 -10 -5 0 5 10
100 000 wood - CFB - 840C
time to agglomeration [minutes]

Figure 2. Agglomeration occurring in a 10 000

fluidized bed: temperatures start to
deviate and pressure drop changes quickly 1 000

There are many ways to prevent

100
agglomeration. A lower process 0 100 200 300
temperature helps, but often has a hydrocarbon molecular weight [g/mol] per interval of 50
disadvantage in terms of reduced
conversion or worse gas composition. A Figure 3. The content of hydrocarbons in
more practical way is to add another fuel gas from gasification is lower for larger
or additives that dilute and/or actively molecules
bind the harmful elements before they
cause melting. Dolomite, clays, but also It is especially the larger tars that are
sewage sludge, paper sludge, or digestion responsible for problems in downstream
residue (digestate) may help reducing the units. These heavy tars condense at
risk of melting. surfaces and form a sticky layer that soon
leads to complete plugging of the lines.
3. Tar The temperature where tars start to
Since biomass is relatively reactive condense can be as high as 400-500°C.
compared to e.g. coal, 750-900°C is This is called the tar dew point. A tool to
sufficient for high conversion. Besides, calculate the dew point of tars can be
higher temperatures are undesired for the found at www.thersites.nl.
risk of agglomeration. The produced gas at The tar dew point model has been used to
750-900°C is far from thermodynamic determine the amount of tar that may
equilibrium. High amounts of methane condense on a (heat exchange) surface of
and other hydrocarbons are present in the a certain temperature. In Figure 4, this
gas. This mostly concerns ethylene, relation is shown for experiments
benzene and tars. Together these performed at different temperature. It all
hydrocarbons represent easily 50% of the concerns the same feedstock (wood) and
heating value of the gas. the same gasifier technology (MILENA
Tars are defined as anything larger than indirect gasifier). It is shown that a lower
benzene and can be very large. At ECN, we gasifier temperature leads to much less
are capable of quantitatively analyse tars fouling of cooler surface.

24
tar that condenses [mg/Nm3] 10 000 challenge for the catalyst. Moreover, high
1 000 tar concentrations may cause coking and
high amounts of steam are required to get
861°C
100 this at an acceptable level. Finally,
819°C
10 reforming is an endothermic process that
775°C
will cause a temperature drop that needs
1 to be compensated by injecting air/oxygen
735°C
0 to burn part of the gas, causing possible
100 200 300 400 500 600 700 temperature control issues.
temperature [degC]

Figure 4. The amount of tar that will In-bed tar reduction

condense on a surface with given More ideally, the tar concentration is
temperature; values are calculated from reduced inside the gasifier. The dual
measured tars; lines refer to tests with fluidized bed gasifier developed by the
wood in MILENA gasifier at different Technical University in Vienna, and firstly
temperatures. demonstrated in Güssing, uses a
catalytically active bed material: olivine.
Tars will form condensates below the tar The iron in the olivine is acting as a
dew point, but also above the tar dew reformer catalyst under the steam-rich
point, tars may cause issues. In that case, conditions that are applied in the
tars are thought to be responsible for coke technology. In these plants, the tar dew
formation. This can be coking of e.g. point is well below 200°C and thus a
reforming catalysts. Especially Nickel conventional particle filter can be used
catalysts are famous for their coking without plugging and fouling risk.
tendency and heavy tars certainly play a Important for sufficient olivine activity is
role. Another tar issue at high the “activation” process, where iron
temperature is visible when using high migrates to the surface of the olivine
temperature filters. Quick plugging of the particle. This activation takes place during
filter, called filter blinding, is thought to be the heat treatment before use, but
caused by tars. This mainly happens at continues during the first days of
temperatures above 600°C [1]. operation [2]. Methods to accelerate this
have been identified by ECN and
Catalytic reforming implemented in the larger gasifier in
Solving the tar problem has been subject Göteborg, which is using above-
of much research. Ideally, tar removal mentioned TU Vienna technology. More
takes place at high temperatures in order direct methods for “in-bed tar reduction”
to avoid tar condensation. Tar removal are available as well. Limestone and
inside the gasifier or directly downstream dolomite are the most well-known
the gasifier theoretically is the solution, additives used to suppress tar formation.
turning downstream units into more These materials however, have the
conventional processes. Catalytic tar disadvantage of being relatively soft. This
reforming is one of those possible means that the additive quickly leaves the
solutions. It however, requires a catalyst fluidized bed as fine powder and
that can withstand the harsh environment constantly needs to be supplemented.
of the gases exiting the gasifier. That gas The next solution for tars is to remove it
contains catalyst poisons like sulfur, but downstream to protect the subsequent
also the particles in the gas offer a units such as engine, compressor, and also

25
catalytic upgrading reactors. Also water cooling. The cooler did not work properly
washers should preferably be operated in a gas containing potentially condensing
without tar to prevent troublesome tars and had to be modified several times.
water/tar mixtures. I will mention the Another example is the “logic” to have a
main ones. cyclone upstream the cooler. This is
generally a bad choice in gasification
RME scrubbing processes, since particles are required to
Washing with biodiesel (RME: Rapeseed keep the cooler clean.
Methyl Esther) is often used to remove As a final example, HDS (Hydro-
tars from gas in a washing unit. Since RME DeSulphurization) can be mentioned. This
is costly and the typical consumption is 1 is a conventional process in petro-
kg RME per kg tar removed, this method is chemistry with well-developed catalysts,
only economically viable if tar content is which can be used to treat the organic
already low. Approximately 5 gram/Nm3 sulphur present in the gas from e.g. a
tar is considered acceptable for RME fluidized bed gasifier. The presence of
scrubbing. ethylene in the gas however, results in a
temperature increase due to ethylene
OLGA scrubbing hydrogenation. Additionally, water-gas-
ECN has been developing a two-step shift will even further increase the
scrubbing process called OLGA. The temperature control issue in HDS.
~500°C gas is first cooled to just above the
water dew point to condense the heavy 5. Conclusions
tars, whilst keeping the water in the vapor Biomass gasification holds many promises
phase. In the second step, the light tars in renewable energy and chemistry.
are removed in a absorption process. This Biomass gasification however, still has
also operates above the water dew point. several challenges. Technical issues often
Separated tars are available for recycling relate to feeding, agglomeration, tar, and
to e.g. the gasifier. Since OLGA can integration of process units.
remove high concentrations of tars
economically viable, it creates the 6. References
freedom to optimize the upstream gasifier [1] S. Tuomi, E. Kurkela, P. Simell and M.
process for anything like efficiency Reinikainen: Behaviour of tars on the
without having to worry about tars [3]. filter in high temperature filtration of
biomass-based gasification gas. Fuel 139
(0) 220-231 (2015).
4. Integration
[2] F. Kirnbauer and H. Hofbauer: The
Gasification never comes alone. Upstream,
mechanism of bed material coating in
it needs feeding and possibly pre- dual fluidized bed biomass steam
treatment. Downstream, there are often gasification plants and its impact on plant
multiple units that clean/upgrade and optimization. Powder Technology 245
finally use the gas. All these process steps 94-104 (2013).
have to work together to make the overall [3] www.royaldahlman.com/renewable/
process work. Even if all steps concern download-portal/
proven technologies, which often is not
the case, the integration of the units is far
from trivial.
There are examples where producer gas
cooling was considered similar to flue gas

26
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Bioenergy Sustaining the Future (BESTF) – a pan-European funding

mechanism for bioenergy demonstrators.
Megan Cooper1
1 Department of Energy and Climate Change, United Kingdom

1. Introduction material. Extensive research and

BESTF aims to strengthen the EU’s development on such advanced bioenergy
technology leadership by supporting the technologies has been conducted in the
next generation of bioenergy production. past, but there are few examples of
The ERA-NET Plus initiatives bring together commercial realisation. Since the EIBI
national and regional ministries and Implementation Plan [2] suggests that the
agencies and the European Commission to year 2020 should see advanced bioenergy
launch joint calls for proposals on being commercially available at large
bioenergy demonstration plants. Public scale, it is vital to test and prove such
funding from these partners will enable technologies at demonstration stage.
large-scale private investments, and thus To help shape the EIBI
help to achieve key objectives of the
European Industrial Bioenergy Initiative 3. Approach
(EIBI). Each BESTF initiative involves a single joint
call for proposals and is managed by a
2. Purpose consortium of national / regional
BESTF was established in response to programme managers. Each partner made
European and national goals of increasing substantial budget available for the calls,
the share of renewable energy production which was then ‘topped up’ with funding
and decreasing CO2 emissions, e.g. the EC from the EC (33% of the total call budget
target to reduce GHG emissions by 20% comes from the EC).
and to increase the share of renewable Each call involved two stages:
energy to 20% by 2020.
It is acknowledged [1] that bioenergy will Stage 1 – eligibility:
play a major role in achieving those Proposals were assessed for eligibility
targets. However, further development of against BESTF and relevant national
bioenergy paths will have to take into criteria.
account public concerns such as real
and/or perceived competition for land Stage 2 – full technical and economic
between different uses (food, feed, assessment:
materials, energy), and concern of adverse
effects on the environment. Eligible proposals were assessed by a
If bioenergy is to remain a major part of panel of external experts against defined
Europe’s RE portfolio, it will be necessary and published criteria.
to develop and deploy technologies that
make efficient use of biomass, and are
flexible in the type of biomass used as raw

27
4. Scientific innovation and relevance 5. Results
BESTF aims to facilitate a major step Two BESTF competitions have now taken
towards commercial deployment of place with three projects underway from
advanced bioenergy technologies. the first competition and six projects
Therefore, the consortium only supports selected for funding from the second
projects that present a strong business competition.
case, that are industry-led and that clearly The table below summarises the results of
contribute to achieving the Key the calls.
Performance Indicators set by the EIBI.
Table 2: Summary results from two BESTF
Scientific / technological innovation is one
calls.
of the key criteria for selection of projects
for funding and includes innovative BESTF1 BESTF2
technologies or an innovative combination No. 1st stage
11 45
/ use of existing technologies. applications
No. proposals
To ensure relevance, projects must also fit
invited to stage 8 13
within one of the EIBI bioenergy value chains
that reflect the diversity of feedstock options,
2
processing options, different national No. proposals
3 6
bioenergy markets, and bioenergy outputs. selected
Table 1: EIBI value chains. Value chains
1,2,3,5,6 2,4,5,6
represented
Thermochemical Pathways
Total project
1 Synthetic liquid fuels and/or 33,456,193 22,006,282
value
hydrocarbons (e.g. gasoline, naphtha,
kerosene or diesel fuel) and blending Total grant
11,605,153 14,553,270
components through gasification. awarded
2 Bio-methane and other bio-synthetic
gaseous fuels through gasification. BESTF 1 projects are due to complete in
3 High efficiency heat & power 2017, while BESTF 2 projects will end in
generation through thermochemical 2018.
conversion (propose limit e.g.: el >
45%) 6. Conclusions
4 Intermediate bioenergy carriers through The ERANET plus mechanism has brought
techniques such as pyrolysis and together European countries with a
torrefaction common interest in promoting the
Biochemical Pathways demonstration of bioenergy projects that
5 Ethanol and higher alcohols through can help meet challenging GHG and RE
chemical and biological processes targets. The two BESTF initiatives have
6 Hydrocarbons (e.g. diesel and jet fuel) enabled the provision of support from
through biological and/or chemical national and EU programmes to innovative
synthesis from biomass containing collaborative projects in need of
carbohydrates assistance to instigate private sector
7 Bioenergy carriers produced by micro- investment and increase their chances of
organisms (algae, bacteria) from CO2 commercialisation.
and sunlight

28
7. References
[1] Commission Communication of 10
January 2007: "Renewable Energy Road
Map. Renewable energies in the 21st
century: building a more sustainable
future" [COM(2006) 848 final - Not
published in the Official Journal].
http://europa.eu/legislation_summaries/
energy/renewable_energy/l27065_en.ht
m
[2] European Industrial Bioenergy Initiative
(EIBI), Boosting the Contribution of
Bioenergy to the EU Climate and Energy
ambitions, Implementation Plan 2013 –
2017, Version of 24 January 2014.
https://setis.ec.europa.eu/system/files/Bi
oenergy%20EII%202013-2017%20IP.pdf

29
Biiom
meeth
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H
Hennßstraße 9, D-99 942
23 WeWeim
mar
Biioggas TTel +49
9 (0
0)3 643
3 - 7 40
4 23
2 64
6
FFax +49
9 (0
0)3 643
3 - 7 40
4 23
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6
m
mail info o@
@bioogaasundeneergie.d
de

Wasste
W e Ma
Manaaggem
meentt htttp:///ww m/prrofile/Frrankk_Scholw
ww.xxing..com
de.linkediin.co pub/ffrankk-sch
om/p holw
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nergy sys
En s ste
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m in atio
on

Co
onntribu n in rese
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onnsu
ultingg & K
Knnow
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dge er

Exxpert rep
r portiingg

30
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Small-scale upgrading of biogas with in-situ methane enrichment and

wood ash filter
Johan Andersson1, Henrik Olsson1, Mats Edström1 and Åke Nordberg2
1
Swedish Institute of Agricultural and Environmental Engineering (JTI)
2
Department of Energy and Technology, Swedish University of Agricultural Sciences (SLU)

1. Introduction The Swedish Institute of Agricultural and

Farm-based biogas production from Environmental Engineering (JTI) and the
manure and other organic matter offers Swedish University of Agricultural Science
an opportunity to increase generation and (SLU) are developing two upgrading
use of renewable energy, thereby technologies (in-situ methane enrichment
reducing greenhouse gas emissions. While and wood ash filter) suitable for small-
the Swedish techno-economical biogas scale biogas plants (<5 GWh/yr). The
potential from manure is estimated to be advantage of these technologies in
1 300 – 2 800 GWh/yr [1], Swedish farm- comparison to current commercially-
based biogas production was only 77 GWh available upgrading technologies is that
in 2013 [2]. Today, biogas from farm- they are both operated close to
based production is mainly used for atmospheric pressure (thus no need for
combined heat and power production. high pressure vessels). Furthermore, the
However, due to current low electricity two upgrading technologies can be
prices and problems with monetising heat, operated separately as standalone
farm-based biogas plants often face technologies as well as in combination.
difficulties being economically viable. One
way to achieve better economic viability
2. In-situ methane enrichment
for small-scale biogas plants is to upgrade
The saturation solubility of carbon dioxide
the biogas (i.e. remove the carbon dioxide
(CO2) is much higher than that of methane
to increase energy density) to vehicle fuel
(CH4) in digester sludge. This fact is utilized
quality, thus reducing dependence on
by the in-situ methane enrichment
fossil fuels such as diesel and petrol.
process where digester sludge rich in
There are currently several upgrading dissolved CO2 is circulated to an external
technologies on the market, e.g. water vessel; the desorption unit (Figure 1). Air is
scrubber, chemical scrubbers, pressure injected into the bottom of the vessel and
swing adsorption (PSA) and membranes. the aeration of the sludge results in
However, the low gas flows at small-scale desorption of CO2. The air with desorbed
biogas plants results in high upgrading CO2 is then evacuated from the top of the
costs with these conventional techno- vessel, while the “CO2-poor” sludge is
logies [3]. To reduce the upgrading cost, returned to the digester. The process
there is a need to explore alternative, results in the continuously removal of CO2
simple and inexpensive upgrading techno- from the digester and hence an increase in
logies suitable for small-scale biogas the CH4 concentration of digester gas.
plants. However, since the digester content also
contains small amounts of dissolved CH4, it

31
is unavoidable that some CH4 is also We are studying the ability to upgrade
desorbed during the process, giving rise to biogas with a fixed bed of wood ash rich in
CH4 emissions from the system. The in-situ CaO. Prior to testing, the ash is mixed with
methane enrichment process as described water to create a liquid to solid ratio (L/S)
above was initially studied by Richards et of 0.2-0.4 and the humid ash is then
al [4]. loaded into a vessel, the ash filter. When
the digester gas passes through the ash
bed, CO2 and hydrogen sulphide (H2S) are
chemically fixed (Figure 2).

Figure 1. Process overview of in-situ Figure 2. The digester gas is led through a
methane enrichment. Digester sludge is bed of humid wood ash where CO2 and H2S
circulated to the desorption unit where air are chemically bound.
is injected for desorption of CO2.
Initial experiments have been conducted
Initial pilot-scale experiments performed at laboratory scale (20 L) where the
by JTI and SLU in collaboration with the ingoing CO2 (35%) has been effectively
Royal Institute of Technology showed that captured in the ash bed (0% CO2 in the
a CH4 concentration of 87% in the digester outgoing gas). Besides upgrading the
gas could be reached [5]. However, the biogas, the accelerated carbonation
CH4 losses during these experiments were process (i.e. fixation of CO2) leads to an
8%, which was unsatisfactory. efficient stabilisation of the ash, which
Nevertheless, computer simulations results in decreased pH by 2-3 units. This
revealed that optimisation of sludge and stabilisation is essential if the ash is to be
air flow could reduce CH4 losses to <2% recycled back to the forest to compensate
[5]. Therefore, new pilot-scale for the removal of nutrients in conjunction
experiments were conducted to achieve with logging and harvesting of tops and
efficient CO2 removal while keeping CH4 branches.
losses <2% of CH4 production.
3. Wood ash filter 4. Experimental set-up
In the ash filter, CO2 from biogas is Based on promising results from previous
captured based on the principle of separate studies with in-situ methane
carbonation; i.e. calcium oxide (CaO) is enrichment and wood ash filter, new
reacting with CO2 under the formation of experiments were conducted where the
calcite (CaCO3). The method has been two technologies were combined. The
studied by Mostbauer et al [6] where a idea was that in-situ methane enrichment
fixed bed of bottom ash from Municipal should remove the majority of the CO2
Solid Waste Incineration (MSWI) has been and the wood ash filter would act as a
used for upgrading biogas/landfill gas.

32
final polishing step where any remaining total CH4 production. The in-situ methane
CO2 would be captured. enrichment also showed good ability to
reduce H2S in the digester gas as the
JTI’s mobile biogas plant with a digester reduction amounted to more than 80%
volume of 5 m3 (Figure 3) was fed a compared to the reference period (mobile
mixture of liquid pig and cattle manure biogas plant operation without in-situ
during the experiment. The mobile biogas methane enrichment and ash filter).
plant was equipped with in-situ methane
enrichment where the volume of the All the ingoing CO2 to the ash filter was
desorption unit was 5% of the digester initially chemically bound in the ash and
volume. The sludge and air flows to the the outgoing gas concentration was 97%
desorption unit were chosen to reduce CH4 CH4, 1% H2O and 2% nitrogen (N2). The
emissions to <2% of total CH4 production. presence of N2 could be explained by the
aeration of the sludge where some N2 was
The active volume of the wood ash was injected into the digester. The CO2
180 L and the ash filter was placed in a breakthrough (i.e. when 1% CO2 in the
separate container next to the biogas outgoing gas was reached) was observed
plant. The ash originated from combustion after 9 days of operation. The CO2 fixation
of wood pellets and had a high CaO capacity of the ash until the time of
content (44% of DM). breakthrough was 0.14 kg/kg DM ash.
Furthermore, the wood ash showed good
H2S removal performance where all the
ingoing H2S from the digester gas was
chemically bound in the ash bed.

6. Conclusions
In-situ methane enrichment has shown
good ability to remove a major part of the
CO2 and H2S from digester gas, while the
Figure 3. JTI´s mobile biogas plant consists methane emissions from the system was
of a digester (5 m3), storage tank for liquid kept to <2%. However, with continued
substrates, dual shafted grinder and two optimisation of the design and operational
tanks for pasteurisation of substrate. settings of the process, it is expected that
the CH4 enrichment could be further
5. Results improved, while at the same time
While detailed results from the pilot-scale reducing the CH4 loss 1%. The hypothesis
experiment with the combination of in- is that in-situ methane enrichment can be
situ methane enrichment and wood ash applied for upgrading of biogas to “L-gas”
filter will be published in a scientific paper quality ( 85% CH4) with reasonable
later during 2015, the following is a brief methane emissions from the system.
summary of the experiment outcomes.
Wood ash filter is a flexible upgrading
The CH4 concentration in the digester gas technology which can handle a wide range
was increased from 60% to 81% when in- of ingoing CO2 concentrations. It can
situ methane enrichment was applied, therefore be used either as a final
while CH4 emissions were kept to 1.9% of polishing step (after in-situ methane

33
enrichment, membrane separation, etc.) the BABIU process – Upgrading of landfill
or as a single upgrading technology. gas or biogas with the use of MSWI
Additionally, it is a very simple technology bottom ash. Waste management 34
with few moving parts, and operation (2014) 125-133.
conditions close to atmospheric pressure
and ambient temperature. The pressure
drop over the ash bed is very low and the
overpressure from the digester is more
than enough to drive the biogas through
the filter.

When removing CO2 and H2S from biogas,

the ash is simultaneously stabilized, which
is of great importance if the ash is to be
recycled to the forest.

7. References
[1] Luostarinen, S., (2013). Energy potential
of manure in the Baltic Sea region.
Knowledge report, Baltic manure WP6
Energy potentials. Feb, 2013.

[2] Energimyndigheten & Energigas Sverige,

(2014). Produktion och användning av
biogas och rötrester år 2013. ISSN 1654-
7543.

[3] Bauer, F., Hulteberg, C., Persson, T. &

Tamm, D. (2013). Biogas upgrading –
Review of commercial technologies. SGC
2013:270. Malmö, 2013.

[4] Richards BK, Herndon FG, Jewell WJ,

Cummings RJ, White TE. In situ methane
enrichment in methanogenic energy crop
digesters. Biomass Bioenerg
1994;6(4):275-282.

[5] Nordberg, Å., Edström, M., Uusi-Penttilä,

M. and Rasmuson, Å.C. (2012). Selective
desorption of carbon dioxide from
sewage sludge for in-situ methane
enrichment: Enrichment experiments in
pilot scale. Biomass and Bioenergy 37
(February 2012), 196-204.
doi:10.1016/j.biombioe.2011.12.012

[6] Mostbauer, P., Lombardi, L., Olivieri, T.,

Lenz, S., (2013). Pilot scale evaluation of

34
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Hydrogenotrophic methanogenesis: Performance and robustness of a

self regenerative biocatalyst
Savvas Savvas, Richard Dinsdale, Tim Patterson and Sandra Esteves

Wales Centre of Excellence for Anaerobic Digestion, Sustainable Environment Research Centre, Faculty of
Computing, Engineering and Science, University of South Wales, Pontypridd, CF37 1DL Wales, UK.

1. Introduction hydrogenotrophic methanogens could

The thermodynamic stability of CO2 has benefit from syntrophic relations with
been a real challenge for many other microbial populations, which can
technologies that explore its use as a increase the robustness of the system.
substrate for the formation of This study aims to evaluate the response
hydrocarbons. If the challenge could be of a mixed mesophilic anaerobic culture in
viably met, it would be expected to terms of conversion rates, efficiency and
present a major solution to the current flexibility when subjected to different
issue of renewable energy storage as well stress conditions, i.e. changes in the
as a cost effective method for biogas feeding rate and composition, nutrient
upgrading. Hydrogenotrophic methano- starvation, carbon starvation and expo-
genesis is a biological process that has sure to oxygen.
shown great promise in laboratory trials
[1]–[3], with advantages including high 2. Materials and methods
conversion yields and low energy inputs. The reaction vessel comprised a glass
In contrast to metal catalysts, the cylinder of 1.5 L working volume. A
microbes involved do not suffer as a result centrifugal pump was attached to a port at
of impurities in the gas stream and require the side of the reactor so as to vertically
significantly lower temperatures and recirculate the liquid media at constant
pressures. Furthermore the molar CO2 to flowrates (6 L/min) by taking the liquid
CH4 conversion ratio can reach the value from the bottom side of the reactor and
of 1 [4]. reintroducing it at the top. A gas inlet was
A major precondition for the successful attached to the bottom of the glass
commercialisation of biological cylinder so that the gas was directly
methanation of carbon dioxide is the sucked into the pump as soon as it
ability of the system to adapt to the entered the cylinder. No microporous
unsteady operational conditions that are diffusers were used. The liquid media
inherent in biogas plants and renewable consisted of mesophilic anaerobically
energy generation. These include uneven digested sewage sludge collected from a
substrate feeding rates and composition, full scale anaerobic digester filtered down
periods of inactivity, as well as the to 125 m. No chemical buffers or
occasional inadvertent exposure to nutrients were used throughout the
oxygen. Previous studies with pure or experiment. The gas feedstock was a
enriched cultures focus entirely on the mixture of CO2 and H2, both supplied from
hydrogenotrophic biome. However, as in compressed gas cylinders. The gas
the case of biomass digestion, flowrate and composition were

35
continuously monitored by a series of gas contained all the necessary microbes
sensors and flow meters and adjusted involved in the stages of hydrolysis,
accordingly. The temperature of the liquid acidogenesis, acetogenesis, and aceto-
media was maintained at 37oC throughout clasis.
the experiment. Redox and pH were also The ability of the culture to work at
continuously monitored. different gas feeding flowrates and
compositions while achieving constant
3. Results conversion efficiency was also
Figure 1 shows the volumetric conversion investigated. As shown in Table 1 the
efficiency of the reactor during a period of culture seemed to adapt well to erratic
6 months. Apart from sporadic changes for changes in the gas feeding rate (from 28.1
experimental purposes, the gas inflow was to 200 L/L.d) with conversion efficiency
kept constant at 36 L/L.d and the gas returning to its pre-change value within
composition at an approximate volumetric hours.
ratio of 78/22 - H2/CO2.
Table 1. Conversion efficiency at 5
different gas feeding rates (CO2/H2 ~ 0.28),
at 5 different dates.

Inflow 28.1 36.0 51.8 60.5 200

(L/L.d)
CH4% in 90.3 94.4 99.3 98.9 90.1
outflow

A scenario was tested where the same

Figure 1. Conversion performance over a 6 biomethanation unit would be required to
month period. work with different substrates sources, i.e.
energy to hydrogen from a renewable
During this period the culture was kept in source or an anaerobic digester biogas.
continuous mode in terms of carbon and The biomethanation reactor culture was
energy but in batch mode in terms of first left without any external feeding for 2
essential micro and macro nutrients. days and then after it had reached a
Under these conditions, nutrient limitation steady state in terms of conversion, the
was expected to bring a decline in gas composition was altered to include
metabolic activity which did not occur as CH4 in the feeding gas.
there was an average increase in Figure 2 shows the response of the culture
conversion efficiency. Also, despite the from recovery after fasting and after a
fact that cell yield has been shown to be swift change from the ‘’power to gas’’
proportional to CH4 production [2], [5], mode to the ‘’biogas upgrading’’ mode.
biomass concentration remained directly Under a steady gas feeding rate of
proportional to the total elemental 72.7 L/L.d, the conversion efficiency
concentration throughout the experiment reached stability (>90% CH4) after a period
(data not shown here). All the above show of two hours whereas the change in gas
that there was a cell recycling system composition caused a disruption of 47 min
where the limited micro and macro after which conversion went back to the
nutrients where continuously released initial value.
from dead cells since the initial inoculum

36
 of fasting, half of the hydrogenotrophic
population was still expected to be alive.
This would not be the case for isolated
pure populations, as in experiments with
Methanobacterium M-20 and Methano-
sarcina barkeri strains, cell survival rates
where zero after just one month of
starvation [8].
Unintentional or unavoidable exposure to
Figure 2. The effect of the presence of CH4 oxygen can have damaging effects to
in the gaseous substrate after 2 days of strictly anaerobic populations [8].
starvation (simulating biogas upgrading) However, as previously reported [9] mixed
cultures have an advantage over pure
It must be noted that due to the structural cultures, firstly due to the presence of
design of the system, gas feeding rates facultative fermentative microbes that can
strongly affected the time needed for the scavenge dissolved oxygen and secondly
converted gas to reach the sensors and due to the shielding mechanism of
therefore the values from Figure 3 include biofilms where methanogens may have
an approximate delay of 30 min (the time protection behind layers that act as
needed for the sensors to detect any diffusion barriers. To test the effect of
changes in the gas outflow at the specific oxygenation, the liquid media was sparged
feeding rate). with a gaseous mix of 20% CO2 / 80% air
Mixed anaerobic cultures have been v/v for 14 hours before returning to a
reported in the past to have good 78/22 H2/CO2 environment. Figure 4
recovery rates even after prolonged shows that recovery was complete after
starvation periods [6]. Figure 3 shows less than 24 hours.
hydrogenotrophic activity after a
starvation period of 45 days. As it can be
seen conversion efficiency achieved over
90% in less than 48 hours.

Figure 4. Recovery after 14h sparging with

a mix of 20% CO2 / 80% air.

4. Conclusions
Figure 3. Recovery after fasting for 45 days The robustness of a mixed mesophilic
anaerobic microbial population was
A value of 0.016 d-1 has been reported for tested, under various gas feeding regimes
the death rates of mesophilic hydro- and in terms of recovery after exposure to
genotrophic methanogens in mixed two different stress conditions, starvation
anaerobic cultures during starvation [7], and oxygenation. The results from the
which would indicate that after a month present study indicated that mixed

37
anaerobic cultures have the ability to digester biogas by CO2-to-CH4
convert mixtures of H2 and CO2 at fast conversion with H2,” Archaea, vol.
rates of 200 L/L.d and 52 L/L.d achieving 2013, 2013.
over 90 and 99% of CH4 output gas quality
and responded well to the unsteady [3] M. Burkhardt and G. Busch,
“Methanation of hydrogen and carbon
operating conditions that are present in
dioxide,” Appl. Energy, vol. 111, pp.
biogas plants as well as the intermittency 74–79, 2013.
of renewable energy generation.
Furthermore, this performance was under [4] J. C. Lee, J. H. Kim, W. S. Chang, and D.
restricting conditions in terms of the Pak, “Biological conversion of CO2 to
availability of essential micro and macro CH4 using hydrogenotrophic
nutrients, and even then the mesophilic methanogen in a fixed bed reactor,” J.
culture showed clear signs of self Chem. Technol. Biotechnol., vol. 87, no.
regeneration, which indicated that February, pp. 844–847, 2012.
bacterial metabolisms were continuously
active and responsible for the recycling of [5] Z. Y. Zhang and T. Maekawa, “CH4
Fermentation Using Acclimated
cell material. This novel self regenerative
Methanogens on a Continuous Feed
biomethanation system responded well as
Substrate of Mixed Carbon Dioxide and
a catalytic converter with gas and Hydrogen,” J. Soc. Agric. Struct., vol.
electricity being the only inputs for long 24, no. 4, pp. 207–214, 1994.
periods of time.
[6] K. Hwang, M. Song, W. Kim, N. Kim,
5. Acknowledgements and S. Hwang, “Effects of prolonged
The authors would like to acknowledge the starvation on methanogenic population
University of South Wales Centenary dynamics in anaerobic digestion of
Scholarship for Savvas Savvas and the funding swine wastewater,” Bioresour.
provided by Welsh Government (WG) (Zero Technol., vol. 101, no. 1, pp. S2–S6,
Waste programme) and by A4B (WG and 2010.
European Regional Development Fund) for the
Knowledge Transfer Centre for Advanced [7] X. Hao, Z. Cai, K. Fu, and D. Zhao,
Anaerobic Processes and Biogas Systems “Distinguishing activity decay and cell
(AAPBS), which has supported the purchase of death from bacterial decay for two
equipment and consumable resources types of methanogens,” Water Res.,
required for this work. vol. 46, no. 4, pp. 1251–1259, 2012.

6. References [8] D. Morozova and D. Wagner, “Stress

response of methanogenic archaea
[1] J.-P. Peillex, M.-L. Fardeau, and J.-P. from Siberian permafrost compared
Belaich, “Growth of Methanobacterium with methanogens from
thermoautotrophicum on H2-CO2: high nonpermafrost habitats,” FEMS
CH4 Productivities in Continuous Microbiol. Ecol., vol. 61, pp. 16–25,
Culture,” Biomass, vol. 21, pp. 315– 2007.
321, 1990.
[9] D. Botheju, B. Lie, and R. Bakke,
[2] M. R. Martin, J. J. Fornero, R. Stark, L. “Oxygen effects in anaerobic digestion
Mets, and L. T. Angenent, “A single- - II,” Model. Identif. Control, vol. 31, no.
culture bioprocess of 3901, pp. 55–65, 2010.
methanothermobacter
thermautotrophicus to upgrade

38
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Cleaning Biomass Derived Syngas with Fluid Bed Reforming Catalysts

Kimberly Magrini-Bair1, Whitney Jablonski, Matthew Yung, Yves Parent, Jessica Olstad,
Steven Deutch

1National Renewable Energy Laboratory, National Bioenergy Center, 15523 Denver West Parkway, Golden,
CO, USA

1. Introduction cellulosic ethanol production via indirect

Catalytic conditioning of biomass-derived gasification, both a nickel alumina
syngas by tar and hydrocarbon steam fluidizable catalyst and a fixed bed
reforming has been conducted with rhodium based catalyst were synthesized
catalysts developed at NREL and industry. and used for conditioning biomass-derived
Supported nickel-based catalysts with syngas in the integrated ethanol synthesis
various promoters have been the most demonstration run. The work reported
widely studied class of materials and here describes catalyst performance and
generally show good initial activity, but the pre- and post-use physical and
are susceptible to deactivation from chemical properties of both catalysts
contaminants in raw syngas, such as during > 200 h of use for conditioning oak
hydrogen sulfide, ammonia, hydrogen derived syngas with the goal of
chloride, tars, and other trace understanding how to best deploy these
contaminants. These impurities require catalysts for future use.
removal, usually through catalytic
conditioning, in order to produce a quality 2. Reforming Catalysts
syngas for end-use synthesis of liquid fuels The nickel fluidizable catalyst preparation
such as ethanol and hydrocarbon fuels. used in this work is described in detailed
Reforming the hydrocarbon contaminants in a US Patent [Parent et al., 2011]. In
in raw syngas to additional syngas results brief, a fluidizable -alumina support is
in higher carbon utilization of the biomass prepared at CoorsTek by spray drying an
feedstock and requires that the catalyst be alumina precursor solution with resultant
able to reform recalcitrant olefins and spherical alumina particles collected in the
methane, which can make up to 20 vol% size range of 180-250 μm. The alumina is
(dry basis) of biomass-derived syngas. then custom calcined to provide hardness
Methane is recalcitrant to reforming and is and surface area that is useable for
generally reformed in to additional syngas catalyst preparation and capable of
in a downstream steam methane fluidization at high temperatures. The
reformer. To avoid the need for an SMR, a calcined support is impregnated with the
sulfur tolerant reforming catalyst catalyst components in a two-step
developed by Johnson Matthey was used incipient wetness process interspersed
to completely convert residual methane with air calcination. The first step adds an
left after primary reforming using an NREL aqueous solution of magnesium and
developed nickel based catalyst. To potassium nitrate salts (Mg(NO3)2•6H2O
complete the U.S. Department of Energy and KNO3) to the support, which is
Biomass Program’s 2012 demonstration of calcined at 650 ºC in air for two hours to

39
break down the metal salts into their with a Malvern Instruments Hydro 2000G
oxide forms on the support surface (MgO particle size analyzer.
and K2O). The magnesium and potassium
containing support is then impregnated 3. Syngas from Biomass Gasification
with an aqueous solution of Ni Biomass gasification was performed in a
(NO3)2•6H2O and calcined again using the 20.3 cm ID, electrically heated fluidized
same conditions. The finished catalyst is bed reactor as part of NREL’s
then characterized for reforming thermochemical pilot development unit
performance in a microactivity test system process. A loss-in-weight feeder supplied
(MATS) with model syngas based on steam white oak pellets to a pellet crusher
gasified oak containing model tars and through rotary valves that provided
methane. Physical and chemical pressure isolation from the feeding
characterization comprises surface area system. Crushed biomass entered the
and particle size distribution bottom of the fluid bed gasifier through an
measurements, elemental analysis via auger. Superheated steam and carbon
inductively coupled plasma spectroscopy dioxide fluidized 25 kg of olivine (250 μm
(ICP), temperature programmed reduction average particle diameter) to produce a
to assess Ni crystal size, and crystal bubbling bed. The gasifier product flowed
structure via x-ray diffraction (XRD). MATS through a thermal cracker, which has a
tests were used to assess reforming volume of 0.028 m3, to further crack large
performance of each drum of material via hydrocarbons. Two cyclone separators in
a core sample. All catalysts performed series removed solids (char, ash, and
similarly with model reformate. entrained olivine) that were subsequently
cooled and collected in char pots.
To achieve > 99% methane conversion, a Representative oak derived syngas
polishing reforming catalyst comprised of composition is shown in Table 1.
supported rhodium was used after the
primary reformer to deliver clean syngas Table 1. Average dry, nitrogen free syngas
for downstream mixed alcohol synthesis. composition for dual stage gasification.
This catalyst, a proprietary material
synthesized by Johnson Matthey [Steele et Dual Stage
al., 2013], consisted of 1-cm cloverleaf Component Gasification
shapes of supported rhodium promoted (mol %)
by ceria.
Helium (tracer) 2.17
Pre and post use catalyst samples were Hydrogen 35.64
characterized for chemical properties with
Methane 12.52
XRD and ICP analyses; physical
characteristics were assessed with particle Carbon Monoxide 19.17
size distributions. X-ray diffraction (XRD) Propylene 0.15
was conducted on powdered catalyst Propane 0.018
samples using a Rigaku Ultima IV Carbon Dioxide 26.13
diffractometer with Cu K X-ray source Acetylene 0.40
and a dTex detector. Elemental analysis
Ethane 0.36
was provided by a Spectro Arcos
inductively coupled plasma spectrometer Ethylene 3.43
and particle size distributions determined Hydrogen Sulfide 39 ppmv

40
4. Tar and Methane Reforming of the reactor. Alumina beads (0.003-
After passing through the cyclones, tars, 0.006 m diameter) were loaded on top of
and light hydrocarbons in the raw syngas the catalyst to improve heat transfer to
were reformed using a fluidized bed the incoming gas. The catalyst bed
primary tar reformer and a secondary consisted of 0.006 m cloverleaf-shaped
(polishing) packed bed steam methane pellets. Post reactor gas analysis was
reformer operated in series. The fluidized conducted with an online gas
catalyst was used primarily for tar and chromatograph as described above.
benzene destruction and the packed bed
reformer was used to reform any 5. Results
unconverted methane and light hydro- The NREL60 catalyst was highly effective
carbons. Fig. 1 left shows the fluidized bed for benzene and tar reforming.
tar reformer. The fluidized bed reformer is Conversions of benzene, naphthalene, and
almost identical in design to the fluidized heavy tars are shown in Table 2. Inlet
bed gasifier described above. 100 kg of concentrations averaged 1840, 430, and
fluidizable catalyst was added to the 350 ppmv for benzene, naphthalene, and
reactor and reduced in 10% H2 in N2 until heavy tars, respectively. Benzene was
H2 uptake stopped for 0.5h. The catalyst converted over NREL60 at 73% and to 97%
was fluidized with a mixture of raw syngas after the second (polishing) reformer.
from the gasifier/thermal cracker and Naphthalene was converted to 90.9 and
makeup N2. Product syngas exiting the 99.9% and heavy tars were converted to
reformer was measured every 3 minutes 99.2 and 100%, respectively.
with an Agilent online, rapid scanning gas
chromatograph. Figure 2 shows the primary gas compon-
ents of clean syngas (H2, CO, CO2, and CH4)
during the 100 hour test as measured
after the polishing reformer. Methane,
carbon monoxide, and carbon dioxide
concentrations (inclusive of nitrogen)
averaged 40, 14, 35, and 0.7 mole %,
respectively.
8

100 7
CH4 Conv.
Methane Conversion, %

6
Figure 1. Left) Primary fluidized bed tar 80
H2/CO Ratio

5
reformer and right) secondary packed bed Target Conv.
60 4
methane reformer.
H2/CO
3
40
The polishing packed bed reformer (PBR)
2
is shown in Fig. 1 right and comprises a 20
tubular reactor containing 6 - 9 kg of a 1

supported rhodium proprietary catalyst 0 0

0 25 50 75 100 125 150
provided by Johnson Matthey. The system
Time (hours)
is operated as a down-flow reactor. The
catalyst bed is heated with three bayonet Figure 2. Methane conversion across the
type heaters and monitored with a multi sum of reformers and H2: CO ratio at
zone thermocouple that spans the length scrubber exit.

41
Table 2. Tar concentrations determined by Particle size distributions (not shown) as a
on line mass spectrometry and taken after function of time on stream did not vary
the gasifier, after the primary reformer, greatly for the 100 h run with a range
and after the secondary reformer. observed from 240-300 μm, which is
typical of fresh catalyst. Taken together,
Concentrations Post Post pre and post catalyst characterization
-1 3 Post PBR
(g/N -m )* Gasifier Reformer indicate that the bulk of the reforming
catalyst remained reasonably constant
Argon 6.37 3.57 3.57
with respect to physical and chemical
Benzene 7.18 2.26 0.29
characteristics though some attrition did
Toluene 1.11 0.02 0.00
occur during extended reforming
Phenol 0.05 0.00 0.00
operations.
Naphthalene 2.78 0.33 0.00
Anth, Phen 0.92 0.04 0.00 6. Conclusions
Other Tar 3.66 0.03 0.00 From this study we conclude that
Heavy Tar 4.70 0.01 0.00 gasification and reforming operations
Total Tar (>78) 13.2 were successful in producing a clean
*Normal cubic meter. syngas from oak for mixed alcohol
synthesis. H2, CO, CO2, and methane
Elemental analysis of reforming catalyst concentrations averaged 40%, 15%, 31%
samples taken periodically during 100 and 0.8 mole %, respectively. Tar
hours of reforming is shown in Table 3. conversions of greater than 99% were
For the run, catalyst nickel, magnesium demonstrated for two-stage reforming,
and potassium contents do not vary much exceeding the target level of 99%. Average
from that of the fresh catalyst. benzene conversion levels for two stage
reforming were 97.0%, below the 99%
Table 3. Inductively coupled plasma conversion target level. 99% benzene
elemental analysis of catalyst samples conversions were demonstrated for short
from the primary reformer as a function of periods of time. Increasing reforming
time on s stream (hours). reactor severity (temperature) in future
Sample Wt% Wt% Wt% TOS (h) operations should increase benzene
Ni K Mg conversions to target levels. The
Catalyst* 5.41 0.29 2.03 0 fluidizable nickel alumina primary
R600-S21 5.14 0.32 2.03 10 reforming catalyst exhibited little change
R600-S23 5.11 0.39 1.87 34 in morphology and composition as
R600 S24 5.13 0.41 1.73 54 determined by elemental (ICP), structural
R600 S26 4.15 0.28 1.47 63 (XRD), and particle size distribution
R600 S27 4.94 0.38 1.75 73 analyses. The Johnson Matthey rhodium
*Fresh catalyst reduced in H2. based polishing reforming catalyst as well
maintained methane reforming activity
The XRD patterns of all of the catalysts
throughout the duration of the run.
obtained from both runs closely resemble
one another, showing the same reflections
7. References
as the fresh catalyst. This indicated that [1] Parent, Y. O., Magrini, K. A., Landin, S. M., Ritland,
the main crystalline phases of the catalyst M. A. U. S. Paten 7,915,196 B2, March 29, 2011.
are largely unchanged over a period of 100 [2] Steele, A. M., Poulston, S., Magrini-Bair, K. A.,
Jablonski, W. (2013). Catal Today, vol. 214, 74-81.
hours of time-on-stream during syngas
conditioning.

42
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

oG‰ƒ•…Ž‡ƒ‹‰Ƭƒ…–‹˜‹–‹‡•
Ersin Üresin1, Alper Sar o lan1, I l I k-Gülsaç1, Parvana Aksoy1, Yeliz Çetin1, Orçun Er1,
Fehmi Akgün1
1 TÜB TAK Marmara Research Center Energy Institute, P.O. Box 21, 41470 Gebze, Kocaeli, TURKEY.

1. Introduction x Hot gas clean-up technologies

Gas clean-up technologies are essential x Cold gas clean-up technologies
technical processes for industrial systems As shown in Figure 1, a semi-pilot scale
to remove pollutants and minimize their system was built up in TÜB TAK Marmara
effects on materials and environment. Research Center Energy Institute to carry
Syngas produced by coal, biomass and out gasification and gas clean-up tests. In
waste gasification contains main order to produce syngas from coal, 150
impurities such as particulates, tar, kWth circulating fluidised bed gasifier was
hydrogen sulphide (H2S), carbonyl used in the studies. Gas clean-up system
sulphide (COS) and ammonia (NH3). consists of granular filter, heat
Particulates and tar condensation can exchangers, bag filter, scrubbers and zinc-
cause plugging and fouling of the oxide bed. The product gas from the
condenser and process piping. Hydrogen outlet of gasifier enters into the gas clean-
sulphide and ammonia are hazardous up system and gaseous pollutants
gaseous pollutants for health and can (particulates, tar, H2S, COS, NH3) were
cause corrosion in pipelines which can removed. Granular filter was used to
affect the life of a plant. They also poison remove coarse particulates and bag filter
the catalyst strongly. Therefore, in many was used for fine particulates removal in
cases, an effective gas clean-up the system. Scrubbers for H2S, NH3
technology is required to reduce the removal and polishing zinc-oxide bed were
pollutant concentrations to low values used to reduce the H2S concentration
[1,2]. The focus of gas clean-up studies in below 1 ppmv in cold gas clean-up system.
TÜB TAK covers the development of more
effective and economic syngas cleaning
processes for Fischer-Tropsch (FT),
methanol production, and Combined Heat
and Power (CHP) systems. Removal of
sulphurous components and CO2 of biogas
to trace amounts is another important
issue, in order to use methane for various
applications.

2. Technology description
In TÜB TAK Energy Institute, gas cleaning Figure 1. Semi-pilot scale system. 1-
R&D studies are conducted following Gasification system 2- Hot gas clean-up
three main technologies: system 3- Integrated cold gas clean-up
x Gas clean-up techniques in gasifier bed system

43
Also, a pilot scale system was built up in calcined at 1073 K under the air
Soma, Manisa (Figure 2). The pilot system atmosphere. BET surface area, pore
suitable to be fed with both coal and volume and pore size of the calcined
biomass is under construction and consists sample were determined 11.3 m2/g,
of gasification, gas clean-up, water-gas- 0.2513 cc/g, and 889.5 Å, respectively.
shift, CO2 separation and Fischer-Tropsch
units.

Figure 4. Schematic of the test system

Figure 2. Pilot scale system in Soma- [1,3].
Manisa, TURKEY
Tar removal studies: The same test system
3. Experimental (Figure 4) was used for these tests. Tar
The catalytic effect of dolomite on sulphur removal performance of dolomite has
and tar removal was investigated in our been investigated by using the surrogated
bench scale system and results are compounds of tar, namely benzene,
discussed in this paper. The results were toluene and xylene at changing tar loads
used for pilot scale system design. and temperatures.

Sulphur removal studies: In order to 4. Results

simulate coal derived syngas atmosphere Sulphur removal studies: In Case 1, the gas
for bench scale H2S removal studies, gas fed to the reactor was composed of 1460
mixtures containing H2S were prepared ppmv H2S in a 27 vol% H2 and 73 vol% N2
from pure permanent gases (H2, CO, CO2, atmosphere. All H2S was captured by
N2). Feed gas compositions on a wet basis dolomite and the composition of the
are given in Table 1. The gas cleaning reactor effluent gas did not change. This
experiments were carried out by using an indicates that no other reaction took place
experimental set up schematically shown except chemisorption of the H2S. H2
in Figure 4. Details of the experimental set behaved like an inert gas and;
up can be found in our previous studies consequently, the results obtained in H2S
[1]. In all experiments, the total gas flow removal in H2-N2 mixture have been
rate was kept at 10 L/min, providing a gas similar to that obtained pure nitrogen. In
hourly space velocity (GHSV) of ~5600 h-1 Case 2, experiments undertaken with a
on a dry basis and a superficial velocity of gas mixture of 10 vol% CO2 in balance N2
13.3 cm/s. The reactor temperature was containing 1800 ppm H2S. The results
set to ~1023 K. Dolomite, (CaO (36.9 wt%), revealed that the dolomite was still very
MgO (16.8 wt%), SiO2 (0.08 wt%), Fe2O3 effective in capturing sulfur under these
(0.09 wt%), Al2O3 (0.12 wt%), and trace conditions, reducing the H2S level from
amounts of MnO4 and Na2O) which 1800 ppmv to around 3 ppmv. The
supplied from Eski ehir province of Turkey equilibrium H2S concentration under these
with the particle size of around 2-3 mm conditions was calculated to be ~1.3
was used in the experiments. Prior to the ppmv. No change was observed in the
experiments, the dolomite samples were composition of the inlet gas during the

44
experiment indicating that there were no reaction (Eq.2). The water vapor reduces
other reactions occurred. the activity of dolomite toward H2S. This
situation most likely originated from the
Table 1. Removal of H2S from binary, lower H2S removal efficiency which
tertiary and simulated gasification outlet allowed more H2S available to react with
gas mixtures by dolomite. CO/CO2.

CO2 + H2 CO + H2O (2)

In Case 5, the possibility of (WGS) reaction

was investigated. The H2S concentration
was reduced from 1564 ppm to about 157
ppm, with an efficiency of about 90 %.
Gas composition changed considerably
during the desulfurization process
resulting in 5.7 vol % CO2 and 8.4 vol % H2
in the product gas. This was indicated that
In Case 3, 10 vol % CO in balance N2 with the gas atmosphere with water vapor
1800 ppmv H2S was fed to the dolomite enhanced the (WGS) reaction on the
bed under the prescribed conditions. The dolomite surface. Consequently, as it
inlet gas composition was changed during might be expected, the CO concentration
the experiment. The CO concentration in drastically decreased from 11.5 vol % to
the mixture was decreased from 10 vol% 3.5 vol % on a dry basis.
to 7.7 vol% while 1.6 vol% CO2 was
measured in the reactor effluent gas Tar removal studies: Tar removal
stream. CO2 existence in effluent gas performance of dolomite has been
indicated that the Boudouard reaction investigated by using a gas mixture given
(Eq.1), is taking place according to the in Table 2.
following scheme.
Table 2: The changes of gas composition
2CO CO2 + C (1) and contaminant levels with temperature
for tar removal on dolomite. Feeding: 10
The experiments were carried out with a NL/min feed gas, 5.5 g/h H2O and GHSV of
gas stream composed of 10 vol % CO2, 26 ~6000-1 h.
vol % H2, 64 vol % N2 plus 1280 ppm H2S
(Case 4), about 90% of H2S removal was
achieved. However, the concentration of
H2S in the reactor effluent gas stream
measured as a128 ppm, which was higher
than the equilibrium H2S concentration of *on dry basis; B-benzene; T-toluene; X-xylene
50 ppm predicted by thermodynamic
calculations. This H2S removal efficiency As seen in Table 2 the formation of CO
was lower than that obtained with the might be attributed to the RWGS (Eq.2).
binary gas mixtures (Case 1-3). This might Dolomite showed a low degree of tar
be attributed to the existence of CO2 in removal activity as seen in Table 2. The
the reactant gas stream, and the water concentrations of xylene and toluene were
vapor that produced as a result of (WGS) decreased whereas the concentration of

45
benzene was increased in the outlet The observed increase in methane
stream. High operating temperature of concentration during tar removal study on
750°C on dolomite bed is believed to be dolomite at 750°C was a result of
the result of thermally/catalytically broken hydrodealkylation of methyl groups of
methyl groups in toluene producing alkyl aromatics by releasing benzene
benzene and methane. Xylene was under the experimented conditions.
dealkylated similarly into toluene and Thermal decomposition of aromatic
benzene, consecutively in the presence of compounds seemed to be the prevailing
excess hydrogen. The increase in methane reaction as proved by the observation of
percentage from 3.2% to 4.0% supported blackened inner reactor surface of the
this suggestion. Total amount of 8.67 g dolomite bed and a decrease in total tar
C/Nm3 aromatic tar compounds, were fed load at the outlet stream.
with the gas mixture into dolomite bed
and 7.28 g C/Nm3, were measured at the 6. Acknowledgement
outlet stream of the dolomite bed. We greatly acknowledge The Scientific and
Converted tar compounds, equivalent to Technological Research Council of Turkey
1.40 g C/Nm3 might be coked by giving (TÜBiTAK) for supporting of “Liquid Fuel
pure carbon on the hot surfaces. Production from Biomass and Coal Blends”
Observation of blackened inner reactor project (Contract code: 108G043) in which
surface supported this hypothesis since it these studies were carried out.
is known that benzene molecule is cracked
by gas phase reaction when being subject 7. References
to temperature as high as 800°C in the [1] Ay, ., Atakül, H., Sar o lan, A., Akgün, F.,
absence of catalyst. Gülsaç, I.I., Çetin, Y., Üresin, E., Er, Ö.O.,
Aksoy, P. Hot gas clean-up with
5. Conclusions dolomites: Effect of gas composition on
sulfur removal activity. The Canadian
In the present study, hot gas H2S removal
Journal of Chemical Engineering. In Press,
was studied in the presence of calcined
(2015).
dolomite. In addition to H 2S
chemisorption, the WGS and RWGS [2] Üresin, E., Saraç, H. ., Sar o lan, A., Ay, .,
reactions were seen to occur depending Akgün, F. An experimental study for H2S
on gas composition, possibly due to the and CO2 removal via caustic scrubbing
presence of iron in the dolomite. Direction system. Process Safety and
of the reactions was dictated by the gas Environmental Protection, 94, 196-202
composition in a way to reach the (2015).
thermodynamic equilibrium. The
Boudouard reaction was another concern [3] Sar o lan, A. Tar Removal on Dolomite
to be taken into account. and Steam Reforming Catalyst: Benzene,
toluene and xylene reforming.
International Journal of Hydrogen Energy
According to our results, water vapor in
37, 8133-8142 (2012).
the dolomite bed had an inhibiting effect
on sulfidation reactions. CO2 might not
have an inhibition effect on sulfidation
reactions, but it could be a suppressor for
decomposition of CaCO3 to CaO.

46
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Innovative bioelectrochemical-anaerobic-digestion coupled system for

ammonia recovery and biomethane production from ammonia-rich
residues.
Yifeng Zhang1 and Irini Angelidaki1
1 Department of Environmental Engineering, Building 113, Technical University of Denmark, DK-2800
Lyngby, Denmark.

1. Introduction MFC or MEC could be a potential new

Anaerobic digestion (AD) is an attractive approach to prevent ammonia toxicity
technology widely used for organic waste during AD process by ammonia recovery.
treatment and simultaneously energy Nevertheless, the exoelectrogenic activity
production in the form of biogas [1]. in the anode of MFC or MEC may also be
Livestock manures together with organic inhibited at high ammonia levels (>4 g
industrial wastes are widely applied as NH4+-N/L) due to direct exposure of anodic
substrate, however, their high ammonia biofilm to the ammonia-rich streams
content can inhibit the digestion process, [16,23]. Moreover, the processes may
resulting in serious economic losses to the reduce the organic contents of the waste
biogas plant [2-6]. Both biotic and abiotic for the following AD process. All these
technologies have been developed to challenges need to be addressed before
counteract the ammonia inhibition by practical application. Operation of MEC as
means of removal and/or recovery [7-13]. an abiotic electrochemical reactor has also
However, most of the methods are been attempted, but the electric energy
uneconomical, requiring high energy cost is much higher compared to biotic
input, have low efficiency, and need operation [24]. One of the most recent
addition of chemicals, and thus, fail for BES which is so called microbial
practical application. desalination cell (MDC) may offer a new
Recently, the bioelectrochemical system solution [25-28]. MDC was initially
(BES) has drawn attention as a renewable designed for water desalination, but it
technology producing energy or products shares several common characteristics
from wastes [14-17]. Microbial fuel cell with MFC, such as high pH in the cathode
(MFC) and microbial electrolysis cell (MEC) due to OH- accumulation [29]. Moreover,
as typical BES have been demonstrated as NH4+ as a cation can also pass through
promising technologies to recover CEM [16-19]. Therefore, we hypothesize
ammonia from urine or reject water with that MDC could be a new method to
net energy production and no additional recover ammonia and thereby preventing
chemical costs [18-20]. An MFC-based ammonia toxicity, by integrating AD of
system has also been recently developed ammonia-rich residues into the
to remove/recover both ammonium and desalination chamber. The MDC could not
phosphorus from wastewater with power only inherit the advantages of MFC or
supply [21]. MFC has even been employed MEC for ammonia recovery, but also avoid
to remove ammonia from Arthrospira the risks of ammonia toxicity on the
maxima biomass before AD process [22]. anodic biofilm and the reduction of

47
organic contents. Besides, this new tion of the integrated SMDC-CSTR system
method involves a unique integration of for ammonia recovery and biogas
AD with ammonia recovery instead of enhancement. The effects of ammonia
simply connecting the two processes in concentration, external resistance and
series, leading to an alternative way for ionic concentrations on the system
both nutrient recovery and bioenergy performance were investigated. The
production. However, the feasibility of microbial community structure and
MDC for ammonia recovery has never diversity in such new system were studied
been reported. Furthermore, in order to using Ion Torrent PGM sequencing based
reduce the costs upon the integration of 16S rRNA genes analysis.
the MDC and AD process, an in-situ Resistor
applicable MDC design that can utilize e- e-
Organic waste
existing AD infrastructures such as Organic waste NH3 .Air
continuous stirred tank reactors (CSTR)
O2
should be pursued. Cl- CO2
H2O
Both AD and BES are complex processes Q-
H+ OH-
involving various biochemical reactions

Bacteria
NH4+
catalyzed by a large number of Organic
microorganisms [15,30]. It is crucial to matter Q+

understand the microbial ecology AEM Anode Plate Cathode CEM

especially when these two processes are
Figure 1. Schematic of the SMDC (A) and
integrated. However, most of the BES
the image of the integrated SMDC-CSTR
studies were focusing on the ammonia
recovery, while the impact of the recovery (B). Q+ and Q- are unspecified cations and
process on the microbial communities anions, respectively.
enriched in the both systems has never 3. Results
been reported. As shown in Figure 2, the CH4 production
2. Technology description rate decreased immediately by about 47%
A novel hybrid system consists of a in the CSTR 1, CSTR 2 and CSTR 4 after
submersible MDC (SMDC) and a CSTR elevating the total ammonia concentration
reactor was developed in this work as an to 6 g-N/L and the NLR to 0.4 g-N/L/d.
alternative approach to counteract After another 55 days of operation, the
ammonia toxicity during anaerobic CH4 production rate in the CSTR 1
digestion by means of in-situ ammonia gradually increased back to 83% of the
recovery and electricity production. The value that was observed in the CSTR 3.
SMDC contains only two chambers, i.e. Comparatively, no significant increase in
anode and cathode chamber, and the CH4 production rate was observed in CSTR
conventional desalination chamber is not 2 and CSTR 4. At this condition, 112%
required (Figure 1). This special design extra biogas was produced due to
makes it in-situ applicable to existing alleviation of the ammonia inhibition as
biogas infrastructures (e.g., CSTR), and the ammonia level in the reactor was
thereby may lower the construction, reduced. In the CSTR 1, the ammonia
operation and maintenance costs upon concentration decreased with time and
the integration. Such reactor design has reached to a stable level of 3.1±0.1 g-N/L
never been applied for ammonia recovery from day 60, resulting in a recovery rate of
or integrated with AD process. This work 86 g-N/m2/d (based on the area of CEM).
provided a proof-of-concept demonstra- To the contrary, there was no significant

48
 change of ammonia concentration in the toxicity during anaerobic digestion by
CSTR 2 and CSTR 4. It was also observed means of in-situ ammonia recovery and
that the total VFA in the CSTR 1, CSTR 2 electricity production using integrated
and CSTR 4 increased immediately after SMDC-CSTR system. Furthermore, for the
ammonia elevation (approx. 2.5 g-HAc/L), first time, we applied the newly launched
indicating ammonia inhibition. Unlike to Ion Torrent PGM high-throughput
the other reactors, the total VFA in the sequencing technology to reveal the
CSTR 1 decreased gradually with the microbial community diversity and
ammonia level. structure that enriched in such new
0.07 g-N/L/d NH4+ addition, 0.4 g-N/L/d 8.5
system.
2 5. References
[1] Weiland, P. Biogas production: current
CH4 production rate (L/L/d)

Ammonia nitrogen (g-N/L)

1.6 6.5

Current density (A/m2)

state and perspectives. Appl. Microbiol.
1.2 Biotechnol. 2010, 85(4), 849-860.
OLR (g/L/d)

4.5
[2] Hansen, K. H.; Angelidaki, I.; Ahring, B. K.
0.8
Anaerobic digestion of swine manure:
2.5 Inhibition by ammonia. Water Res. 1998,
0.4
32(1), 5-12.
0 0.5 [3] Nielsen, H. B.; Angelidaki, I. Strategies for
0 30 60 90 120
optimizing recovery of the biogas process
CH4, CSTR 1 Time (d) CH4,CSTR 2
CH4, CSTR 3 CH4, CSTR 4 following ammonia inhibition. Bioresour.
OLR Ammonia,CSTR 1 Technol. 2008, 99(17), 7995-8001.
Ammonia,CSTR 2 Ammonia, CSTR 3
Ammonia, CSTR 4 Current density [4] Smith, B. E. Nitrogenase reveals its inner
secrets. Science 2002, 297(5587), 1654-1655.
Figure 2. The system performance during
[5] Angelidaki, I.; Ahring, B. K. Thermophilic
continuous reactor operation.
anaerobic-digestion of livestock waste - the
The mass balance analysis on nitrogen effect of ammonia. Appl. Microbiol.
showed that 40.8% of the input ammonia Biotechnol. 1993, 38(4), 560-564.
was recovered by the SMDC. The [6] Nielsen, H. B.; Ahring, B. K. Effect of
tryptone and ammonia on the biogas process
preliminary energy balance analysis
in continuously stirred tank reactors treating
indicated that net energy (8.77 kWh/kgN,
cattle manure. Environ. Technol. 2007, 28(8),
data not shown) was produced during 905-914.
continuous operation. It must be noted [7] Ahn, Y. H., Sustainable nitrogen elimination
that this preliminary analysis was made to biotechnologies: A review. Process Biochem.
compare different recovery methods. The 2006, 41(8), 1709-1721.
organic carbon requirement in the anode [8] Fotidis, I.; Karakashev, D.; Angelidaki, I.
for the ammonia recovery is about 1 g- Bioaugmentation with an acetate-oxidising
COD/g-N. The acetate modified buffer was consortium as a tool to tackle ammonia
used here to mimic waste streams in the inhibition of anaerobic digestion. Bioresour.
anode, but wastewater or the supernatant Technol. 2013, 146, 57-62.
[9] Siegrist, H. Nitrogen removal from digester
effluent from anaerobic digester (e.g.,
supernatant-Comparison of chemical and
CSTR) could be used as anode carbon
biological methods. Water Sci. Techno. 1996,
source for the full scale implementation, 34(1-2), 399-406.
giving synergistic advantages for both [10] Tada, C.; Yang, Y.; Hanaoka, T.; Sonoda,
process simplification and energy savings. A.; Ooi, K.; Sawayama, S. Effect of natural
4. Conclusions zeolite on methane production for anaerobic
This study demonstrated a novel digestion of ammonium rich organic sludge.
technology for counteracting ammonia Bioresour. Technol. 2005, 96(4), 459-464.

49
[11] Doyle, J. D.; Parsons, S. A. Struvite Wastewater Using a Bioelectrochemical
formation, control and recovery. Water Res. System. Bioresour. Technol. DOI:
2002, 36(16), 3925-3940. 10.1016/j.biortech.2014.05.105.
[12] Mondor, M.; Masse, L.; Ippersiel, D.; [22] Inglesby, A.E.; Fisher, A.C., Enhanced
Lamarche, F.; Masse, D. I. Use of methane yields from anaerobic digestion of
electrodialysis and reverse osmosis for the Arthrospira maxima biomass in an advanced
recovery and concentration of ammonia from flow-through reactor with an integrated
swine manure. Bioresour. Technol. 2008, 99, recirculation loop microbial fuel cell. Energy
(15), 7363-7368. Environ. Sci. 2012, 5(7), 7996-8006.
[13] Ippersiel, D.; Mondor, M.; Lamarche, F.; [23] Nam, J.-Y.; Kim, H.-W.; Shin, H.-S.,
Tremblay, F.; Dubreuil, J.; Masse, L. Nitrogen Ammonia inhibition of electricity generation in
potential recovery and concentration of single-chambered microbial fuel cells. J.
ammonia from swine manure using Power Sources 2010, 195(19), 6428-6433.
electrodialysis coupled with air stripping. J. [24] Desloover, J.; Woldeyohannis, A. A.;
Environ. Manage. 2012, 95, S165-S169. Verstraete, W.; Boon, N.; Rabaey, K.
[14] He, Z.; Minteer, S. D.; Angenent, L. T. Electrochemical resource recovery from
Electricity generation from artificial digestate to prevent ammonia toxicity during
wastewater using an upflow microbial fuel anaerobic digestion. Environ. Sci. Technol.
cell. Environ. Sci. Technol. 2005, 39(14), 5262- 2012, 46(21), 12209-12216.
5267. [25] Cao, X.; Huang, X.; Liang, P.; Xiao, K.;
[15] Logan, B. E.; Hamelers, B.; Rozendal, R.; Zhou, Y.; Zhang, X.; Logan, B. E. A new method
Schroder, U.; Keller, J.; Freguia, S.; Aelterman, for water desalination using microbial
P.; Verstraete, W.; Rabaey, K. Microbial fuel desalination cells. Environ. Sci. Technol. 2009,
cells: methodology and technology. Environ. 43(18), 7148-7152.
Sci. Technol. 2006, 40(17), 5181-92. [26] Mehanna, M.; Saito, T.; Yan, J.; Hickner,
[16] Kuntke, P.; Geleji, M.; Bruning, H.; M.; Cao, X.; Huang, X.; Logan, B. E. Using
Zeeman, G.; Hamelers, H. V. M.; Buisman, C. J. microbial desalination cells to reduce water
N. Effects of ammonium concentration and salinity prior to reverse osmosis. Energy
charge exchange on ammonium recovery from Environ. Sci. 2010, 3(8), 1114-1120.
high strength wastewater using a microbial [27] Jacobson, K. S.; Drew, D. M.; He, Z., Use of
fuel cell. Bioresour. Technol. 2011, 102(6), a liter-scale microbial desalination cell as a
4376-4382. platform to study bioelectrochemical
[17] Rabaey, K.; Rozendal, R. A., Microbial desalination with salt solution or artificial
electrosynthesis-revisiting the electrical route seawater. Environ. Sci. Technol. 2011, 45(10),
for microbial production. Nature Rev. 4652-4657.
Microbiol. 2010, 8(10), 706-716. [28] Chen, X.; Xia, X.; Liang, P.; Cao, X.; Sun, H.;
[18] Wu, X.; Modin, O., Ammonium recovery Huang, X. Stacked microbial desalination cells
from reject water combined with hydrogen to enhance water desalination efficiency.
production in a bioelectrochemical reactor. Environ. Sci. Technol. 2011, 45(6), 2465-2470.
Bioresour. Technol. 2013, 146C, 530-536. [29] Chen, S.; Liu, G.; Zhang, R.; Qin, B.; Luo, Y.
[19] Kuntke, P.; Smiech, K. M.; Bruning, H.; Development of the microbial electrolysis
Zeeman, G.; Saakes, M.; Sleutels, T. H. J. A.; desalination and chemical-production cell for
Hamelers, H. V. M.; Buisrnan, C. J. N. desalination as well as acid and alkali
Ammonium recovery and energy production productions. Environ. Sci. Technol. 2012, 46(4),
from urine by a microbial fuel cell. Water Res. 2467-2472.
2012, 46(8), 2627-2636. [30] Pavlostathis, S. G.; Giraldogomez, E.,
[20] Ieropoulos, I.; Greenman, J.; Melhuish, C., Kinetics of anaerobic treatment-a critical
Urine utilisation by microbial fuel cells; energy review. Crit. Rev. Env. Contr. 1991, 21(5-6),
fuel for the future. Phys. Chem. Chem. Phys. 411-490.
2011, 14(1), 94-8.
[21] Zhang, F.; Li, J.; He Z. A New Method for
Nutrients Removal and Recovery from

50
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

BioCat Project - Taking Biological Methanation to Market Readiness

Dominic Hofstetter1
1 VP of Business Development, Electrochaea GmbH, 82152 Planegg, Germany

1. Introduction step, hydrogen is combined with carbon

The increasing deployment of renewable dioxide (CO2) and catalytically reacted to
energy is creating challenges for managing methane (CH4), the principal component
the electricity system. In today’s grid, of natural gas. If the composition of the
electricity demand and supply need to be product gas meets the gas quality
balanced at all times. With a growing requirements of the natural gas network,
share of wind and solar energy, which it can be injected into a natural gas
generate electricity intermittently and pipeline at the point of production
generally independent of demand, the (analogous to biomethane).
electricity grid will experience more
frequent and prolonged periods of
supply/demand imbalances. Such
imbalances will lead to more volatile
power prices and, in severe cases where
grid capacity is constrained, to the
curtailment of wind and solar energy
production.

Energy storage is being proposed as a

powerful solution to address these
problems. Figure 1. The Power-to-gas concept.

2. Technology description Once in the network, the gas can be

In power-to-gas (P2G) energy storage, stored for days, weeks, or even months.
electrical energy is converted to chemical The large storage capacity of the gas grid
energy in the form of methane. If wind, combines with low leakage rates to enable
solar, or other sources of renewable seasonal storage, a functionality of
energy is used, a low-carbon gas can be particular importance in regions with large
produced that is fully compatible with the seasonal swings in renewable energy
currently existing gas delivery and production.
utilization infrastructure.
The P2G product gas can also be
The first step in the P2G production chain transported geographically through
consists of the production of hydrogen existing pipelines to demand centres
and oxygen through electrolytic water further away. This is useful in regions with
splitting. 70-80% of the electric energy power grid bottlenecks or location
required for electrolysis is conserved in mismatches between power demand and
the hydrogen (H2) molecule. In the second renewable energy resources.

51
3. Utilization Pathways input gases to be of high purity so as to
The chemical identity between P2G avoid catalyst contamination. Its relatively
product gas and natural gas means that high operating temperatures (300-400°C)
electric energy from intermittent pose particular challenges for heat
renewables can be made available for a management and constrains a Sabatier
broad range of energy sectors. reactor’s ability to ramp up and down in
response to fluctuating flows of hydrogen.
The most obvious utilization pathway is to
use the gas for power production in Electrochaea is using a selectively evolved,
combined-cycle gas turbines (CCGTs). Such not genetically modified strain of
CCGT plants are anticipated to be required methanogenic archaea for the
in future energy systems to balance the methanation reaction. Archaea have
power grid, and P2G can deliver a low populated Earth for more than three
carbon fuel to these turbines. billion years and are believed to have been
among the first living organisms on the
Another important utilization pathway is planet. Along with bacteria and
the heat sector, which in many countries is eukaryotes, they form the third kingdom
difficult to decarbonize due to the limited of life in the phylogenetic taxonomy.
amount of biomass (for biomethane
production) that can be soured Methanogenic archaea are single-celled,
sustainably. P2G offers an opportunity to autotrophic organisms and feed
increase the share of low carbon gas in the exclusively on hydrogen and carbon
gas grid without additional biomass. dioxide, while producing almost
exclusively methane. The strain used by
Lastly, product gas from P2G can also be Electrochaea has been evolved under
used in compressed natural gas (CNG) selective pressure by professor Laurens
vehicles to decarbonize the transportation Mets, PhD, at the University of Chicago.
sector. The German carmaker AUDI AG The strain exhibits many characteristics
was first to launch a vehicle (A3 g-tron) that make it particularly suitable for
that can be purchased with e-gas, Audi’s industrial environments:
renewable gas product generated entirely x Extremely fast reaction rates;
from wind energy. Renewable gas will also x Very high tolerance to contaminants
be a fuel of choice to decarbonize parts of (H2S, O2, particulates, etc.)
the transportation industry that cannot be x High substrate and product gas
electrified, such as long-distance heavy- selectivity
duty vehicles. x Mild operating temperatures (60-65°C)
x High longevity (self-reproducing, self-
4. The Electrochaea Process maintaining)
Electrochaea is pioneering the x Fast ramping rates (quick response to
development of biological methanation. fluctuations in H2 supply)
x Very high carbon conversion efficiency
The conventional method of producing (98.6% of carbon is converted to CH4)
methane from hydrogen and carbon
dioxide is a thermochemical process The high contamination tolerance of the
known as the Sabatier Process, which uses microbes allows the process to use a wide
a catalyst based on nickel. While a proven range of carbon dioxide sources, including
technology, the Sabatier Process requires untreated biogas.

52
 NEAS Energy. AUDI AG provides
Electrochaea believes that the technical engineering and operating advice, while
characteristics of its microbes will Insero Business Services provides project
translate to lower capital and operating management and communications
costs as well as higher operating flexibility support.
compared with the Sabatier process.
Once operational, the BioCat facility will
5. The BioCat Project be the world’s largest P2G plant operating
with biological methanation.

To find out more about the BioCat Project,

visit the project’s website at:
www.biocat-project.com

The BioCat Project marks the last step in

Electrochaea’s scale-up and de-risking
pathway. Building on a pre-commercial
demonstration project executed in 2013 in
Denmark, BioCat is anticipated to lift the
company’s technology to market
readiness. The Project is partially funded
by ForskEL, a technology development
support program administered by the
Danish transmission grid operator
Energinet.dk.

The BioCat Project is located at the

wastewater treatment plant Avedøre
south of Copenhagen, Denmark, which is
operated by BIOFOS. It will use hydrogen
produced from a 1-MW alkaline
electrolyzer manufactured by Hydrogenics
Europe. The carbon dioxide is delivered
from untreated biogas produced through
the anaerobic digestion of sewage sludge
by the wastewater plant. The product gas
is injected into a 4-bar distribution grid
managed by HMN Naturgas, while the by-
products heat and oxygen are recycled in
the on-site wastewater operations. The
electrolyzer is anticipated to deliver
balancing services to the Danish power
grid and will be operated according to an
optimized trading strategy developed by

53
 For a better world

“I am convinced that the fossil fuels are merely a parenthesis in the history of mankind
and that the transfer to a sustainable energy system is not only wishful thinking but a
necessity if we and future generations should be able to have the same quality of life as
today.”
Dr. Jörgen Held, founder, owner and managing director of
Renewable Energy Technology International AB.

Renewable Energy Technology International AB promotes the transfer to a sustainable

energy system and is active within the following areas

Coordination of, and participation in, national and international R&D

projects

Consultancy work – renewable energy

Dissemination activities
- REGATEC conference series
- Renewtec report series

Contact details
Renewable Energy Technology International AB
Skarpskyttev. 10 D
SE-226 42 Lund
SWEDEN

www.renewtec.se +46 723 182 582 info@renewtec.se

54
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Experiences with one year operation of power-to-gas in Rozenburg, NL

Johan Holstein1, Harm Vlap1, Adriaan van der Steen1, Lukas Grond1 and Klaas Bos1
1 DNV GL – Oil & Gas, Energieweg 17, 9743 AN Groningen, the Netherlands

1. Introduction The main purposes for the development

The EU is facing unprecedented energy and implementation of power-to-gas are
challenges until 2020. As part of the ‘20- (i) to deliver flexibility to the energy
20-20 goals’, 20 % of EU’s energy system by offering a controllable power
consumption should be generated by load to facilitate the implementation of
renewable energy sources (RES) in 2020, a intermittent renewable energy sources
20 % greenhouse gas emissions reduction into the existing energy system and (ii) to
(relative to 1990 levels) should be realized enhance decarbonisation of the gas sector
and EU’s energy efficiency should be by establishing the conversion of
improved by 20 % [1]. Such a boost for the renewable power into hydrogen or
implementation of renewables will synthetic methane as a natural gas
encourage technological innovations, substitute for the mobility sector or as
technological development and increased feedstock for the chemical industry [4].
employment in Europe. Adoption of
enabling technologies by industrial DNV GL - a leading technical advisor to the
companies is inevitable for realizing EU’s global oil and gas industry - has
renewable energy targets. technologically supported the Dutch
Specifically, the Netherlands reached a distribution grid operator Stedin in
society-wide Energy Agreement for realizing the first Dutch power-to-gas
Sustainable Growth in September 2013 facility, by defining engineering guidelines,
which shows a consensus on doubling validating the selected technology and
planned energy efficiency savings to 1.5% ensuring gas grid injection compliance.
by 2020 and deploying more renewable This first Dutch power-to-gas
energies (14% by 2020 and 16% by 2023). demonstration project supports
It promotes sustainable energy at local decarbonisation of the gas sector and has
level, network investment and a strong EU the objective to show the value of power-
Emissions Trading Scheme [2]. to-gas as a smart gas grid technology that
enables power accommodation as
Power-to-gas (P2G) is considered to be synthetic methane, which is used by
such an enabling technology, to support households in Rozenburg, a city in the
the integration of renewables [3]. Power- municipality of Rotterdam.
to-gas as a technology to provide flexibility
to the energy system or to generate low 2. Technology description
carbon gas is currently heavily debated in Power-to-gas is the functional description
relation to the energy transition and is of the conversion of electrical power into
considered to be a new and innovative a gaseous energy carrier like e.g. hydrogen
technology. and/or methane [3]. The production chain
of power-to-gas in this project consists of

55
electrolysis and chemical methanation.
Electrolysis of water is the separation of
water into oxygen and hydrogen using an
electric current. Methanation is the
process of generating methane (and
water) from a synthesis process of
hydrogen and carbon dioxide.
The facility scale (7 KWe and 2.3 kWmethane)
and environment in this project enables Figure 2. Schematic overview of the P2G
demonstration of the entire production project in Rozenburg
change of power conversion into gas that
is immediately distributed and delivered Dutch gas quality (table 1) needs to be
to domestic appliances for local heating ensured continuously in order to comply
and cooking in 30 apartments. to the gas quality standards set by the grid
Alternatively, in periods that the gas operator. To ensure gas quality
demand capacity of the end users drops compliance, after the methanation
below the actual production capacity, process CO2 is added to the product gas
synthetic methane is injected in the local (synthetic methane) to be compliant for
natural gas distribution grid. Figure 1 grid injection.
indicates the gas demand profile of the
apartments over one year. Table 1. Relevant gas quality specifications
Specs.
Wobbe-number [kWh/Nm3] 12.25 –
12.34
CO [%-mole] < 0.1
H2 [%-mole] < 0.1
CO2 [%-mole] < 10.3
H2O dewpoint [oC @ 8 barg] < -10

The main engineering challenge in the

exothermal methanation process is
Figure 1. Load demand curve for gas related to the heat balance. The maximum
operating temperature (MOT) limits the
In this project, a commercially available heat load generated by the exothermic
Hogen S40 PEM electrolyser is used. The catalytic reaction. Operation at low
chemical methanation process consists of (<200oC) temperatures might support the
different commercially available formation of toxic nickel carbonyl, while
components and specific nickel-based operation at high temperatures (>700oC)
catalytic material with different nickel stimulates the formation of tar. To control
contents. Solar-PV is used as a power heat loads, the methanation process
source, although during off-peak hours consist of four catalytic reactors in which
electricity is obtained from the local water is separated from the gas stream
power grid. Carbon dioxide is currently after each reactor. The reactors are filled
obtained from bulk and meets high quality with catalytic materials with different
standards. A schematic overview of the nickel-loads to ensure that the MOT value
P2G project in Rozenburg is given in figure is not exceeded. Theoretically, to have an
2. optimal balance between the hydrogen

56
conversion ratio (for gas grid compliance) The largest amount of the input mass is
and energetic energy (for economical converted into water.
motives) the ideal operating temperature
of the entire system is 377oC [5]. Energy balance methanation
The energy balance shows that, in general
3. Mass and energy balances continuous operation and ensuring gas
The P2G pilot facility is equipped with quality compliance, 53% of hydrogen is
mass flow meters, thermocouples and converted into methane. Approximately
pressure transducers. The collected data 47% of the (thermal) energy is not utilised
has been used to calculate mass and in the system and is wasted.
energy balances in continuous base-load
operation. All figures given in this chapter
are obtained during continuous base-load
operation, aiming to meet the gas quality
standards. Therefore an input ratio of
1:3.8 is used for H2:CO2, to have an excess
CO2 and therewith realize the highest Figure 4. Energy balance of the
hydrogen conversion rate and the lowest methanation facility
hydrogen content in the product gas.
Within the gas quality boundaries, the gas
Mass and energy balance electrolyser energetic efficiency is 59%, which means
For the PEM electrolyser, the mass that 41% of the hydrogen is converted into
balance shows that 0,944 kg of water is thermal energy, due to the exothermal
converted to 0,098 kg hydrogen. High character of the methanation reaction.
quality water is needed to ensure systems
reliability to split into hydrogen and 4. Results
oxygen. The energy balance shows that For continuous compliance of the Dutch
45% of the electricity is converted into gas quality standards for gas grid injection,
hydrogen, meaning that roughly 55% of the efficiency for methanation is slightly
the (thermal) energy is currently not lower in comparison to the theoretical
utilised in the system. value (71-82%), see figure 5.

Mass balance methanation

The mass balance of the methanation
facility shows a high conversion ratio of
hydrogen in general continuous operation.
Only trace of carbon dioxide and hydrogen
are present in the output gas. Figure 5. Energy balance of the entire
power-to-gas system

The low allowance levels for hydrogen

injections required high conversion ratios,
which is energy intensive for the system.
As an integrated system, including
electrolysis and methanation, the total
Figure 3. Mass balance of the methanation energy efficiency is 24%. Further system
facility optimization is needed to increase energy
efficiency, for example by using a thermal

57
energy stream. Considering the entire 6. Potential future outlook
system, 6.5 kW is thermal energy. This For adopting power-to-gas technologies,
could potentially be utilised locally, qualification and verification of integrated
although there is currently a lack on heat power-to-gas systems in operational, real
infrastructure in Rozenburg. life environments is required to improve
on the technology readiness and is crucial
During continuous operation, gas quality for facilitating possible further market
compliance is ensured using gas penetration. Therefore risk based
chromatograph and specific gas sensor engineering guidelines are required for
measurements. Carbon monoxide levels this technology, rather than based on
are below the detection limit and economics or performance only.
hydrogen levels are marginal within the
gas quality specifications. Over the time, The project in Rozenburg will potentially
the output gas quality was quite constant extended with connections to other
and low CI’s are obtained for CO2 and infrastructures to close (life)cycles and to
Wobbe-number, see table 2. utilize (energy) product streams like heat,
water and carbon dioxide in the most
Table 2. Relevant gas quality output sufficient ways. Although, this requires
parameters, before CO2 blending high quality product streams, like water
Average 95% confidence and carbon dioxide. In a broader
value interval (CI) perspective, there is a potential for setting
Wobbe- 12.32 0.047 up a low carbon autonomous energy
number system in Rozenburg in which the P2G
[kWh/Nm3] facility in Rozenburg can potentially play a
CO [%-mole] 0 - central role.
H2 [%-mole] 0.003 0.009
CO2 [%-mole] 10.02 0.102 7. References
[1] European Commission; the climate and
5. Conclusions energy package. Online:
Because of the required gas quality http://ec.europa.eu/clima/policies/
package/12-5-2014.
compliance for grid injection and the
[2] SER (2013) Energieakkoord voor
exothermal character of the chemical duurzame groei (energy agreement for
methanation reaction, high hydrogen sustainable growth).
conversion ratios need to be achieved, at [3] Grond, L., Schulze, P. and Holstein, J
the expense of energetic efficiencies. (2013) Systems analyses Power to Gas: A
Since there is a strong focus on gas quality technology review. DNV KEMA Energy &
compliance, the energetic efficiency of the Sustainability.
methanation is 53% and far below [4] Grond, L., Holstein, J (2014). Power-to-
theoretical maximum efficiencies. The gas: climbing the technology readiness
total energy efficiency of the system may ladder. Gas for Energy. Issue 2/2014.
be increased, by using exothermic heat. [5] Holstein, J., van der Steen, A.S., Grond, L.
and Vlap, H. (2015) Power-to-gas
demonstration project in Rozenburg. DNV
GL Oil – Gas. Not published yet.

Figure 6. Both considerate approaches for

methanation facility operation

58
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Experiences of catalytic methanation : contexts of P2G concept and

biomass-based processes
Anne-Cécile Roger1, Sébastien Thomas1, Audrey Waldvogel1, Myriam Frey1, Sandra
Capela2, Jérôme Nguyen2, Guilhem Roux3, Geneviève Geffraye3, Alain Bengaouer3, Arnaud
Lahougue4
1 ICPEES UMR CNRS 7515, University of Strasbourg, Strasbourg, 67087, France.
2
CRIGEN, GDF-SUEZ, 361 avenue du Président Wilson, 93211 Saint Denis La Plaine, France.
3
CEA LITEN DTBH, 17 rue des martyrs, 38054 Grenoble, France.
4
ENERCAT, 9 rue Galilée, Parc Technologique de Soye, 56274 Ploemeur, France.

1. Introduction strongly affects the CO conversion where-

The reaction of CO methanation was first as the CO2 conversion is less diminished
investigated to purify H2-rich streams for (less exothermic). For CO methanation,
ammoniac synthesis. Since the 60s this increasing temperature leads to a de-
reaction aimed to produce Synthetic crease of methane selectivity: up to 20 %
Natural Gas from coal through various of selectivity to carbon is obtained around
types of processes based on coal 500°C, whose deposition on the surface
gasification [1]. More recently the carbon leads to strong deactivation of the
source shifted from coal to biomass or CO2 catalyst. In the case of CO2 methanation,
(carbon recycling), leading to important the formation of Csurf is not favoured
changes in the processes. The catalysts thermodynamically. Increasing the
used for the methanation of CO/CO2 equilibrium temperature decreases the
mixtures or for pure CO2 methanation are methane selectivity to the benefit of CO
generally not specific despite the fact that production.
different mechanisms CO/H2 and CO2/H2
may occur, allowing the development of
efficient catalysts for such applications.
These materials may also be of high
interest for the current development of
Power to Synthetic Natural Gas (SNG)
technologies where the strong penetra-
tion of intermittent renewable energies
can be achieved through the storage/
reuse of SNG produced by CO2 (industrial
waste) hydrogenation (from water electro- Figure 1. Equilibrium CH4 yields versus
lysis from electricity overproductions). temperature for CO and CO2 methanation

2. Thermodynamic equilibria It is clear that catalysts efficient to

The methanation of CO2 leads to similar produce durably methane from CO or CO2
CH4 yields as that of CO (see Figure 1) [2]. have to present different features:
Behind these apparent similar behaviours, resistant to C formation (CO methanation)
very different phenomena occur. At or inactive for Reverse Water Gas Shift
isopressure, an increase of temperature (CO2 methanation).

59
3. Mechanism sintering of Ni particles. It can be
The CO methanation proceeds through CO prevented by controlling the physico-
and H2 dissociation on metal particles (Ni chemical properties of the materials.
or Ru) and subsequent hydrogenation of
Csurf. Since the adsorption of CO is
100
favoured compared to that of CO2, the
methanation of CO/CO2 mixtures will first 90

CO2 conversion (%)

produce methane from CO and only when
80
the CO partial pressure will be low enough - 6%
(bottom of the catalytic bed) CO2 would 70 - 14%
be dissociated on metal particle to be - 24%
60
transformed into methane through the
same pathways [3]. 50 - 34%
We recently proposed that CO2 can be 40
efficiently converted into methane using 0 50 100
catalysts whose support oxide phase really Time (h)
participates in the CO2 activation [4]. The Figure 3. Evolution of the CO2 methanation
mechanism is presented in Figure 2 at the activity versus time on stream for various
end of this abstract. The metal sites Ni-ceria-based catalysts
exhibit much higher activity than those of
conventional catalysts (developed for CO 5. Methanation in the context of P2G
activation) due to the bi-functional nature In the case of France, the development of
of the material, the CO2 activation renewable sources electricity is presented
occurring on the oxide surface in the near in Figure 4.
vicinity of metal sites (available for
hydrogen dissociation).

4. Catalytic results for CO2 methanation

and stability
The intrinsic activity of the Ni-ceria-based
catalysts for CO2 methanation can be
controlled by modifying the oxide support
composition (positive effect of zirconia)
[5]. Moreover, their stability under
reaction can be tuned by modification of
the physico-chemical properties (surface
area, porosity) at a given composition [6].
As an example, Figure 3 displays the
evolution of CO2 conversion at 350 °C, 1 Figure 4. French energy mix up to 2050.
bar, stoichiometric conditions CO2/H2,
GHSV=43000h-1, for various Ni-ceria-based As a consequence, large overproductions
catalysts. of electricity are expected: 3.8 TWh in
The deactivation is not due to the 2020, 14 TWh in 2030 and up to 75 TWh in
accumulation of carbon onto the catalyst 2050 (these evaluations can differ from
surface, neither to a reoxidation of the one scenario to another). These global
metal phase under the reaction figures hinder the large diversity of local
conditions, but is mainly due to the specific cases.

60
To valorise these overproductions and Some catalysts (industrial CO methanation
store the excess of electricity via SNG catalyst and specific catalysts for CO2
injection in the gas grid, the P2G concept methanation) have been studied under
offers various technologies [7] (Figure 5). the different reactive mixtures. The results
show that for CO-CO2 co-methanation, the
materials designed for CO2 methanation
are much more efficient that industrial
catalysts, specifically at low temperature
(see Figure 6).
The ageing of the catalysts under the
various mixtures will also be discussed. It
could be one of the key factors for
choosing among the various possible P2G
technologies.

6. Conclusions
Efficient and stable catalysts can be
designed specifically for CO2 methanation.
Figure 5. P2G technologies. A reaction mechanism different from that
of CO methanation on conventional Ni-
Depending on the technology of electro- alumina allow their use for the conversion
lysis (pure water, water-CO2 co-electro- of CO/CO2 mixtures without competitive
lysis) and the way it will be operated, adsorption on the metal active sites.
various types of mixtures can feed the The materials exhibit best catalytic results
methanation reactor : CO2/H2, CO/H2 than conventional catalysts for CO
(reverse water gas shift unit between methanation, especially at low reaction
electrolysis and methanation), CO/CO2/H2 temperature, and could be of interest for
(partial coelectrolysis). P2G processes.
The way they deactivate under the various
reactive mixtures can help the decision for
choosing among the various possible P2G
technologies.

7. References
[1] J. Kopyscinski et al. Production of
synthetic natural gas (SNG) from coal and
dry biomass - A technology review from
1950 to 2009. Fuel 89, 1763-1783 (2010).

[2] J. Gao et al. A thermodynamic analysis of

methanation reactions of carbon oxides
for the production of synthetic natural
gas. RSC Advances 2, 2358–2368 (2012).

[3] S. Eckle et al. What drives the selectivity

Figure 6. COx conversion versus temp-
for CO methanation in the methanation
erature over various catalysts. Reaction of CO2-rich reformate gases on supported
conditions: P = 1 atm, stoichiometric Ru-catalysts ? Applied Catal. A 391, 325-
H2/(CO+CO2) ratio, GHSV = 50 000 h-1. 333 (2011).

61
[4] P.A. Ussa Aldana et al. Catalytic CO2 [6] M. Frey et al. Effect of physico-chemical
valorization into CH4 on Ni-based ceria- properties of ceria-based supports on the
zirconia. Reaction mechanism by carbon dioxide methanation reaction.
operando IR spectroscopy. Catal. Today Adv. Chem. Letters 1, 257-263 (2013).
215, 201-207 (2013).
[7] C. Bouallou, Le stockage d’énergie –
[5] F. Ocampo et al. Effect of Ce/Zr Conversion d’énergie en gaz combustible,
composition and noble metal promotion Presse des Mines, ISBN : 978-2-35671-
on nickel based CexZr1-xO2 catalysts for 204-2 (2015).
carbon dioxide methanation. Applied
Catal. A 392, 36-44 (2011).

Figure 2. Mechanism of CO2 methanation on Ni-ceria-zirconia catalysts.

62
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Methanation technology and planned activities within the SYNFERON

project
Niels Bjarne K. Rasmussen1, Ioannis V. Skiadas3, Hariklia N. Gavala3
and Georgios M. Kontogeorgis2
1 Danish Gas Technology Centre, Dr Neergaards Vej 5 B, 2970 Hoersholm, Denmark
2 Technical University of Denmark (DTU), Department of Chemical and Biochemical Engineering,
Søltofts Plads Building 229, 2800 Kgs-Lyngby, Denmark
3 Aalborg University Copenhagen, Section for Sustainable Biotechnology, A C Meyers Vaenge 15,

2450 Copenhagen SV, Denmark

1. Introduction 2. International co-operation

Gasification of biomass and production of SYNFERON brings together three compe-
syngas (synthesis gas, a mixture of H2, CO2, tent academic research groups from two
CH4 and CO) results in very high (over Danish universities, one technological
90%) conversion efficiency. However, consultancy and development company in
syngas is not suitable for storage and/or the area of energy gases, one company
use in the transportation sector and is not and one SME in the separation process
compatible with the natural gas grid. The area, one German gasification company
SYNFERON project (Optimised SYNgas and a US academic partner expert in
FERmentatiON for biofuels production) biomass gasification and syngas fermenta-
will run from 2015 to 2018. It aims at the tion. It is expected that SYNFERON
development of a new technology objectives combined with the consorti-
platform, which optimally combines um's skills ensure that the project results
thermochemical and biological processing can bring Denmark in the forefront of
of biomass. This is based on biomass energy production from thermochemi-
gasification followed by fermentation of cal/biological processing of biomass,
the produced syngas to biofuels by internationally.
microorganisms producing alcohols or
methane (synthetic natural gas, SNG). The 3. Objectives of the project
ultimate scope is a complete design which SYNFERON will advance the existing
will include highly efficient biomass knowledge on the challenging aspects of
gasification, low-cost fermentation syngas fermentation and separation
processes, advanced product separation process. In brief, the technological focus
and purification technology, process and scientific objectives within SYNFERON
analysis and optimization as well as are:
comparison to competitive market 1) Fermentation of syngas to liquid
technologies. In this way, SYNFERON (alcohols) and gaseous (methane) biofuels
provides a significant contribution to the focusing on innovative fermentation and
promotion of technologies that can be reactor technologies
used in the production of fuels and natural 2) Use of advanced separation methods
gas from renewable sources such as for gentle and cost-efficient purification of
biomass and waste. liquid biofuels

63
3) Development of an optimized process with very low content of molecular
design and comparison with existing nitrogen and, therefore, it is expected that
technologies. its bio-methanation will result in produc-
tion of synthetic natural gas, SNG5-7, which
Figure 1 shows a schematic representation will be allowed to be injected in the grid.
of the project and the work packages. However, the bio-methanation of syngas
also faces mass transfer limitations and in

Figure 1. The link between work packages and a schematic representation of the project

4. The methanation part of the project combination with the low growth rate of
Limited attention has been paid so far to methanogens it results in very low
the fermentation of syngas to CH4 (bio- conversion rates4.
methanation). It is well known that mixed
cultures of anaerobic bacteria and Therefore, the selection of an appropriate
methanogenic archaea convert CO, CO2 bioreactor configuration that could
and H2 into CH41-3. The main biochemical overcome mass transfer limitations and
reactions may take place simultaneously achieve high cell density is important for
leading to a final efficiency of 0.25 mole of efficient syngas fermentation. The most
CH4 per mole of CO plus 0.25 mole of CH4 commonly used bioreactor configurations
per mole of H2. Depending on the syngas reported for conversion of syngas to
composition this may result in an impres- ethanol include conventional stirred tank
sive 0.4 m3 CH4 per kg of organic solids bioreactors, bubble columns, membrane
gasified4, which corresponds to a 75% reactors, trickling bed reactors and moving
conversion efficiency. Finally, the microor- bed biofilm reactors. SYNFERON focuses
ganisms performing the above mentioned also on overcoming rate limitations by
conversion of syngas are massively designing and testing a novel reactor
available in environments like waste/ configuration as well as by controlling the
wastewater treatment processes. They pressure or adding surfactants in the
come, therefore, at no cost and they are fermentation broth.
already adapted to harsh conditions4.
With low N2 content, the produced CH4 Syngas from gasification consists of a
rich gas will be fully compatible with the mixture of H2, CO2, CH4 and CO. In existing
existing natural gas grid. To date, there is chemical methanation plants, a part of the
extensive experience concerning thermal CO of this mixture is first shifted to H2 in a
gasification of biomass in Denmark, but “Shift”-reaction to convert the energy in
the produced syngas has a relatively high CO into H2. When sufficient CO is shifted,
N2 content. The gasification technology the mixture of H2, CO and CO2 is converted
(Agnion Energy GmbH), which will be by thermal methanation to CH4, CO2 and
applied in SYNFERON, produces syngas

64
H2O. The CO2 and water are removed, and After a first cleaning of syngas from a
the remaining CH4 is bio-SNG. thermal gasifier, the gas consists of a
mixture of CO2, CO, CH4 and H2.
These processes can be done by biological
processes instead of chemical/thermal Next, the gas is brought to the first
processes. A study of fermentation reactor, in which CO is converted into any
processes shows that some microbes are mixture of CO2, H2, CH4 and acetate by any
able to convert CO and water to a mixture of the microbes (hydrogenogens, meth-
of H2 and CO23,8. This process is exergonic, anogens and/or acetogens), which can do
and the microbes use that energy for their this work as fast as possible and typically
reproduction. This biological process could at temperatures in the range of 30-70°C.
be called a “biological shift” reaction.
From here, the gases (with only traces of
A combination of this “biological shift” CO) are led to the next reactor, where the
reaction with processes known from the H2 and a part of the CO2 as well as acetate
anaerobic digestion (AD) could form a full are converted into CH4 by methanogens,
biological methanation process for which is a process, present in well-known
converting producer gases from thermal anaerobic digestion.
gasification to bio-SNG. Figure 2 shows in
a diagram an example of the method of The final result is a well-known biogas (like
bio-methanation. biogas from digestion) with only CH4 and
CO2, which can be upgraded into bio-
methane by conventional methods.

Figure 2. Diagram of a bio-methanation method for producing bio-SNG from thermal gasifica-
tion gas (syngas)

65
5. Expected advantages of the bio- [7] Svensson H, Tunå P and Hulteberg C
methanation process (2013) Svenskt Gastekniskt Center (SGC)
The resulting gas will be conventional report 277
biogas and by that subject to subsidies in [8] Barik S, et.al. (1988) Biological Conversion
of Coal Gas to Methane, The Human
parallel to conventional biogas plants. The
Press Inc., 379-392
gasification plant will act as a “thermal
pre-treatment” of the biomass before the
fermentation in the bio-shift and bio-
methanation reactors.

This method is expected to have several

advantages compared to thermal
methanation:

x The methanation unit is less sensi-

tive to changes in syngas concen-
trations
x Easy shut-down and start-up (the
microbes just sleep and wait
dormant for a new start-up)
x The unit could be made both small-
and medium-scale (perhaps large-
scale)
x The output is conventional biogas
x Small footprint for the methana-
tion unit
x Low-priced?

6. References
[1] Henstra AM, Sipma J, Rinzema A and
Stams AJM (2007) Current Opinion in
Biotechnology, 18(3), 200-206
[2] Wise DL, Cooney CL, Augenstein DC
(1978) Biotechnology and Bioengineering,
20(8), 1153-1172
[3] Oelgeschlaeger E and Rother M (2008)
Archives of Microbiology, 190(3), 257-269
[4] Guiot SR, Cimpoia R and Carayon G (2011)
Environmental Science & Technology,
45(5), 2006-2012
[5] Henriksen U, Ahrenfeldt J, JensenTK,
Gobel B, Bentzen JD, Hindsgaul C and
Sorensen LH (2006) Energy, 31(10-11),
1542-1553
[6] Ahrenfeldt J, Henriksen U, Jensen TK,
Gobel B, Wiese L, Kather A and Egsgaard
H (2006) Energy & Fuels, 20(6), 2672 –
2680

66
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Catalytic methanation – the Audie e-gas project as an example of

industrialized technology for power to gas
Gregor Waldstein1
1 ETOGAS GmbH, Germany

1. Introduction shares of volatile renewables into energy

In the presentation ETOGAS shows, how markets at low costs. It makes it possible
the technology of today inside the world to generate electricity at some point of
wide largest ptg plant of audi, with 6
time somewhere and to sell it in the form
MWel, functions and enables commercia-
lized solutions for different stage of of synthetic fuel anywhere and anytime.
industrialized, reliable ptg plants. The PtG facilitates this by creating a
conversion process starts with alkaline connection between the two large existing
electrolysis for dynamical, intermittent energy networks, the power grid and the
operation mode. It follows the fixed bed gas grid with its ample storage and
bundle reactor of methanation of the transport capacity and by continuous
generated H2 with CO2 from biogas
recharging of the gas grid without
scrubbing plant to a synthetic natural gas,
SNG. The system is also operated in timing/technical restrictions.
dynamical mode. The balance of plant In the presentation it will reported about
including all necessary ancillary systems, the technology and project road map, with
the behavior in different power purchase
close to 7MWel installed capacity. In detail
mode will be presented. Also the gained
experiences to improve the technology in it will be presented the utilization of
their different steps toward a cost pressurized high efficiency electrolyzers
reduction pathway for the near future for the production of hydrogen for
industrial markets (green raw material)
2. Technology description and automotive applications (green fuel
PtG is a disruptive technology for building
for FCEVs); and fixed bed methanation
a smart energy ecosystem based on
systems for the production of SNG as a
renewable sources and allows the conv-
green fuel for gas-powered vehicles and as
ersion of volatile renewable electricity into
a feedstock cost optimizer for industrial
durable renewable synthetic gases (H2 or
processes. ETOGAS’ proprietary tech-
SNG), methanol which have an low carbon nology is specifically designed for the
footprint and can be stored, transported requirements of volatile renewable
and eventually commercialized in mobility electricity supply: minimized technology
markets (as green synthetic fuels) and in risk and costs (capex and opex), highest
industrial markets (as green raw material). conversion efficiency and full dynamic
Ptg adds flexibility to energy systems and intermittent operation. The presented
thus enables efficient integration of high technologies for the industrialization are

67
pressurized alkaline electrolyzer tech-
nology: world’s largest cell stack capacity
(300kWel; 62.5Nm3/h Hydrogen) and an
active area per cell (6,000cm2) that is 2-3x
large than usual. Methanation technology
with patented fixed bed plate reactor-
membrane concept allowing for conv-
ersion efficiency consistently at the
theoretic maximum (83%), high gas quality
(up to 99 Vol% CH4) on low standard nickel
catalyst consumption as well as for high
tolerance to the use of a variety of CO2
sources and for integrated reactor cooling
with steam and avoiding hot spot
problems due to high heat transfer
coefficients.
3. Conclusions
Examples of concrete realized projects like
the audi ptg plant, for hydrogen, SNG and
also the use of CO2 as a feedstock for real
hardware production by incorporating
methanation technology will be shown.

68
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Developing the Biomethane Market in Brasil: The Dois Arcos Case and
the Regulatory Challenges
Marcio Schittini and Marilyn Hahn
1 Ecometano Enterprises, Rio de Janeiro, Brasil

1. Introduction of over 6km of vertical and horizontal

Brazil is an enormous country with over collectors built of HDPE, mounted with
200 million people, abundant natural leachate pumps and regulated to collect
resources, a fragile residue treatment gas at <0.2%O2 and <1%N2 ratios.
culture and a superior energetic
consumption history.

Biogas is an up-and-coming energy

resource and its energetic use is yet in
early stages. Biogas insertion into the
energy matrix in Brazil has merits both as
a propeller of the distributed electricity
generation model, as well as biomethane
injected into the grid and used for fossil
fuel replacement.

The Dois Arcos RNG is a first of its kind (in

Brazil) LFG-to-pipeline project, and the
Biogas collected is shipped to a treatment
early stages of its development have
plant (maximum capacity of 1,200m3/h)
supported the development of a
based on a pressurized water scrubber
regulatory agenda involving biogas.
integrated to a process water treatment
plant, an electric substation, an electric
2. The Dois Arcos RNG Project
chiller, a CNG compression and pumping
Located in the Northern Region of the
station and a complete supervisory
State of Rio de Janeiro, in the city of São
system.
Pedro da Aldeia (located within a 2-hour
drive from the city of Rio de Janeiro), the
project collects biogas from the Dois Arcos
landfill and is planned to inject
biomethane into the local natural gas
distribution pipeline located 3.8km away.

The project begins at a biogas collection

system that’s been operating for 2 years at
a 70% collection efficiency history. Setup
in a small-scale landfill (average 700tpd of
MSW), the collection system is comprised

69
Biomethane distribution was projected for
delivery by 3 different modals:
x Local CNG for vehicle fuelling
x Fuelling of CNG trucks for off-site
delivery
x On-site pipeline injection

Current regional demand for natural gas

as vehicular fuel is superior to the
projects’ production capacity, so is local
residential, commercial and industrial
natural gas consumption. Early assump-
tion was that the Project would have no
trouble commercializing the Biomethane 3. Regulatory Framework
produced. While the project was been built, the Rio
de Janeiro State Government issued the
State’s Renewable Natural Gas
Programme, which mandated the natural
gas distribution companies to acquire up
10% of the natural gas they purchase from
available renewable natural gas produced
in the State. The Dois Arcos project is the
first project aimed at exercising the States
Programme.

Although each State is responsible for

However, the inexistence of a proper deciding suppliers and what they are
regulatory framework made it impossible allowed to inject into the distribution
to sell fuel at the regional gas stations. pipelines, the Federal Regulator decided
to intervene and create a federal
Thus, in the meantime, while regulatory Biomethane Programme.
discussions are underway, the Dois Arcos
Project has been experimentally testing Ongoing regulatory procedures have led
the use of urban-based biomethane for to the “birth” of biomethane as an
industrial and vehicular use with large approved fuel nation-wide (even if at this
success, becoming a platform for the stage this only concerns to agriculture-
development of the biomethane market in based biomethane) and will lead to the
Brazil. approval for injection of urban-based
biomethane after there is consensus of a
normalised procedure for proper sampling
and analysis of contaminants.

A thorough discussion on exactly what

sampling and analysis methodologies to
normalise for siloxanes testing and what
VOCs to monitor are current discussions.
Looking at the European Regulatory

70
efforts (Biogasmaxx), and the EPA’s latest
research on biomethane, Brazil is moving
to discuss a contaminant monitoring
procedure in urban-based biomethane
that will tend to elevate renewable natural
gas’ status to a superior fuel.

4. Results
The Dois Arcos Project has been a market
development platform that has achieved:

x Development of 3 State Program-

mes focused on the development
of the local biomethane market
x The “Biomethane Group” was
formed in 2013 by the National
Petroleum and Biofuels Regulatory
Agency seeking to establish a
biomethane-specific regulation
x R-ANP 08/2015 – the BIOMETHANE
norm (even if only for agriculture-
based biomethane) issued in Jan
2015 establishes biomethane as a
regulated fuel
x Commercial supply to both indu-
strial and vehicular applications

5. Conclusions
The Dois Arcos Project marks the birth of
the Brazilian biomethane market.

It’s the first gasp of a market estimated to

be able to supply over 20 million m3 per
day of renewable natural gas from both
agriculture (digester-based) and urban
sites (landfill based).

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Feasibility of renewable natural gas (RNG) projects, an international

overview.
Eberhart Wusterhaus Gomez1
1 International Business Manager, Schmack Carbotech GmbH, Natorpstraße 27, Essen, Germany.

1. Introduction cultural, solid and liquid organic waste) or

The biomethane industry is picking mom- through elements which can be recycled
entum in different countries around the to avoid losses in resources.
wold, demonstrating its high potential and
diversity of applications. While the main The RNG generation currently requires a
gas components do not really differ, no treatment to achieve same conditions as
matter the origin of its generation, the the fossil natural gas utilized in the
feasibility of its generation will have a industry. This could involve the CO2, CO,
major impact according to the location, O2, N2 reduction, drying it and removal of
the political views and the local resources. contaminants.

This paper gives an introduction of the The CO2 and CO reduction can simply be
international experiences gathered by the filtration and separation from the gas
Carbotech while developing projects stream or a further methanation process
worldwide, advising the possible future with the hydrogen element.
perspectives in the industry and the
expectation on how a biomethane project 3. Feasibility Overview
is feasible, moreover: self-sustainable fully Basically, the main factor which will define
integrated in the public utility sector. the value of the RNG it is directly linked to
the local resources used for its generation.
2. Technology description
The process for renewable natural gas The current established technologies are
(RNG) production is based on the focused on achieving the highest effici-
generation of methane through a chemical ency with the lowest possible utility
or biological process basically derived consumption; therefore the operational
from elements such as hydrogen and expenses should generally define the
carbon based compounds. Most typical attractiveness of turnover on healthy
non-natural occurrence processes are projects.
through the anaerobic digestion and
gasification of biomass, however emerging The capital investment of the technologies
technologies like the power-to-methane for its production and processing will have
process is capturing the attention of the a major impact but in most of the cases
industry. this should not be the major driver of the
RNG production price.
When specifically referring to renewable
natural gas, the sources of its production The sale price of the RNG has been
can be understood as biomass (agri- incentivized in many countries; nonethe-

72
less it is important to recognize that
political views for supporting the
developing of these technologies are only
considered in a short term base. Con-
sequently it is imperative to find solutions
and opportunities which will provide a
self-sustainable business delivering the
maturity to this industry being accepted as
a reliable energy source sector.

4. Conclusions
Based on the diverse business models
executed in different countries, the key for
a successful industry relies on the recovery
and recycle of sources usually classified as
waste or rejected for primary use.
Furthermore, it is important that the
concept to be implemented is effectively
integrated in established infrastructures
presently operated in the municipalities.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Experiences from Sweden´s largest biogas plant, Jordberga

Pia Ekelund1
1 Production support/biogas technichan, Swedish Biogas International, Linköping, Sweden

1. Introduction Jordberga Biogas produces 110 GWh of

methane per year, which corresponds to
Swedish Biogas International [1] is a
11.7 million Nm3 vehicle fuel. The raw
privately owned company that owns and
material (substrate) is mainly locally
operates biogas plants and offers
produced crops and other agricultural
complete process and production solu-
waste and by-products. In addition to
tions for biogas. We operate in an
biogas is produced a high quality digestate
international market with the main focus
which is returned to the region´s
on Sweden and Northern Europe. We have
agriculture. This closes the cycle of
vast experience in co-digestion with many
nutrients and replaces large amounts of
different substrates, and broad expertise
mineral fertilizers.
on various technical solutions.
Vehicle fuel is the main use of the biogas,
but Jordberga Biogas is also the first
supplier of biogas into the Swedish natural
gas grid, and thus we get in an efficient
and environmentally friendly way access
to a larger market, including industries
who want to use biogas.

Figure 1. Facility map, SBI

Jordberga Biogas is Sweden’s largest

biogas plant and is located on an old sugar
mill area near Malmö in the south of
Sweden. The plant is co-owned and
Swedish Biogas International is the Figure 2. The Swedish gas grid on the west
majority owner. SBI has driven the project coast
from start and now operates the facility. Picture: Swedegas [2]

74
2. Technology description We use a air purification equipment,
MEGTEC [4], which burn hydrocarbons.

3. Mass and energy balances

Raw material in 100,000 tons per

year

Water in 70,000 tons per year

Biogas out 110GWh/11,7Nm3

per year

Digestate out 170,000 tons per

year

Reduced carbon 28,000 tons per year

dioxide emissions
Figure 3. Jordberga Biogas

Digestion Technology 4. Ownership and investment

The digestion process is anaerobic, meso- Swedish Biogas International 55 %

philic CSTR- Continuous Stirred Tank E.ON 20 %
Reactor. The temperature is 38oC and the SB3 20 %
HRT-Hydraulic Retention Time, is about 60 Nordic Sugar 5 %
days. The digested sludge is used as
Total investment; 22.5 million euro.
digestate.
Jordberga Biogas was commissioned in
Gas upgrading system
April 2014 and the first gas was delivered
The gas is led from the digesters to the gas in July 2014.
upgrading system, a water scrubber,
5. References
Malmberg COMPACT® [3], where carbon
dioxide and hydrogen sulphide is [1] Swedish Biogas International
separated. Before the gas is delivered to www.swedishbiogas.com
the pipeline propane is added to achieve
natural gas quality. [2] Swedegas
www.swedegas.se
RTO- Regenerative Thermal Oxidizers
[3] Malmberg Water AB
The residual gas coming from the gas www.malmberg.se
upgrade contains impurities that should
not be released directly into the air, such [4] MegTec
as hydrogen sulphide and methane. www.megtec.com/oxidizers

75
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

State of the art biomass gasification for CHP production – the Ulm plant
Friedrich Kirnbauer1, Frank Maierhans2, Matthias Kuba1 and Hermann Hofbauer3
1 BIOENERGY 2020+ GmbH, Location Güssing, Wienerstrasse 49, 7540 Güssing, AUSTRIA
2 SWU Energie GmbH, Karlstraße 1-3, 89073 Ulm, GERMANY
3 Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna

AUSTRIA.

1. Introduction Villach/Austria. The plant in Ulm/Germany

Electrical energy produced from biomass which went in operation recently is twice
may make redundant partly the randomly the size (15 MW thermal power) of the
produced electricity from wind and plants before. Further scaling up of the
photovoltaic materials because biomass is process is carried out in the GobiGas Plant
stored by nature and can be utilized by in Gotenborg/Sweden (32 MW thermal
proper technology with varying energy power) where the same DFB gasification
loads at any time. technology is used but the product gas is
A proven technology for the utilization of further used for the synthesis of BioSNG.
woody biomass for electricity generation The plants in Güssing and Oberwart are
is biomass steam gasification in a dual operated with wood chips with the origin
fluidized bed (DFB) gasifier. In this process, of residual wood from forestry. It is
biomass is gasified thermally and the delivered mainly as log wood and chipped
product gas is used in a gas engine to at the plant.
generate electricity and heat. Various The plant in Senden is operated with
studies are ongoing for the utilization of logging residuals such as cut-off root ends,
the product gas to produce fuels for and tops and branches and even
transportation [1,2], making the driftwood from hydro power plants. This
technology even more suitable for usage fuel is cheaper and easier to access at the
and electricity production with different middle European market but it is higher in
loads depending on the demand of the ash content and inorganic material such as
consumers. The polygeneration of stones and sand. Due to the decentral
electricity, fuels and heat is considered to chipping (mainly by forest industry) the
be more efficient for the utilization of particle size distribution and water
biomass and higher profits can be content varies heavily.
generated compared to single-product
plants [3]. Biomass gasification is 2. Technology description
described as a key technology for the A basic flow sheet of the plant is shown in
reduction of greenhouse gas emissions Figure 1. Biomass is fed into the gasifier
using polygeneration technologies [4]. via a screw system and is gasified in a
The DFB steam gasification process was bubbling bed at around 850 °C using
developed by the Vienna University of steam as a gasification agent. Bed material
Technology and the first industrial scale also containing char is transferred to the
installation went in operation in 2002 in combustion zone, where char is
Güssing/Austria. Later plants were built in combusted in a fast fluidized bed at
a similar size such as Oberwart/Austria or around 930 °C. Air is used for fluidization

76
in the combustion zone. The bed material coke is burnt in the combustion zone.
is separated from the flue gas in the After the separation of the particles from
cyclone and transported back into the the product gas in the product filter, the
gasifier, providing the heat for the gas is washed in a rapeseed methyl ester
gasification. The flue gas is further cooled (RME) scrubber to remove water and tars.
down and the fly ash is separated in the The cleaned gas is then utilized in a gas
flue gas filter. engine to produce electricity and heat. A
The product gas is cooled down after small amount of the product gas is used to
leaving the gasifier and particles are control the temperature of the
separated from the gas stream in the combustion zone.
product gas filter. The fly coke from the Olivine is used as bed material due to its
product gas filter contains inorganic catalytic properties to reduce tar content
matter such as biomass ash, additives, and in the product gas. Inorganic matter enter
products of bed material abrasion as well the system not only with bed material but
as unconverted char and tar. To utilize the also as biomass ash, inorganic pollutants
remaining combustible substances, the fly

Figure 1: Basic flow sheet of the DFB process in Ulm

3. Methods to evaluate the performance

from the wood chips (such as stones) and of the plant
additives prior to the product gas filter or Mass and energy balances are updated
directly into the gasifier. Inorganic matter recently to evaluate the operation of the
is removed from the process via the flue process. Mass balances were also carried
gas filter and the coarse ash removal. out for single species such as nitrogen.

77
Due to the fact that the wood chips which thermal nitrogen oxides which may
were used in the plant in Senden contain exceed the local regulations for the
an inorganic fraction of stones and sand, a emissions of nitrogen oxides in the flue
deeper investigation on the influence of gas of the gas engines. This was avoided at
this inorganic matter on the catalytic the plant in Senden with the installation of
activity and the influence on the a SCR in the flue gas after the gas engine.
fluidization was carried out. The formation of thermal nitrogen oxides
Inorganic matter was analysed using SEM- could not be detected in the combustion
EDX analyses of micrographs of used bed reactor or in the auxiliary boiler where
material. Therefore the samples were product gas is burnt.
mounted in epoxy, grinded and polished. Bed material interaction with biomass ash
The elemental composition was measured Logging residues contains more low
using x-ray fluorescence (XRF) analysis. melting species in the ash compared to log
wood biomass. With the utilization from
4. Results logging residuals in the plant in Senden a
The results indicate the operation layer formation at the bed material is even
conditions within the year 2014 and early more severe than described by Kirnbauer
2015. The efficiencies and key figures are et al from the plant in Güssing [5].(see
summarized in Table 1 (status early 2015). Figure 2). This leads to the risk of fouling
and bed material agglomeration especially
Table 1. Key data and efficiencies
at locations of high temperature in the
Unit Values reactor (e.g. combustion reactor).
Fuel Logging residuals
Fuel power MW 16,5
Electrical power MW 4,8
District heating kW 6,67
output
Electrical efficiency % 29
Thermal efficiency % 41
Overall efficiency % 70
Chemical efficiency % 77
of the gasifier
Bed temperature °C 823
gasifier
Figure 2. Bed material with layer [5]
A focus at the mass- and energy balances It is described in literature [6] that the
was driven to mass balances of impurities formation of a layer at the bed material
such as nitrogen but also inorganic matter. has positive influence on the catalytic
Nitrogen balance activity of the bed material concerning tar
Low quality woody biomass contains high reduction in the product gas. This is in
nitrogen contents (~0,4% dry substance) contrast to the risk of fouling and bed
The results of the nitrogen balance material agglomeration. By the application
showed that around 50 - 65% of the of a bed material management at the
nitrogen which is bound into the fuel is plant in Senden, the risk of fouling and
available in the product gas as NH3. During bed material agglomeration was
the utilization of the product gas in the gas minimized and the impact on the
engine, ammonia is converted also to availability is minor.

78
The influence of bed material modification reaction schemes can be evaluated e.g.
and inorganic matter on gasification the water gas shift reaction and the
properties decomposition of tars respectively.
Inorganic matter is brought into the
process with the biomass. This inorganic 5. Conclusions
matter is in the case of the plant in Senden The experience at the plant in Senden
not only biomass ash but also contains showed that the operation with logging
stones and sand. These pollutants have residuals is possible with minor impact on
the disadvantage that they might dilute availability and efficiency. A high content
the bed material concerning catalytic in nitrogen compounds in the fuel makes a
activity on the one hand and influence the reduction in nitrogen oxides after the gas
bed material size distribution and the engines necessary to fulfil the regulations
fluidization properties of the bed material of Germany.
on the other hand. Besides, this inorganic A consequent control of inorganic streams
matter can interact with bed material and such as bed material, ash and pollutants
biomass ash. Table 2 shows the (stones, sand) is essential for successful
composition of bed material which was in operation.
operation in the plant (particle size smaller Inorganic matter in biomass (stones, sand)
than 1 mm) and coarse grains (particle size have minor negative influence on the
> 1 mm). Operational experience showed gasification process
that a consequent removal of the coarse Efficiencies higher 30% are possible also
particles (>1 mm) below 8% of the total for low quality wood.
bed material mass is required to insure
constant operation. 6. References
[1] Rehling, B.; Hofbauer, H. In ICPS 09 – Int.
Table 2. Bed material and coarse grain Conf. on Polygeneration Strategies; Self-
composition published: Vienna, Austria, 2009.
Bed Coarse grain [2] Rauch, R.; Hofbauer, H.; S c reanu, S.;
material (> 1 mm) Chiru, A. Bulletin of the Transsilvania
University of Brasov, Series I, Engineering
wt-% wt-%
Sciences 2011, 3.
Fe2O3 13,93% 2,81% [3] Chen Y, Adams TA. Barton PI. Optimal
CaO 14,88% 15,27% design and operation of static energy
K2O 1,18% 3,37% polygeneration systems. Ind. Eng. Chem.
SiO2 29,10% 68,55% Res. 2012, 50, 5099–5113.
Al2O3 0,10% 7,56% [4] Wetterlund E, Söderström M. Biomass
gasification in district heating systems –
MgO 38,44% 0,72%
The effect of economic energy policies.
others 2,38% 1,73% Applied Energy 2010, 87, 2914–2922
[5] Kirnbauer F, Hofbauer H. Investigations
Research activities are ongoing concerning on bed material changes in a dual
the influence of the inorganic matter and fluidized bed steam gasification plant in
bed material interaction on the Güssing, Austria. Energy Fuels 2011, 25,
gasification properties and slagging, 3793–3798
fouling and bed material agglomeration. [6] Kirnbauer F, Wilk V, Kitzler H, Kern S,
For the evaluation of the catalytic Hofbauer H. The positive effects of bed
properties of bed material a lab scale test material coating on tar reduction in a
rig is used. In this test rig the influence of dual fluidized bed gasifier. FUEL 2012, 95,
the bed material on different chemical 553–562.

79
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Industrial scale gasification of agricultural and forest residues using

EQTEC gasifier technology coupled to IC engines
Luis Sánchez Angrill 1
1 CEO EBIOSS Energy & EQTEC

1. Introduction
EQTEC is an engineering company and 2. - Gas cleaning system, where synthesis gas is
technology provider, integrated in the filtered and conditioned according requirements
EBIOSS Energy Holding (MAB:EBI). The of equipment, which is going to use it as fuel.
headquarters of the company are located in
3. - Syngas generator set, where syngas is conv-
Barcelona (Spain) with branches in Bulgaria
erted into electrical power by means of an IC
and Italy and representative offices in more engine and a coupled alternator.
than 20 countries.
2. Technology description
Industrial scale gasification has been a A bubbling fluidised bed gasifier is
reality for many years. Coupling this generating syngas of enough quality to
technology to the use of syngas in IC design a simple syngas purification system.
reciprocating engines in CHP plants has been As a result an efficient and economical plant
a challenging process now developed is producing clean syngas used as fuel in IC
successfully by EQTEC. engines, generating electricity and heat with
a total efficiency of up to 80%.
An Integrated Biomass Gasification Power
Plant (IBGPP) is fuelled with solid biomass, Syngas composition and characteristics
which is converted into gas, so called depends upon biomass type used as fuel.
synthesis gas (syngas) or more commonly Typical LHV is 4.5 – 5.5 MJ/ Nm3 and typical
wood gas. This gas has a certain heating chemical analysis is shown in Table 1.
value, and once conditioned, is used as fuel
in internal combustion engines. When Table 1. Typical syngas composition.
syngas is used in engines, these engines ELEMENT % VOLUME
move an alternator, generating electricity CO 15-19%
and at the same time engines generate heat,
H2 8-14%
in the form of exhaust gases and hot water
CH4 3-5%
from the cooling circuit. This heat could be
CO2 10-15%
used to produce hot water, hot air, and hot
water or even chilled water for air N2 47-55%
conditioning purposes. O2 1-2%
CmHm 0.1-2%
IBGPP is divided into three main areas.
The gasification technology developed has
1. - Gasifier reactor, where biomass (organic demonstrated its reliability using the
matter) is converted into gas, with low heating feedstocks mentioned, solving the problems
value of 4,500-5,500 KJ/Nm3. related to low ash melting point, high alkali

80
metals content in ashes and high chlorine The most significant data is the running
levels. period of MOVIALSA project. This plant has
achieved 40,000 accumulated running hours
3. Advantages of the technology in the three IC engines it has, with regular
The process has proven a major advantage maintenance as scheduled by the manu-
in biomass power plants including District facturer (GE Jenbacher). No big shut-downs
Heating networks or CHP application. or repairs have been experienced in the
gasification island.
The technology of biomass gasification in a
bubbling fluidized bed has great advantages: 5. New developments
New projects are under construction and
9 Integrated Waste Gasification Power development in France, UK, Croatia, Dubai
Plant (IGPP) from 1 MW to 25 MW. and Thailand.
9 High electrical efficiency (26-34%)
9 High global energy efficiency - up to 80% The company is also deploying its
9 Modular power plants gasification technology using SRF/RDF as
(1,200–3,000-5,000-10,000 kW) feedstock.
9 Ultra low emission technology
9 Multi-fuel plant.
9 Simple and safe operation and
maintenance, having accumulated inside
the gasifier very little fuel.
9 Higher mechanical reliability, having no
moving mechanical equipment inside the
gasifier.
9 Reduced operational inertia, allowing a
start / stop comparatively short.

4. Experiences Figure 1. RDF Gasification power plant.

Four main projects have been delivered by
EQTEC using its gasification technology with
agricultural and forest residues as a
feedstock:
x 5.9 MWe plant in MOVIALSA (Spain),
using olive pulp and grape bagasse as
feedstock.
x 1.0 MWe plant in SYNGAS ITALY
(Italy), using wheat straw as
feedstock.
x 1.5 MWe plant in KARLOVO BIOMASS
(Bulgaria), using wheat straw,
manure and forest residues as
feedstock.
x 1.5 MWe plant in HEAT BIOMASS
(Bulgaria), using wheat straw,
manure and forest residues as
feedstock.

81
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Experiences of operating the world’s first industrial scale bio-SNG

facility, GoBiGas.
Malin Hedenskog

Göteborg Energi AB, Gothenburg Sweden.

1. Introduction pressurised to 35 bar and transferred to

The Gothenburg Biomass Gasification the transmission grid in which it can be
Project (GoBiGas) started already in 2005 distributed to all customers who are
aiming at converting forest residues to interested in “green gas”.
bio-SNG. In this work several conversion
paths were considered and evaluated 3. Mass and energy balances
before the final solution was decided. Now GoBiGas aims at proving an exceedingly
a demo-plant in industrial size is finalised. high efficiency rate of transforming 65% or
A dual fluidised bed gasifier has been more of the energy contained in the forest
used, in combination with an advanced residues into bio-SNG. By utilising the
methanation technology, to produce bio- plant’s waste heat in the district heating
SNG, which is mainly used as a high quality grid of Gothenburg, the total efficiency of
transport fuel in Sweden. Now the plant is the plant will reach 90%.
in operation since December 2014.
The GoBiGas project aims at proving that
bio methane can efficiently be produced
in large amounts utilising forest residues.
By successfully running the plant 8,000
hours per year, 160 GWh of bio methane
will be injected into the natural gas grid
annually. This is enough to fuel 16,000
cars that drive 17,000 km/year.

When calculating the environmental

footprint and emissions of greenhouse
gases it can be shown that this pathway,
converting forest residues with high
Figure 1. GoBiGas production process efficiency (gasification) to high quality
transport fuel (CNG or LNG), gives very
2. Technology description low emissions compared to other biofuel
By choosing dual bed (indirect) gasification alternatives.
it is possible to produce SNG with high
methane content and low nitrogen 4. Operational experiences
content without using oxygen. After Total operational hours of the gasification
gasification the synthesis gas is cleaned process were in March 2015 about 3000
from tars, sulphur, carbon dioxide and hr in total. During the first period, high tar
upgraded to 95% methane. The SNG is content caused severe clogging of the

82
syngas cooler and continuous operation of 5. Evaluation
the gasification was limited. After careful The GoBiGas demonstration plant is partly
investigation of the bed material and financed by public funding and the
syngas cooler deposits, the conclusion was operation will thus be evaluated during a
made that wood pellets contains very 7-year period to make the results public.
small amounts of ash components. Those
components seem to be crucial to activate 6. Conclusions
the bed material and accordingly reduce Several studies during the last 10-15 years
tar levels. Decision was made to add have shown promising environmental and
certain amounts of alkali to the gasifier energy efficiency data for bio-SNG
and the gas composition improved production by gasification of forest
dramatically. residues. Now the time has come to test
the performance in practice. Hopefully the
Table 1. Gas composition after the gasifier performance data from the GoBiGas-
project will create the final approval of the
Component Vol%
technology not only theoretically but also
H2 39-42 in real life!
CO 23-25
CO2 20-24
CH4 8.5-10

Increased availability of the gasifier made

way for start focusing on the methanation
process. First delivery of biomethane to
the grid was achieved on December the
15th, 2014.

Table 2. Gas composition to the gas grid

Component Vol%
CH4 96.5-97.5
N2 0.6-0.8
H2 2
CO2 0-0.5
Parameter kWh/Nm3
HH value 10.8
Wobbe index 14.6

Initially wood pellets have been used as

raw material. A fuel handling system for
forest residues is under construction and a
switch over from pellets to forest residues
will take place in the beginning of next
year.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Biomethane in Sweden – statistics and perspectives

Jörgen Held1
1 Renewable Energy Technology International AB, Skarpskyttev. 10D, SE-226 42, Lund, SWEDEN

1. Introduction own district heating system. In 2012 49.9

In Sweden the utilization of upgraded TWh heat was delivered through district
biogas as vehicle fuel is increasing rapidly heating (excluding distribution losses).
and the use of biogas has surpassed
natural gas in the transportation sector1. 3. The electricity production
This paper will give a background to this In 2012 the total electricity production in
development and explain why there is Sweden amounted to 161 TWh out of
such a strong focus on using biomethane which 20 TWh was exported. The electri-
in the transportation sector in Sweden. city production is to a large extent de-
The development will be highlighted in carbonised due to the high share of
terms of production capacity, number of nuclear power, hydro power and biomass
filling stations, number of natural gas and based power and CHP production, and
biogas powered vehicles as well as the hence there is no gain in terms of carbon
amount of sold volumes. The driving dioxide mitigation to replace any of these
forces behind the development will be with electricity produced from bio-
discussed together with the biogas methane.
potential and future prospects, such as
production biomethane through gasifi- Table 1. Electricity production in Sweden
cation and methanation of lignocellulosic 2012.
feedstock. Production [TWh]
Hydro power 78
2. The energy supply
In order to understand the Swedish bio- Wind power 7
methane development it is important to Nuclear power 61
take the total energy supply into Industrial back pressure 6
consideration. In 2012 the total energy CHP 9
supply to Sweden amounted to 598 TWh
out of which crude oil and oil products, 4. Development of natural gas and
coal and coke accounted for 186 TWh and biomethane as vehicle fuel
natural gas 12 TWh. The development started in 1995 when
the first public filling station for comp-
While the fossil fuels stands for 80% of the ressed natural gas was opened. 24 busses
global energy supply the share in Sweden and 20 passenger cars and light duty
2012 was less than half of that, or 33.1% vehicles were in operation that year.
to be exact. Due to the climate the need Upgraded biogas as vehicle fuel was
for heat is obvious and district heating is introduced the year after, in 1996. The
well established. In fact every city with development of biogas as vehicle fuel is
more than 10,000 inhabitants has their shown in Table 2 and 3.

84
Table 2. Development of biogas as vehicle fuel in Sweden (Source: Swedish Statistics)
2009 2010 2011 2012 2013 2014
Biogas as vehicle fuel 42.252 59.147 75.125 83.320 89.847 100.198
[million x Nm3]
Yearly increase 8.512 16.895 15.978 8.195 6.527 10.351
[million x Nm3]
Annual increase [%] 25.2 40.0 27,0 10.9 7.8 11.5

Table 3. The share of biogas used as vehicle fuel in Sweden (Source: Swedish Energy Agency)
2009 2010 2011 2012 2013 2014
Total biogas production 1,363 1,387 1,473 1,589 1,686 n.a.
[GWh]
Total biogas production 1,028 1,089 1,203 1,335 1,446 n.a.
excl. landfill gas [GWh]
Biogas sold as vehicle 410 574 729 808 871 972
fuel [GWh]
Share of biogas (excl. 40 53 61 61 60 n.a.
landfill gas) used as
vehicle fuel [%]

From Table 3 it’s reasonable to assume The number of public filling stations for
that the current share of biogas used as compressed natural gas (CNG) and biogas
vehicle fuel, 60%, is close to the upper (CBG) continues to grow and the
limit. This implies that the continuous development is shown in Table 5.
growth of upgraded biogas is dependent
on new additional biogas production Table 5. Number of public filling stations
capacity. for CNG and CBG in Sweden.

Most of the biogas produced in Sweden

comes from waste water treatment plants
and co-digestion plants. The distribution
between different plant types is shown in
Table 4.

Table 4. The biogas production in Sweden

2013.
Plant type [GWh]
WWTP 672
Co-digestion 580 At the moment there are 155 public and
Farm plants 77 63 non-public filling stations for CNG and
Industrial plants 117 CBG in Sweden. At 6 stations it’s possible
to fill liquefied natural gas (LNG) and/or
Landfills 240
liquefied biogas (LBG). There is currently
TOTAL 1,686 only one production facility for LBG in

85
Sweden. It’s the Lidköping plant with an The big biogas potential (~15 TWh)2 leys
annual production capacity of 60 GWh within the agricultural sector but today
LBG. just a small fraction of this potential is
utilized. Due to economic reasons and the
Table 6. Number of NGVs and sold amount food versus fuel debate energy crops have
of biogas and natural gas as vehicle fuel not been extensively used as substrate in
2014 (Source www.gasbilen.se). Sweden. There is a support scheme to use
manure as substrate and by building large
2014 scale plants such as Jordberga (annual
Passenger cars and light 46,975 capacity of 110 GWh biomethane) the
duty vehicles agricultural based biogas production
Heavy duty vehicles 812 capacity is expected to increase over time.
Buses 2,315
Power-to-gas is probably not an option in
Amount of sold biogas 100.289
Sweden since the intermittent power
[million x Nm3]
production is relatively small and the need
Amount of sold natural 58.482 for additional balancing power, besides
gas [million x Nm3] hydro power, is insignificant.

5. Discussion and perspectives The really big potential for biomethane

Since the biomethane market growth is (~59 TWh)2 leys within gasification and
hampered by the slow increase in the methanation of woody biomass. The first
biogas production there is a strong need step in this direction is the demonstration
for new production capacity. Basically taking place in Gothenburg where the
there are five ways to meet the growing world’s first industrial scale bioSNG plant,
demand for biomethane: GoBiGas, now is in operation.
x Import of biomethane
x Upgrade landfill gas and use it as There are plans to build a second GoBiGas
vehicle fuel plant3 with ~100 MWbioSNG capacity and
E.ON Sweden has at several occasions
x Increase the agricultural based
presented their Bio2G project involving a
biogas production
~200 MWbioSNG plant. However, for these
x Produce renewable methane
large scale facilities to be realized there
through Power-to-gas
have to be long term stable conditions and
x Produce biomethane through
political ambitions, policies and instru-
gasification and methanation of
ments in place to promote renewable
woody biomass
fuels in a transparent way.
Import of small volumes of biomethane
has been a reality for the last years but it’s Another option is to go for small scale
not seen as long term solution to the bioSNG plants (~10 MWbioSNG) and take
growing demand for biomethane. advantage of the latest development in
the fields of indirect gasification and
Since 2005 there is a ban to landfill organic catalytic tar reforming4. Small scale plants
material and hence the landfill gas are normally associated with higher
production is declining. Even if it’s specific investment and operating cost as
technically feasible to upgrade landfill gas well as lower efficiency. However, this
there are no initiatives in this direction. may to a certain extent be circumvented

86
by choosing technology adapted for small [3] Held, J. Gasification – Status and techno-
scale production. The low economic risk, logy. Swedish Gas Technology Centre,
the good possibilities to secure the 2012.
feedstock supply and integrate the excess
[4] Held, J. Small and medium scale bioSNG
process heat with the local heat demand
production technology. Renewtec Report
are strong reasons in favour of small scale
001:2013, ISSN 2001-6255. Renewable
production. Energy Technology International AB
(2013).
In a recent study5 the production cost for
small scale bioSNG has been shown to be [5] Held, J. and Wiklander, L. Småskalig
in a, for Swedish conditions, commercially förgasning. Renewtec Report 002:2014,
interesting interval, 70-130 cent/Nm3 ISSN 2001-6255. Renewable Energy
bioSNG with a methane content of 97%. Technology International AB (20014).

6. Conclusions
The strong development of biomethane as
vehicle fuel in Sweden is a consequence of
the de-carbonised power production,
ambitions to replace fossil fuels by
renewable alternatives and cut green-
house gas emissions.

There is an existing biomethane market in

Sweden and the need for new biomethane
production capacity is evident.

As a result of the ongoing development

demonstration plants for liquefied biogas
and biomethane through gasification and
methanation of woody biomass are now in
operation in Sweden.

The large potential for new biomethane

production capacity leys within gasifi-
cation and methanation of woody bio-
mass.

7. References
[1] Scholwin, F.; Held, J.: Biomethane from
Anaerobic Processes – Experiences and
Perspectives; in: Meyers, Robert A. (Ed.):
Encyclopedia of Sustainability Science and
Technology; Springer New York; ISBN 978-
0-387-89469-0; chapter 317 pp. 1-13

[2] Linné, M. Et al. Den svenska biogas-

potentialen från inhemska restprodukter.
Avfall Sverige, 2008.

87
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Renewable methane in France and Europe – an industrial perspective

Olivier Guerrini1
1 GDF Suez

NOT AVAILABLE AT THE TIME OF PRINTING

88
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Syngas production in sewage treatment plants: development of a

single catalyst for tar conversion and direct biogas reforming
M. Benito1, I. Ortiz1, J. M. Sánchez1, L. Rodríguez and G. Muñoz
1Energy Valorisation of Fuels and Wastes Unit. Energy Department. CIEMAT, Av. Complutense 40, 28040
Madrid, Spain

1. Introduction 2. Experimental
Anaerobic digestion of sewage produces a Catalyst synthesised was tested in a
biogas stream that can be valorised into microactivity equipment with a fixed-bed
methane and furthermore into hydrogen, tubular quartz flow reactor (3/8” o.d., 330
obtaining sludge as by-product. In order to mm length) operating isothermally and at
minimize the environmental impact, atmospheric pressure. Catalyst samples
sludge can be valorised into syngas or (200 mg, grain size of 0.42-0.50 mm for
hydrogen by gasification. Direct biogas dry methane reforming, and 1750 mg for
reforming is an optimal option opposite to toluene reforming with the same grain
gas separation in order to produce renew- size) were mixed with inert diluter (SiC) in
able hydrogen [1]. The key factor to apply 1:4 weight ratio.
this process is to develop catalysts with Biogas simulated stream consisted in 100
enough stability capable of overcoming mLN·min-1 with a CH4:CO2 ratio 1:1. In the
deactivation by coking. In the case of case of a simulated sewage sludge
sludge gasification, tar removal represents fluidised bed gasification, the composition
the main limitation for syngas valorisation of the gas stream was 11% H2, 48.1% N2,
due to produce corrosion and pipe 17.7% CO2, 3.4% CH4, 7.8% CO, 12.1% H2O
plugging. From this point of view, catalytic and 25 g·m-3 of toluene, being the total
tar conversion could be an environmental flow 105 mLN·min-1. Two types of reaction
friendly option opposite to thermal tar experiments were performed: conversion/
cracking, reducing the reaction tempera- products distribution vs. temperature, and
ture below gasification process, and there- vs. time at reaction temperature selected.
fore increasing the overall process energy The reaction products were analysed with
efficiency. Nevertheless, catalytic deact- an AGILENT 7890A chromatograph
ivation by coking is the limitation stage for connected on line and equipped with two
this technology. TCD and 5975C Mass detectors. Helium
was used as carrier gas.
Therefore, catalysts deactivation by coking
in both processes involved in sewage 3. Results
energy valorisation is the process to The figure 1 represents toluene
overcome. Taking into account than conversion, main products distribution
biogas and tar conversion processes and by-products concentration (tar) vs.
proceed with a similar reaction mech- time in a long-term up to 100 h
anism, a single catalyst to perform both experiment at 700 oC. Toluene conversion
processes was designed and tested. achieved 100 % in the time range studied.
It is important to note the great stability of

89
the catalyst performance. Complex tar electron microscopy and temperature
(by-products) produced by secondary programmed oxidation. The results
reactions were not detected. obtained revealed the lack of coke
110 deposits, responsible of catalyst
100
Toluene conversion (%)

90
deactivation, in good accordance with the
80 long-term reaction results obtained for
70
60 both processes.
50 100
40
30 80

Conversion (%)
20
60
Products distribution (d.b) (%)

55 00 60
10 20 30 40 50 60 70 80 90 100 110
50
45 40
40 H2 CH4
35 N2 CO2
20
30 CO2
25 CH4
20 0
CO
15 50 0 10 20 30 40 50 60 70 80 90 100 110

Products distribution (%)

10
5 40
0
8
H2
By-products concentration (g/m )
3

7 00 10 20 30 40 50 60 70 80 90 100 110 30
CO
6 CO2
20 CH4
5
H2O
4 10
Benzene
3 Toluene
2 Ethylcyclohexane 1.4
0
EthylBenzene 0 10 20 30 40 50 60 70 80 90 100 110
1
1.2
0
-1 1.0
00 10 20 30 40 50 60 70 80 90 100 110
X/Y

0.8
time (h)
XCH4/XCO2
0.6 H2/CH4
Figure 1. Long-term experiment performed H2/CO
0.4
on a gasification simulated stream. 0 10 20 30 40 50 60 70 80 90 100 110
time (h)
The catalyst was also tested in a biogas Figure 2. Long-term experiment performed
simulated stream in a long-term on a biogas simulated stream.
experiment (100 h) at 700 oC and W/F = 10
mg·min·mL-1. The figure 2 represents 4. Conclusions
methane and carbon dioxide conversions, The catalyst designed achieved total
products distribution and different ratios toluene conversion with the lack of tar as
vs. time. It is a remarkable fact the catalyst consequence of secondary reactions, and
performance stability. On one hand, equilibrium values for conversion in biogas
methane and carbon dioxide achieved the reforming process, showing a great
equilibrium values. Carbon dioxide stability in the endurance tests performed.
conversion was higher than methane Catalyst synthesised could be scale up for
conversion in all time range as a energy valorisation in sewage treatments
consequence of reverse water gas shift plants.
and reverse Boudouard reactions. On the
other hand, products concentration was 5. References
[1] Muradov, N., Smith, F. & T-Raissi, A.
maintained stable without signs of
(2008). Int. J. of Hydrogen Energy 33,
deactivation. Water was detected as 2023-2035.
reaction product as a consequence of [2] Hawkes, A. D. (2011). Tecno-economic
reverse water gas shift contribution, assesment of small and microcombined
favoured at high reaction temperature. heat and power (CHP) systems. Edited by
Post-reaction characterisation of spent R. B. (Ed.), pp. 60-68. Oxford: Woodhead
samples was performed by scanning Publishing Limited.

90
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Energy production during wastewater treatment through combination

of biogas production and microalgae culture

I. de Godos, Z. Arbib, R. Cano, E. Serrano, M. Fernández, F. Rogalla, Lamas, B. and E. Lara

FCC aqualia, Av. del Camino de Santiago, 40, edificio 3, 4ª planta, 28050 Madrid

1. Introduction effluents at Hydraulic Retention Time

The potential of biogas production in between 3 and 7 days depending on
wastewater treatment plants can be the season.
considerable increased if anaerobic - A harvesting unit consisting in
digestion is applied to sieved wastewater Dissolved Air Flotation (DAF) allowing
and microalgae are used as secondary for the generation of biomass with a
treatment instead of activated sludge. A concentration around 3-4% and final
demonstration unit based in Chiclana de la effluent of less than 30 mg Total
Frontera (South Spain) has been Suspended Solids/L.
developed to generate energy by - Laboratory algal digesters: two sets of
combination of anaerobic digestion with four identical continuously stirred
microalgae culture. The plant consists in tank reactors (CSTR), with 4 L each of
anaerobic pretreatment of the effective volume, fed with the
wastewater in UASB (Upflow Anaerobic microalgae from HRAPs and harvested
Sludge Blanket) reactors before with DAF system.
microalgae culture in HRAP (High Rate - An innovative up-grading and cleaning
Algae Ponds) (Fig.1). As the harvested and system using primary treated
concentrated algae biomass is digested, wastewater as absorbent for CO2 and
two biogas streams are generated which H2S.
can be cleaned and up-graded to obtain a
Biomethane
biomethane useful as fuel as final product. Effluent

2. Technology description
DAF

A pilot plant has been operated for more Wastewate

UASB HRAP Digestor
r
than 2 years in order to evaluate the
potential and strategies of operation. Up-grading
Energy and mass balance has been
calculated using the data collected in this
pilot plant consisting in: Figure 1. Diagram of the process develop-
- Three UASB (Upflow Anaerobic Sludge ed in pilot scale and projected for demon-
Blanket) reactors of 20 m3 each, fed stration
with municipal wastewater and
operated at HRT of 18 h. 3. Results
- Six HRAPs mixed by paddlewheels and The pilot plant has been optimized during
pH control through CO2 injection with 2 years of operation resulting in a high
a net surface of 32 m2 each and water quality of the final effluent with average
depth of 0.3 m, fed with UASB removals of nitrogen, phosphorous and

91
chemical oxygen demand of 60, 70 and registered with the number:
90%. It must be stressed that this EP15382087.3.
performance is achieved without aeration,
Considering that the biomethane prod-
thus the external inputs of energy are
uced along the process could be sold for
considerable lower than conventional
transportation in vehicles in a petrol sta-
treatment plants based on activated
tion, the overall process will result in an
sludge. Beside this, the significantly higher
energy producing treatment plant, with a
biomass production of this system and the
positive net energy balance of 0.5 kWh
higher conversion of organic matter to
th/m3 and generation of a final effluent
biogas, resulted in a complete different with very low levels of contamination.
scenario in terms of energy recovered.
Compared with a conventional plant with
The mass and energy balances calculated average consumption of 0.51 kWh el/m3
in the pilot units where used to scale-up
(equivalent to 1.53 kWh th/m3), the
and design a projected 10 hectare plant
demonstration unit not only consumes
(most of surface occupied by the HRAP
half the energy (0.74 kWh th/m3), but it
units) allowing for the treatment of 5,000
also generates an important biofuel
m3/day of wastewater (25,000 PE.). To
output of more than 100 L CH4/m3,
allow all biogas to be used as biofuel after
corresponding to 0.08 kg CH4/m3 of
upgrading, a biomass boiler that burns
wastewater, and would allow to run a
olive pits provides heat to the digesters
methane fuelled car around 2.8 km. This
and CO2 to the HRAPs. At this point it must
calculation was made on the basis that an
be pointed that the calorific values average consumption of the car model VW
considered to convert mass flows into Eco Up is 2.9 kg CH4 per 100 km.
energy flows were 4.65 kWh th/kg for
olive pits biomass and 11 kWh th/Nm3 for 4. Acknowledgments
bio-methane. A conversion efficiency of The authors wish to acknowledge the
33% has been adopted in order to support of the EU FP7 Programme
homogenize the results from thermal to ENERGY.2010.3.4 1: Bio-fuels from algae
electrical energy, considering a typical (Grant Agreement no. 268208) and the
conversion value from combined heat and Centre for Industrial Technological
power systems. Development (CDTI) of the Spanish
Ministry of Economy and Competitiveness,
A very low energy consumption in cleaning IDI-20141342
and up-grading of the biogas (0.05 kWh
per Nm3 of biogas treated) was reached in
a water scrubbing column using the
wastewater as absorbent resulting in the
generation of biomethane with a 87.5% of
CH4 concentration. The very low
concentration of H2S in the produced
biomethane 100 ppmv can be easily
removed in a polishing step with specific
absorbents at very low maintenance cost
since most of this contaminant is dissolved
in the wastewater (up to 98%). The
simultaneous cleaning and up-grading
system is patented by FCC aqualia and

92
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Thermo-economic and experimental investigation of small to

medium-scale integrated biomass gasification solid oxide fuel cell
systems
Stephan Herrmann1, Matthias Gaderer1 and Hartmut Spliethoff1
1 Lehrstuhl für Energiesysteme, Technische Universität München, Garching, 85748, Germany

1. Introduction
Table 1. Tar concentrations in g/Nm³.
High temperature fuel cells, such as solid
oxide fuel cells (SOFC) are amongst the Tar Typical Maximum
most efficient devices for conversion of compounds concentration concentration
gaseous fuels to electricity. At the same Phenol 1.19 5
time biomass is one of few renewable Toluene 1.50 5
energy sources which can, in contrast to Naphthalene 1.79 5
wind and solar energy, be used in a Flouranthene 0.11 0.25
reliable fashion, and even to balance other
non-reliable renewables. Thus, combining 3. Thermo-economic evaluation
biomass with SOFC by means of Complementary to the experimental
gasification offers a highly efficient, investigation concepts are studied in
reliable way of producing electricity thermo-economic simulations with the
without net CO2 emissions. In combination aim to achieve higher system efficiency,
with carbon capture and storage or usage increased flexibility, heat recovery and
(CCS/U) even a negative CO2 balance is lower costs.
possible.

2. Experimental investigation
Thus in the frame of the FCH-JU project
SOFCOM contaminant limits for integrated Gas cleaning

biomass gasification SOFC systems are Gasifier

Particles Tar ChlorineSulfur
studied experimentally by means of single Steam

cell testing with contaminant loaded

gases. The main focus of the research is H2O Heat- Pipes

the effect of tar compounds on SOFC

Anode
anodes, especially different tar classes SOFC
present in bio-syngas. Cathode
Experimental investigation is carried out
using a FUELCON Evaluator C1000-HT
Air
SOFC test station in combination with a tar
mixing station. The tar mixing station is Exhaust

capable of supplying variable mixtures of

tars in different concentrations. Typical Figure 1. Integrated SOFC heat-pipe
concentrations are shown in Table 1. reformer system

93
This is achieved by rigorous heat and 5. Conclusions
material stream integration. One system Based on the observations in this study it
example is shown in Figure 1, where an can be concluded that combined
SOFC is thermally integrated with a gasification SOFC systems are a promising
gasifier by means of heat pipes. The technology for highly efficient conversion
investigations are carried out using a of biomass to electricity. However, the
combination of ASPEN Plus and the technology is not yet mature enough for
Matlab based optimization algorithm commercial operation.
OSMOSE, which has been developed by
the Ecole Polytechnique Lausanne [1]. 6. References

4. Thermo-economic results [1] Gassner, M. and Maréchal, F.,

For an 8MWth feedstock system analogous Methodology for the optimal thermo-
to the scheme shown in Figure 1 the economic, multi-objective design of
thermochemical fuel production from
resulting optimized heat integration curve
biomass. Computers & Chemical
is shown in Figure 2.
Engineering 33 (3) , 769-781, 2009.

[2] Bundesministerium für Umwelt.

Naturschutz und Reaktorsicherheit:
Vergütungssätze. Degression und
Berechnungsbeispiele nach dem neuen
Erneuerbare-Energien-Gesetz (EEG) vom
04. August 2011 (‚EEG 2012’). Available
September 24th 2013 from:
http://www.bmu.de/fileadmin/bmu-
import/files/pdfs/allgemein/application/p
df/eeg_2012_verguetungsdegression_bf.
pdf
Figure 2. Q-T diagram for integrated
system

As can be seen from the figure almost all

available heat is used. Due to the
optimized heat integration the electrical
efficiency of the system rises to 49.5%
based on LHV of the feedstock.
However, the specific investment costs of
the systems under study do not yet fulfil
the constraint of economic viability. The
specific investment costs are still as high
as 15,925 $/kWel, mainly because of the
very high cost for the SOFC. Thus, not
even at high subsidy rates, for example
around 14ct/kWh for biomass based
electricity in Germany [2], the systems can
be operated commercially.

94
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Room temperature synthesis of synthetic natural gas using a catalytic-

dielectric barrier discharge (DBD) plasma reactor
Teresa Andreu1, Magdalena Nizio2, Inês Graça3, Katherine Villa1, M. Carmen Bacariza3,
Carlos Henriques3, Simeon Cavadias2, Jacques Amouroux2, Joan R. Morante1,4
1 Catalonia Institute for Energy Research (IREC), J. Dones de Negre, 1, 08930 Sant Adrià de Besòs, Spain
2 Université P. et M. Curie – Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005 Paris, France.
3 IBB, Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical Engineering,

Instituto Superior Técnico, UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
4 Electronics Department, University of Barcelona, C/Marti i Franqués, 1, Barcelona, 08028, Spain

1. Introduction peak is applied to the HV electrode. As

Chemical storage appears to be the most reaction take place at high temperatures,
suitable solution for storing large amounts exhaust gases are cooled in order to
of excess of renewable electrical energy, collect the liquid products. To analyze CO2
to face up the challenge of matching we use a specific detector, the other
power demand and production. In this gaseous products are analyzed by gas
context, CO2 hydrogenation to methane chromatograph, FTIR and mass
(Sabatier process) has recently renewed spectrometer. The condensable products
its interest, since CH4 can be stored and are collected for further analysis.
distributed safely in huge quantities
through infrastructures that are already in
place for natural gas (NG), solving the
issues related to a “hydrogen economy”.
The exothermicity of Sabatier reaction
leads to an increase of temperature,
requiring a good thermal management to
keep the reactor in the range of 300 to
400ºC, to avoid RWGS reaction and ageing
of catalyst.
In this context, catalytic-DBD plasma
process was sought to solve some
drawbacks by activating the process at low Figure 1. Experimental setup of catalyst-
temperatures and promoting water DBD plasma reactor
desorption on the catalyst for a higher
yield of the process. 3. Results
As the DBD reactor is working with the
2. Technology description catalyst activated by the generated
The DBD discharge reactor used (Figure 1) plasma, there are two working regions
in the experiments consisted of two (Figure 2). In the first one, the reactor
coaxial cylinders with OD 3mm and ID does not need extra heating supply and it
8mm. The Ni/(Ce+Zr) mesoporous based is working under adiabatic. So, the
catalyst is placed in the annular space (gap process starts at room temperature and as
of 2.5mm), its volume is 0.5ml. Sinusoidal the discharge increases the temperature
high voltage current around 14KV peak to due to the exothermicity, the process is

95
carried out until a new steady state is 4. Conclusions
reached, stabilizing the working point of In this work, it was showed that the
the reactor at this isothermal condition in catalytic properties of a Ni/(Ce+Zr)
the range of 130-160ºC depending of the mesoporous based catalyst are extremely
thermal conductivity of overall system enhanced and activated at room
including specially the catalyst. Here the temperature due to the interaction with
combination of nickel and ceria/zirconia the generated plasma using a DBD reactor.
play a basic role in the catalytic These characteristics allow the production
functionality, since classic nickel of synthetic methane with an interesting
supported on alumina or zeolite does not energy balance and catalyst life time to
show activation at low temperatures. facilitate better cost of the methane.
Under isothermal conditions, in the range Moreover, the presented technological
200°C-420°C, the reactor must be approach can be easily scaled up for a
externally heated for achieving these large production volume of synthetic
thermal values independently if plasma is natural gas production from reusing CO2
or not used. Nevertheless, better with a high throughput.
selectivity and conversion are achieved
always with plasma. 5. Acknowledgements
This work was supported by the
Under adiabatic conditions, at low Framework 7 program under the project
temperatures, selectivity close to 100% is CEOPS (FP7-NMP-2012-309984).
achieved for the production of synthetic
methane using 20% of CO2 and 80% of H2
with a CO2 conversion around 80-85%.
Under conventional conditions, selectivity
is maintained and conversion stays above
80% up to 300ºC. For higher temperature
conversion decreases a little bite although
the selectivity and conversion percentages
are always much better than without
plasma.

Figure 2. CO2 conversion using a Ni/(Ce+Zr)

mesoporous based catalyst

96
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

BIOGAS+. Enhancing anaerobic conversion of biomass and biogas

production by controlled dosing of iron to Archaea bacteria via
designed iron oxide nanoparticles.
Victor Puntes1
1 Applied Nanoparticles S.L, Barcelona, Spain

1. Introduction in a promising approach to the treatment

The conversion of biomass to biogas and of the increasing amount of biomass.
biomethane (CH4) is one of the possible
solutions to energy and environmental Biogas+ FeNPs act as a unique Fe source
problems that challenge the world today: because of their density, size and
decrease of fossil fuel reserves, global reactivity, especially in the anaerobic
increase in energy demand and the need methanogenic conditions of the reactor.
to improve the processing of organic
waste into a sustainable waste
management.
In addition, biogas production is presented
as a solution to the energy supply in
isolated areas of the grid. But despite the
obvious benefits, the current technology is
not powerful enough to significantly grow.
Besides, iron ions (Fe) are essential for life
of bacterial consortia responsible for the
degradation and transformation of organic
matter into CH4.

2. Technology description
The Biogas+ process consists on the
introduction of iron based nanoparticles
(FeNPs) in anaerobic digesters that
controllably provide Fe ions yielding to
accumulative biogas production boost
along with a significant increase of the CH4
content. This has been tested and
enhancements of biogas production up to
200% have been consistently observed.
This enhanced Fe induced metabolic
activity of methanogenic Archaea bacteria
implies both higher biomass processing
rates, less end-of waste digestate Figure 1. As synthesized Iron Oxide NPs
production and better quality fertilizer for (top) and Iron Oxide NPs in the digester
the same digestion periods, what results (bottom).

97
3. Results
The study shows that BIOGAS+ increase up
to 200% the production of biogas.

Figure 2. BIOGAS+ increasing biogas prod-

uction by 200%. Patent No. WO 2012/
123331 A1 (September 2011)

4. Conclusions
Biogas+ through improving conversion
efficiency will also enlarge the biomass
feedstock basis and improving the
economic, environmental and social
benefits relative to available biomass, and
therefore minimizing the demand on
natural resources, enhancing energy
balance, reducing GHG emissions (non-
processed CH4 is 20% of the GH) and
developing of rural areas where large
amounts of biomass are produced.

5. References
[1] Casals E., Barrena R., García A., Gonzalez
E., Delgado L., Busquets M., Font E.,
Arbiol J., Glatzel P., Kvashnina K., Sánchez
A. & Puntes V.F. (2014) Programmed iron
oxide nanoparticles disintegration in
anaerobic digesters boost methane
production. Small, 10 (14), 2801-2808

98
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Biomass gasification using pure oxygen instead of air

Alexander Bacq1, Thibault Andre1, Van Tuan Bach1, Frédéric Burgois1 and Jérôme
Partos1
1 XYLOWATT SA, R&D Department, Centre Monnet; Avenue Jean Monnet 1; 1348 Louvain la Neuve;

BELGIUM

1. Introduction Tests were realized on:

The NOTAR® gasification process has been - A pre-industrial gasification NOTAR®
validated as compatible with electricity reactor, with a capacity, when using air, of
production with a CHP engine. First 300 kg/h dry wood, corresponding to
generation industrial plants have now around 1 MW of LHV in the syngas
been operating for several years. The - A bench marking NOTAR® pilot plant
merit and demerit of using pure oxygen as reactor, with a capacity, when using air, of
oxidizer instead of air has been evaluated. 45 kg/h dry wood, corresponding to
This development program is selected and around 0,15 MW of LHV in the syngas
supported by the EU program Life +OxyUp
13 ENV/BE/000517. 3. Mass and energy balances (MEB)
Values from typical runs at the same
2. Technology description power with air and oxygen are shown in
Table 1 and 2. Those are neither optimal
nor mean values as explained in “4.
Results” section.

Table 1. Input and output flow

Using air Input flow Using Oxygen
40,3 kg/h Wood 47,6 kg/h
85,5 kg/h Air 24,8 kg/h
0 kg/h Oxygen 13,6 kg/h
Using air Output flow Using Oxygen
1,1 kg/h Ash 3 kg/h
3,1 kg/h Condensate 5,5 kg/h
131,7 kg/h Syngas 77 kg/h
Table 2. Parameters of MEB on test
Using air Parameter Using Oxygen
4595 kJ/Nm³ Syngas LHV 7652 kJ/Nm³
147,4 kW Power 155,4 kW
-10% Mass balance 0%
14% Energy balance 17%
80,58% Yield (cold, dry)1 70,89%
94,15% Yield (hot, dry)1 78,39%
Figure 1. Two chambers down draft fixed 1
= Power of syngas (based on LHV) / (total
bed gasification NOTAR® reactor. power of inputs)

99
Nota: these are spot data. Taking into - First generation industrial gasification
account the evaluated standard deviation, NOTAR® reactor, has a capacity, when
a difference of 8-10 % is not significant using Oxygen, of 600 kg/h of dry wood
Gas composition is continuously recorded (1 (instead of 300 kg/h dry wood when using
point / 5 sec) and gives LHV and power by air), corresponding to around 2 MW of
meaning. Gas flow rate are also continuously LHV in the syngas
recorded but solid/liquid flowrate are batch- - Bench marking NOTAR® pilot plant
weighted.
reactor, has a capacity, when using
Oxygen, 90 kg/h of dry wood (instead of
4. Results
45 kg/h dry wood when using air),
The inner pressure drop is a key operation
corresponding to around 0.6 MW of LHV
parameter and is directly related to the
in the syngas.
oxidizer flow rate. As with pure Oxygen for
the same quantity of entering total gas
5. Conclusions
volume, the oxidizer itself (O ) is doubled,
Based on the observations in this study
then gasification capacity of twice the
the following points can be confirmed:
biomass amount is confirmed.
- Oxygen as an oxidizer has been
confirmed as enabling stable operating
Table 3. Syngas optimal composition with
parameters. At moderated power, syngas
air as oxidizer
LHV almost doubled compared to air
gasification
- Within an identical gasification reactor,
biomass consumption can be increased
and even doubled compared to air
gasification, thus improving the economics
of the system

6. References
A second result is that, when using Oxygen [1] Milhé M, van de Steene L, Haube M,
instead of air only, the syngas content of Commandré J-P, Fassinou W-F and Flamant G,
Nitrogen is reduced. Consequently, the Autothermal and allothermal pyrolysis in a
syngas LHV is increased. Doubling capacity continuous fixed bed reactor. J. Anal. Appl.
(and power) was observed for tests at Pyrolysis, 2013. 103: p. 102-111
300kW with Oxygen. Then, general profile
of syngas produced using pure Oxygen [2] H. Jeanmart, F. Bourgois, A. Bacq, X.
would lead to Table 4 data: Kuborn., Impact of the pyrolysis quality on the
tar concentration in the syngas of a new low-
tar gasifier In : Proceedings of the 16th
Table 4. Syngas optimal composition with
Biomass Conference & Exhibition, Valencia,
Oxygen as oxidizer Spain, 2 - 5 june, 2008

100
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Green Gas by Gasification of Wet Biomass in Supercritical Water

Angela J. Kumalaputri 1,2, V. Hornillos 3, L. Carnaúba1, K. Krawczyk3, A. Kloekhorst1, B. L.
Feringa3, H. J. Heeres1
1 Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The
Netherlands
2 Department of Chemical Engineering, Parahyangan Catholic University, Ciumbuleuit 94, 40141 Bandung,
Indonesia
3 Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen,
Netherlands

1. Introduction 2. Technology description

Biomass is an attractive renewable source The experiments were carried out in a
for bioenergy and biofuels production and homemade batch reactor (14.2 mL, Fig. 1).
has attracted high interest in recent years. After loading with water, glycerol and
However, particularly the use of wet catalyst, the reactor was closed and
biomass sources still poses considerable placed in a temperature controlled
challenges and in most cases an expensive fluidized sand bath. After the desired
drying step is required before subsequent reaction time, the reactor was taken out
processing. A potentially very attractive the sand bath and was cooled in a second
conversion technology for wet biomass to, fluidized sand bath at room temperature
among others green gas, is the gasification for about 5-10 min.
in supercritical water (> 374°C, > 22.1
MPa). The major advantages compared to
anaerobic digestion, the currently used
technology for green gas production, are
much higher reaction rates (minutes
compared to weeks) and production of a
gas at high pressures, eliminating the use
of an expensive compression step [1,2].
Figure 1. Batch reactor set-up
The gas typically consists of CH4, CO, CO2,
H2, and trace of higher hydrocarbons, the 3. Mass and energy balances
exact composition being a function of the The gas samples were analyzed by GC-
process conditions and the type of catalyst TCD. The liquid samples were analyzed by
used. Glycerol was used as the biomass TOC analyzer to calculate the yield of CH4,
model component, though it may also be carbon to gas conversion, carbon
a viable biomass source as it is available in conversion, and the extent of char
large quantities from biodiesel production formation.
units [3]. In this study, the use of various
supported Ru and Ni catalysts as well as Mass balance
unsupported nanoparticles for the The carbon conversions are around 80-
synthesis of methane from glycerol in 90% for the Ru supported catalyst and less
supercritical water. than 70 % for the Ni supported catalyst.

101
4. Results Acknowledgement
The results for various supported Ru and The Energy Delta Gas Research (EDGAR)
Ni catalysts as well as for an unsupported program is acknowledged for financial
Ru catalyst are shown in Table 1. All support. AJK thanks the Indonesian
experiments were performed at the same Directorate General of Higher
condition: glycerol (10%-wt on water), Education (DIKTI) for a grant to perform a
10%-wt catalyst intake on glycerol at a PhD program at the University of
temperature of 400oC for 20 minutes Groningen.
reaction time.

Table 1. Experimental overview.

Catalyst Carbon to Glycerol CH4
gas conversion (%mol)
efficiency (%-wt)
(%-wt)
Ru/TiO2 79.8 84.4 48.9
Ru/C 82.1 89.7 33.1
Ru/Al2O3 64.7 80.2 43.7
Ru np 48.0 n.d. 34.3
Meth Cat (Ni) 54.0 65 25.7
Ni/ SiO2.Al2O3 53.3 67 16.2
Ni/ Al2O3 28.7 50.9 13.7

5. Conclusions
The best results were obtained using
supported Ru catalysts. Ru/TiO2 showed
good performance in batch with a carbon
to gas efficiency of 80%, and a gas phase
containing 49%-mol CH4. Also Ru
nanoparticles seem to have potential and
gave a gasphase with 34%-mol of CH4.

6. References
[1] J.G. van Bennekom; V.A. Kirillov; Y.I.
Amosov; T. Krieger; R.H. Venderbosch; D.
Assink;, K.P.J. Lemmens ; H.J. Heeres,
Journal of Supercritical Fluids, 2012. 70,
171–181
[2] Yun-Duo Long and Zhen Fang, Biofuels,
Bioprod. Bioref., 2012. 6, 686-702
[3] Elena Marko i ; Boris Kramberger; Joost
G. van Bennekom; Hero Jan Heeres; John
Vos; eljko Knez, Renewable and
Sustainable Energy Reviews, 2013. 23, 40-
48

102
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Application of a modular and interdisciplinary approach to the

development of a biological methane production (BMP) process
Sebastien Bernacchi1 and Christoph Herwig1
1Institute
of Chemical Engineering, Research Area Biochemical Engineering, Vienna University of
Technology, Gumpendorferstraße 1a, 1060 Vienna, Austria

1. Introduction
BMP process is a very promising 4th
generation biofuel process for upgrading
industrial waste gases containing hydro-
gen (H2) and carbon dioxide (CO2) to
methane (CH4) and water (H2O) [1].
However, BMP process is a tendentiously
gas limited bioprocess. Therefore, new
approaches are needed.

2. Technology description
The BMP process is centred on a Figure 1. Process efficiency simulation [3].
bioreactor where methanogenic archaea
stirred in the liquid phase are put in 3.2 Evaluating the use of real industrial
contact with H2 and CO2. The bioprocess is gases
performed in continuous operational The next module consists of methods
mode with a constant feed of nutrients maintaining gas transfer rate and reactive
and harvest of the reaction broth. Temp- gas fraction constant in order to evaluate
eratures and pressures belong to the the use of real industrial gases such as raw
range of mild operating conditions. biogas or syngas as feeds [4].
Methane Evolution Rates (MER) up to 950
mmolCH4*L-1*h-1 were achieved [2]. 3.3 Developing rational media

3. Modular approach for a BMP process

development
Our BMP setups are well described in
literature [2, 3, 4, 6,] with online balancing
and control strategies.

3.1 Evaluating BMP process efficiency

The first module proposed is the technical
analysis of the process. Overall process Figure 2. Sampling method for media
efficiency was simulated in ASPEN to quantification by ICP-OES [5].
estimate the influence of key process A feeding strategy was developed by rat-
parameters such as the dilution of ional media design based on physiologic
reactant gases or the compression energy. requirements. An ICP-OES method with

103
radial line-scans was developed for the full 5. Conclusions
quantification of media components. A modular and interdisciplinary approach
for developing gas fermentative bio-
3.4 Varying growth to product yield processes was presented. This approach
The last module consists of multivariate was applied for the establishment of the
DoE, univariate and dynamic experimental process conditions to apply for two
methods for screening multiple para- different applications of a BMP process.
meters influencing the growth to product CH4 was produced in the BMP process with
yield. a single bioreactor step at a MER of 132
mmolCH4*L-1*h-1 with a CH4 purity > 92
[Vol.%] both using raw biogas or under
intermittent process conditions.

6. References
[1] Martinez Porqueras, E, Rittmann S,
Herwig C (2012) Biofuels and CO2
neutrality: an opportunity. Biofuels 3(4):
413-426.
[2] Seifert AH, Rittmann S, Herwig C (2014)
Analysis of process related factors to
Figure 3. Variation of the growth to increase volumetric productivity and
product yield as function of CNH4+ [6]. quality of biomethane with Methano-
thermobacter marburgensis ApplEnerg
4. Modular approach application 132: 155–162.
The proposed approach was applied for [3] Bernacchi et al. (2014) Process efficiency
defining process conditions to apply for simulation for key process parameters in
two different applications of a BMP biological methanogenesis. AIMS bio-
process: engineering 1: 53–71.
[4] Seifert AH, Rittmann S, Bernacchi S, et al.
(2013): Method for assessing the impact
of emission gasses on physiology and
productivity in biological methanogenesis
Bioresour Technol 136: 747–751.
[5] Winfried Nischkauer, Sébastien Bernacchi
et al (2014): Radial line-scans as
representative sampling strategy in dried-
droplet laser ablation of liquid samples
Figure 4. Application of a BMP process in a
deposited on pre-cut filter paper disks;
power to gas intermittent scenario. SpectrochimicaActa Part B Atomic
Spectroscopy 11/2014
[6] Bernacchi et al (2014): Experimental
methods for screening parameters
influencing the growth to product yield
(Y(x/CH4)) of a biological methane
production (BMP) process performed
with Methanothermobacter marbur-
gensis, AIMS bioengineering Volume 1,
Issue 2,Pages: 72 - 86,2014
Figure 5. Application of a BMP process for
upgrading raw biogas.

104
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Effects of influent methane concentration on biogas upgrading and

biogas slurry purification under various LED light wavelengths by
using of microalgae Chlorella sp.
Cheng Yan1
1 School of Environmental Studies, China University of Geosciences, Wuhan 430074, Hubei, PR China

1. Introduction 7:3. Three monochrome LED light

The raw biogas always shows a very low wavelength control treatments were used
heating value because only a biogas CH4 using monochrome red, blue, and white
concentration higher than 90% meets the LEDs.
requirement of high-efficiency combustion The microalgae Chlorella sp. used in this
in burners or boiler units[1]. Chemical study was derived from the stock cultures
absorption, water washing, membrane kept in our laboratory, whose highly
separation, and pressure-swing adsorption biogas-tolerant characteristics have been
are the four methods usually used for confirmed. Three synthetic biogas
biogas upgrading[2]. However, these treatments were employed with influent
methods not only need large amount of CH4 concentrations of 45.21% ± 3.72%
energy, auxiliary materials, and chemicals (low), 55.46% ± 3.08% (moderate), and
but also generate waste and wastewater 65.92% ± 5.81% (high) in this research.
that can pollute the environment[3]. The biogas slurry came from a local
Moreover, the CO2 separated from the anaerobic digester. To prevent potential
upgraded biogas using the above- interference from other sediments and
mentioned methods is usually released microorganisms, the biogas slurry was
directly into the atmosphere[4]. pretreated using an ultraviolet sterilizer
This study focused on the performance of for 5 min and then filtered using a glass
biogas upgrading and biogas slurry microfiber filter (GF/C, Whatman, USA).
purification under various influent biogas
CH4 concentration and LED light 3. Results
wavelength (mixed and monochromatic) The biogas CH4 concentration of the
treatments using microalgae Chlorella sp. upgraded biogas (Fig. 1) increased during
in a photobioreactor. The optimal the experimental period. They were
parameters were determined by analyzing similar with those of the microalgae
the removal efficiency of the biogas CO2 growth shown. Only the treatment with
and biogas slurry nutrient. red:blue mix ratio of 5:5 achieved the
biogas grade required for combustion
2. Technology description with values of 91.94% ± 2.15%, 92.60% ±
A transparent polyethylene bag photo- 2.24%, and 91.65% ± 2.07% for the low,
bioreactor was used in this study. The LED moderate, and high influent CH4
used in this study was purchased from a concentration, respectively (Fig. 1). The
light company. Three mixed LED light low influent CH4 concentration treatment
wavelength treatments were performed achieved the highest biogas CO2 removal
with red:blue mix ratios of 3:7, 5:5, and efficiency, whereas the moderate influent

105
CH4 concentration treatment achieved the ATP), in power reduction (e.g., NADH), and
best biogas upgrading. Therefore, the LED as components for the backbone of the
light wavelength with the red:blue mix microalgae[5]. The microalgae can also
ratio of 5:5 under the moderate influent utilize the cumulative ATP from the
CH4 concentration was the most metabolism of organics in the biogas
appropriate treatment for biogas slurry culture during autotrophic
upgrading. metabolism as an enzyme activator[6].
100
Therefore, the microalgae CO2 removal
Biogas CH4 concentration (v/v, %) Biogas CH concentration (v/v, %) Biogas CH4 concentration (v/v, %)

a
red:blue = 3:7 efficiency was enhanced by the existence
90
red:blue = 5:5
of the biogas slurry.
red:blue = 7:3
80
In the mixed LED light wavelength
70
treatments, the photosynthetic efficiency
of the microalgae was enhanced by
60
simultaneously providing both red and
50
blue light wavelengths, which met the
entire wavelength ranges required by the
40

100
microalgae photosynthesis[7].
b
90 5. References
[1] N. Tippayawong et al. Biogas quality
80
upgrade by simultaneous removal of CO2
70 and H2S in a packed column reactor.
Energy 2010 35, 4531-4535..
60
[2] L. Deng et al. Techno-economic
4

50
evaluation of biogas upgrading process
using CO2 facilitated transport
40 membrane. Int. J. Greenhouse Gas
100
c Control 2010 4, 638-646.
90
[3] K. Raab et al. Innovative CO2 separation of
biogas by polymer resins: operation of a
80 continuous lab-scale plant. Eng. Life Sci.
2012 3, 327-335.
70
[4] R. Baciocchi et al. Regeneration of a spent
60 alkaline solution from a biogas upgrading
unit by carbonation of APC residues.
50
Chem. Eng. J. 2012 179, 63-71.
40
[5] S.C. Rittenberg. The roles of exogenous
0 24 48 72 96 120 organic matter in the physiology of
Time (h) chemolithotrophic bacteria. Adv. Microb.
Figure 1. CH4 concentration of upgraded biogas
Physiol. 1969 3, 159-196.
under mixed LED light wavelength treatments:
[6] E.C. Moore et al. Effects of
(a) low, (b) moderate, and (c) high influent CH4
arabinonucleotides on ribonucleotide
concentrations.
reduction by an enzyme system from rat
tumor. J. Biolog. Chem. 1967 242, 2116-
4. Conclusions 2118.
The accumulated materials from the [7] C. Yan et al. Influence of influent methane
metabolism of the biogas slurry nutrient concentration on biogas upgrading and
were utilized during the autotrophic biogas slurry purification under various
metabolism of the microalgae. Generally, LED light wavelengths using Chlorella sp.
they are used as energy sources (e.g., Energy. 2014 69, 419–426.

106
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Biolimp-Siloxa. Technology for biogas cleaning for its use as biofuel.

Joaquín Reina Hernández1
1 Department of biogas, Energy & Waste S.L, Terrassa 08221, Barcelona-Spain.

1. Introduction The aim of the work is describe the

technology Biolimp-Siloxa, its construction
The biogas is a gases mixture formed and its application for biogas cleaning, like
mainly by methane (CH4), CO2 and traces a multipurpose plant where are combined
of other components. The biogas has several removal techniques.
dangerous compound that should be
removal for its use as biofuel. For an 2. Technology description
adequate use of biogas as biofuel for
example in CHP-equipment or for In the biogas cleaning plant appearing
biomethane production, the biogas must different unit operations with the aim to
be cleaned to remove all the dangerous get a high biogas quality, among them,
compounds like water vapour, dust, cooling, washing, filtration, mist separator
particle, foam, siloxanes, H2S and heavy and adsorption on activated carbon.
hydrocarbon, all of them dangerous for
the useful life of the machine used for this All this operations allow removing water
application. vapour, dust, foam, siloxanes, H2S and
heavy hydrocarbon from the biogas with a
Currently appears two types of biogas high removal yield.
according its source.
The Biolimp-Siloxa technology account
Biogas from uncontrolled systems, that is, with different equipment, for example
is produced of natural way. For example energy recuperator, heat exchanger and
gas from landfills. This kind of biogas is adsorption filter on active carbon. The
characterized by the presence of moisture recuperator is an important part of the
(water vapour), siloxanes, halogenated technology, due to, allowing to minimizing
compound, heavy hydrocarbons and some the energy consumption and the same
cases hydrogen sulphide (H2S). time prepares the biogas for its inlet to
the active carbon filter.
Biogas from controlled systems, i.e.
anaerobic biodigestion process. In this In this manner is recovered around 10-20
case, both the process and the reactor can % of the energy for biogas cleaning or
be selected, as well as the operating more. This level of recovering depends on
conditions too. This kind of biogas is of the inlet biogas temperature and its
characterized by the presence of moisture flow.
(water vapour), siloxanes, hydrogen
sulphide (H2S), hydrocarbon, dust, foam By mean of this method is reduced, at the
and particle. same time, the amount of active carbon

107
for biogas cleaning, as well as is reduced efficiency for each component and the
the operation cost of the process. saving energy that it gets with the use of
energy recuperator.
Other important aspect is the vertical
position of the heat exchanger The table 1 shows the result of the
equipments which by its position improves practical application of Biolimp-Siloxa
the heat transfer coefficient and facilitates technology. Arico landfills, Tenerife Island.
drainage of the condensate. This avoids Spain
the possibility of water freezing inside the Table 1. Data from practical application.
tubes when the biogas temperature is low,
3
for example in winter season. Flow 3,000 Nm /h, Temp inlet 50 °C, Pressure inlet -200 mbar
Component Inlet Outlet Removal Energy saving
3 3
(mg/Nm ) (mg/Nm ) (%) (%)
This technology have been applied both to Siloxanes 38 <1 >97.3 21
landfill as the WWTP plant with good H2S 120 <1 >99.2
result in this both cases. BTEX 750 <5 >99.3
Hydrocarbons 3,957 <20 >99.5
o
Biolimp-Siloxa Technology Weight 10,000 kg, N . Filters 2, Lifespan 2 months, Cost 1.9 Φ/kg
Máquina de
refrigeración
aguaM10 ºC

E-3
T-2a T-1a

Raw biogas
3. Results
T-1g

Equipment
T-2g
M1 CHILER

E-2
M2 PUMP
E1 HEAT EXCHANGER
E2 RECUPERATOR
E3 AC FILTER
The major results of this project has been
Light Hydrocarbon

the developments of an integrated system

siloxanes + H 2S Instrument
T-4g T-3g Moist
Temperature
Pressure
Level

E-1
Know How
of biogas cleaning for producing a high
cleaning quality and introduce a new
Know How
Bre aking down T-1A
the rmodynamic
equilibrium
Water + heavy hydrocarbon
siloxanes + H 2S

M2
Condensate system
technology on the biogas cleaning market
and other gases.
Figure 1. Flow diagram of the Biolimp-
Siloxa Technology. 4. Conclusions

The plant can be split in two parts. The The combination different operation
first related with the gross removal. This inside of the same technology is a good
part involves removing water vapour, manner for biogas cleaning. The energy
heavy hydrocarbon, particle and certain recuperator plays a fundamental roll for
amount of siloxanes by cooling until 2 ºC. save energy only when the biogas
temperature and its flow are high.
The second part related with removing
siloxanes, traces H2S and low molecular 5. References
weight hydrocarbon by adsorption on [1] J. Reina. Biolimp-Siloxa. Planta
activated carbon. In this step play a multipropósito para la limpieza del biogás. 85-
fundamental roll the right selection of the 86. Infoenviron. Julio/agosto. (2008)
activated carbon, the velocity of biogas in
the bed and it’s the relative humidity. [2] BIOGAS UPGRADING AND UTILISATION.
IEA Bioenergy. Task 24: Energy from biological
conversion of organic waste.
Table 1 show the results achieved in the
practical application of this technology in [3] J. Reina. Biogas cleaning/conditioning. A
cleaning the biogas from landfill. In the requirement for optimal runing of CHP
same are presented in turn the removal Systems. Futurenviro. July-August. (2014).

108
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Operation window for advanced SOFC system operated with natural

gas or biogas
Noora Kaisalo1, Johanna Kihlman1, Pekka Simell1
1 VTT Technical Research Centre of Finland, P.O. Box 1000, FI-02044 VTT, Finland.

1. Introduction 2. Results

Solid oxide fuel cells (SOFC) can be used to Thermodynamic calculations considering
convert natural gas or biogas efficiently to the secondary reformer operation were
heat and power in small scale units (5-50 done with HSC 8.0 simulation program.
kW). In SOFC systems, the inlet Biogas was assumed to be 40% of CH4 and
hydrocarbon stream must be reformed for 60% of CO2. For natural gas two different
the fuel cell stack to protect the stack compositions were assumed: one
from carbon formation and too large representing Russian natural gas with low
thermal gradients. amount of C2+ hydrocarbons and one
representing Danish natural gas with
The hydrocarbons may be converted by higher amount of C2+ hydrocarbons.
steam reforming which leads to high
efficiency but complicated and failure The gas compositions of mixed fuel and
prone system due to steam generation. anode off-gas streams are presented in
Another possibility is to convert Table 1.
hydrocarbons by catalytic partial
oxidation, but the efficiency is decreased Table 1. Gas compositions used in
because part of the fuel is burned. thermodynamic calculations for the
Solution to these problems is an advanced secondary reformer.
hybrid SOFC system developed in this
project. Here the anode off-gas is used for Biogas
reforming of natural gas or biogas by O/C 1.3 1.6 2
connecting two fuel cell stacks in series CH4, vol-% 30.24 20.21 11.05
and using the outlet of the first stack to CO, vol-% 2.98 3.98 4.90
reform inlet of the second [1]. For the first CO2, vol-% 33.98 31.95 30.10
smaller stack, the inlet can be reformed by H2, vol-% 3.74 5.00 6.15
CPOX. By this way high efficiency with H2O, vol-% 16.42 21.96 27.01
robust system can be achieved. N2, vol-% 12.64 16.90 20.79
C2H6, vol-% 0.00 0.00 0.00
However, there is a risk of carbon C3H8, vol-% 0.00 0.00 0.00
formation in the second stage where Russian natural gas
anode-off gas is used to reform fresh fuel O/C 1.3 1.6 2
stream. This work concentrates on the CH4, vol-% 23.10 17.38 11.65
practical operation window where the CO, vol-% 2.63 2.83 3.03
reformer can be used without carbon CO2, vol-% 11.92 12.83 13.73
formation in the advanced SOFC system. H2, vol-% 5.50 5.93 6.35

109
H2O, vol-% 23.54 25.35 27.15 In practice, it was observed that carbon
N2, vol-% 32.97 35.44 37.91 formation can be avoided when working
C2H6, vol-% 0.20 0.15 0.10 on thermodynamic carbon formation
C3H8, vol-% 0.13 0.10 0.07 region. Thus, also experiments without
Danish natural gas catalyst were performed to test whether
O/C 1.3 1.6 2 the system is prone to thermal carbon
CH4, vol-% 19.07 14.22 9.46 formation. With natural gas it was
CO, vol-% 2.69 2.88 3.07 observed that the carbon formation does
CO2, vol-% 12.46 13.25 14.03 not occur in lower temperatures but starts
H2, vol-% 5.64 6.04 6.43
at higher where carbon should not be
formed according to thermodynamic
H2O, vol-% 24.13 25.84 27.51
calculations.
N2, vol-% 33.68 36.03 38.34
C2H6, vol-% 1.41 1.05 0.70
3. Conclusions
C3H8, vol-% 0.92 0.69 0.46

Based on the thermodynamic equilibrium

The thermodynamic calculations for
calculations biogas seems to be more
carbon formation limit are presented in
prone to carbon formation than natural
Figure 1. In the results there was no
gas even though it does not contain higher
difference between Russian or Danish
hydrocarbons as some natural gases
natural gases even though Danish gas had
contain. The reformer fed with the anode
higher concentration of C2+ hydrocarbons,
off-gas can be operated, in practice,
thus in the figure there is only one line to
trouble-free in conditions favouring
represent natural gas.
carbon formation. This is an advantage
since it leads to higher efficiency of the
With the same O/C ratio, biogas was more
SOFC system.
prone to carbon formation than natural
gas. Around 15-20 °C higher temperatures
4. References
are required with biogas than natural gas [1] http://www.stage-sofc-
to get on the area where there is no project.eu/?page_id=8, accessed
carbon formation according to 9.3.2015
thermodynamics.

Figure 1. Limit for carbon formation in

thermodynamic calculations.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Challenges in the design and automatic operation of an anaerobic

digestion machine - experiences from the ORION project
J.B. Michel1, N. Zoppi1, S. Esteves6, B. Fernández2, V. Pastor2, S. Angeloni4, M. Aragno1, A.
Chong6, S. Crelier1, R. Dufresne1, J. Maguire7, C. M’ahmed1, F.R. Mahrer3, M. McCormick1,
D. Mettler1, S. Pantalei5, K.Persaud5
1HES-SO University of Applied Science Western Switzerland, 2IRTA, Spain, 3DIGESTO Sàrl, Switzerland,
4CSEM, Neuchâtel, Switzerland, 5University of Manchester, UK, 6University of South Wales, UK, 7DOMMRS,
Ireland

1. Introduction
Every year SME agro-food industries have
to manage large quantities of organic
waste: 239,871,940 tonnes of organic
waste were produced in 2006 [1]. The
specific management of such waste,
regarding the existing EU regulations,
involves costly treatment for the SMEs
and potential hygiene issues on-site.
The aim of the ORION project is to develop
a small automatic user-friendly digestion
machine that enables the on-site Figure 1. Deployed container
treatment of a wide range (100-5000 t/y) 3. Automation strategy
of organic wastes at low cost (~50 /t) and Very few attempts have been made so far
with low maintenance. Biogas is also to develop inexpensive and reliable
valorised locally to produce hot water and diagnostics to optimize digester operation.
increase SME autonomy and profitability. The development of local and remote
maintenance and process improvement
2. Technology description
strategies is therefore an important part
The digester, which is operated in
of the Orion project.
thermophilic mode, comprises several
The overall control architecture proposed
concentric compartments and specific
consists of 3 levels. The level 1, for local
components such as combustion and
controls and diagnostics, corresponds to
sensor modules. The whole unit is
unmanned automatic operation of the
enclosed in a container which is deployed
system. The level 2, or maintenance (local
on-site (Figure 1).
and remote) and complete diagnostics
During the Orion project an automated
(full or detailed), corresponds to the
biogas combustion system has been
intervention of a skilled maintenance
tested allowing high combustion efficiency
technician, off-site (for diagnosis) or on-
with reduced emissions when methane
site (for diagnosis and repair).
content is above 55% v/v. In the case of
Maintenance software is ported on a
lower methane content, a flare is
laptop and standard communication links
operated to avoid methane emissions and
are used. This level can also be used for
heat is provided by a secondary
basic remote monitoring (e.g. from a back-
conventional boiler.
office) of more than 80 process variables

111
but not for remote operation of the Control strategy
system due to safety reason. Real-time control strategies typically
Finally, the level 3 corresponds to the employed can only deal with one input-
monitoring part of level 2 and enables the output parameter and deliver on-off or
modification of some level 1 operational PID based actions, which tend to provide
parameters. It also includes the data reduced performance when applied to
transfer, organisation and storage non-linear response processes such as
required for the high level optimisation of anaerobic digestion [4]. A fuzzy control
the system. strategy has been designed and
Sensors for preventive action implemented successfully through a
It is known that early detection of simulation platform using a modified
dysfunction of biological processes is a key ADM1 model, providing the high level
factor to prevent complete failures. On- control strategy for the ORION system.
line parameters such as pH or biogas flow
only provide indications of the goodness 4. Conclusions
of the anaerobic digestion process. These A compact digester design has been
are not good early indicators of biological developed and equipped with automated
dysfunction. Volatile fatty acids (VFA) modules for biogas combustion and on-
might be among the most promising early line measurements. A sensor array has
indicators of unstable digesters. been calibrated for VFA, ammonium and
Due to the buffering capacity of biogas composition analysis that became
digestates, VFA accumulation may not the input of an automatic control module
result immediately in a pH drop. In this previously tested using a modelling
case, VFA increment would then be the platform on anaerobic digestion process.
earliest warning of a system failure. When Based on what was observed during
this detection is early enough, and the laboratory and prototype experiments,
cause is recognized, a well defined action the next part of the project will consist in
(e.g. to decrease or stop feeding) would long term validation tests using different
avoid an unbalance and make it possible industrial organic wastes. Complete
to maintain an optimized organic loading results are expected at the end of 2015.
rate with a high solids removal and biogas
production. 5. References
[1] Eurostat. 2006. From Waste generated
It was concluded by means of previous and treated in Europe. ISBN 92-894-6355-
experiments with thermophilic completely 4.
mixed 1-step systems in the Orion project [2] Drosg B. 2013. Process monitoring in
biogas plants. IEA bioenergy Task 37.
that “early VFA” content limit might be
[3] Aragno M. et al. 2013. Principles of
around 0.1 g/L [2], although it is usually
biomethanisation, management and
accepted that a concentration below 1.0 optimization of the biological process -
g/L (per individual VFA) defines “stable Orion project. Proc. 21st European
process” in full-scale digesters [3]. On-line Biomass Conference and Exhibition, June
sensors were developed in the Orion 2013, Copenhagen.
project, using conducting polymer sensor [4] Esteves S., Wilcox S., Hawkes D., O’Neill
array which has being calibrated to C., Hawkes F. 2001. The Development of
measure in a 0.1-1.5 g/L and 0.1-2.0 g/L a Neural Network Based Monitoring and
ranges for individual VFA and ammonium, Control System for Biological Wastewater
respectively. Treatment Systems. Int. J.COMODEM 4,
3, 22-28.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Air-Steam Biomass Gasification in a Fluidised Bed Reactor in Presence

of Ceramic Filters
Sergio Rapagnà1 and Giacomo Spinelli1
1Faculty of Bioscience, Agro-Food and Environmental Technology, University of Teramo, via C. Lerici,
64023 Mosciano Sant’Angelo, Italy

1. Introduction gasifier, to perform the steam reforming

There is a global effort to diminish of hydrocarbons as well as to eliminate
greenhouse gas emissions through dust [1].
increasing the share of renewable fuels for In this study biomass gasification trials
energy production and to separate and have been performed in a bubbling
capture CO2. Different types of biomass or fluidised bed reactor, by using a mixture of
biomass wastes such as forest, agricultural air and steam as a fluidising medium, in
and organic processing residues with presence of ceramic filters inserted in the
moisture contents lower than 50% can be freeboard of the gasifier, delivered by Pall
gasified with air, or oxygen and/or steam Filter-systems GmbH Werk Schumacher.
to produce syngas. Biomass gasification
process produces hydrogen rich gases that 2. Technology description
can be the building block to produce pure The bench-scale equipment consists of a
hydrogen, diesel or gasoline (Fischer bubbling fluidised-bed gasifier with an
Tropsch synthesis), fertilizers (through internal diameter of 0.10 m and 0.85 m
ammonia) and methanol, for the chemical high, externally heated by means of a 6
industry. kW electric furnace and modified to house
However, biomass gasification integrated the ceramic filter candle in the freeboard.
with gas cleaning technologies is still The detailed description of the plant has
under development and further been reported elsewhere [2].
demonstration of these technologies is
still needed. The technical, economical 3. Mass and energy balances
and environmental viability of these The pilot plant is equipped with mass and
processes depend on achieving effective flow meters, thermo-couples and gas
gas cleaning technologies that may analysers. The tar content in the produced
decrease considerably the contents of tar gas was determined according with UNI
and pollutant precursors like S, N and Cl CEN/TS 15439 protocol and properly
compounds. Fluidized bed reactors, due to stored at 4 °C, before to perform HPLC
their ability to operate continuously, at quantitative analysis. The collected data
high temperatures, and to utilize catalysts has been used to evaluate the effect of
into the reactors and outside can reduce ceramic filters inserted into the freeboard
drastically tar, NH3 and other pollutants in and to achieve auto thermal conditions in
the producer gas. Recently, it has been the gasifier. Almond shells from Southern
proposed to utilize catalytic and non Italy were used for the gasification
catalytic ceramic filters, placed in the experiments having a mean particles size
freeboard of the fluidised bed biomass of 1.1 mm.

113
 tests with ER greater than 0.2. The gas
composition is shown in Table 1.
Table 1. Gas composition.
Test Test Test Test
120 124 125 126
CO [%-vol dnf] 21 18 18 20
H2 [%-vol,dnf] 57.5 42 40 39
CO2 [%-vol,dnf] 20 34.5 36 35
CH4 [%-vol,dnf] 1.5 5.5 6 6
Tars [g/Nm3] 0.283 3.95 6.67 8.6
Figure 1. Sketch of the biomass The air sent to the gasifier in the last three
gasification plant tests, was 10.6 l/min at ambient
conditions.
Mass and Energy balance Observing the tar compositions of the last
The following test has been conducted: three tests it can be assumed that by
x Test 120: catalytic filter in presence performing the gasification of biomasses
of steam and N2; in presence of air, increases the amount of
x Test 124: catalytic filter in presence organic compounds heavier than
of steam and air; naphthalene.
x Test 125: non-catalytic filter in
presence of steam and air; 5. Conclusions
x Test 126: blank test without filter Based on the observations in this study it’s
in presence of steam and air. clear that the presence of filters inserted
In presence of air and steam the overall in the gasifier, enhances the gas
biomass gasification reaction can be production and tar conversion. The
written as: organic compounds produced during the
+ + air-steam biomass gasification process are
+ + heavier than those produced when only
+ + + steam is used as a gasifying agent. In the
Considering the overall balance of carbon, air-steam biomass gasification process
hydrogen and oxygen that enter and leave auto thermal conditions were achieved
the reactor, for the tests performed with with an ER ratio of 19.6%.
air and steam the material balances are
quite perfect. To check if the amount of air 6. References
is sufficient to assure auto thermal [1] S. Rapagnà et al. Hydrogen Rich Gas from
condition in the reactor, the heat of Catalytic Steam Gasification of Biomass in
reaction HR per kg of raw biomass was a Fluidized Bed Containing Catalytic
calculated at bed temperature, Filters. Chemical Engineering
considering that the steam and the air Transactions, 37, 157-162 (2014).
temperatures inlet in the gasifier are 500
°C and 20 °C respectively. [2] S. Rapagnà et al. In situ catalytic ceramic
candle filtration for tar reforming and
particulate abatement in a fluidized-bed
4. Results
biomass gasifier. Energy Fuel, 23, 3804-9
The study shows that, by using a well (2009).
thermal isolated gasifier, it is not necess-
ary to perform air-biomass gasification

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Autothermal gasification system for clean and efficient power

generation
Janina Ilmurzynska, Krzysztof Remiszewski

Thermal Processes Department, Institute of power Engineering, Warsaw, POLAND

1. Introduction
Gasification is a thermochemical process
that converts materials like biomass into
convenient gaseous fuels. A gas may be
applied to product heat, energy or
chemicals. Depending on the use of the
product gas its cleaning need to be very
efficient. The formation of tar is one of the
biggest problems faced during the several
methods of biomass gasification. In this Figure 1. KAJOT reactor
study the multi-stage gasification concept
separating and combining pyrolysis, 3. Mass and energy balances
combustion and gasification to achieve The installation is equipped with
low tar product gas has been studied. A instrumentation for measurement and
specially constructed multi-staged reactor, registration of the temperatures, gas flow
KAJOT, of 20 kWth capacity has been used. and gas composition (H2, CO, CO2, CH4,
CxHy, tar and dust). The feedstock has
2. Technology description been chemically characterized by
The multi-staged reactor, KAJOT, is the 3- proximate and ultimate analysis. The
staged moving bed reactor. At the 1st collected data has been used to calculate
stage biomass is dried and partly mass and energy balances and the
pyrolysed. Then the remaining char is evaluation of gas purity.
gasified with the mixture of air and steam
at the 2nd stage to produce syngas. Mass balance
Volatiles (VM) released during pyrolysis The mass balance shows that 1 kg of
are combusted with air at the 3rd stage to woodchips with a moisture content of 10%
supply the heat for pyrolysis (1st stage) is converted to 2.16 kg of gas with low
and gasification (2nd stage). Flue gas from heating value ca 6 MJ/Nm3 and 1.25 kg
volatiles combustion and syngas flow out flue gas with oxygen content ca 5%vol.
as separate streams. Flue gas is cooled to The carbon conversion is close to 95%.
produce steam for gasification. Due to low
tar content of the syngas, that stream Energy balance
needs to be dedusted only and optionally The energy balance shows that KAJOT
cooled. Condensate released from syngas reactor produce combustible gas with the
cooler is recirculated to gasification as cold gas efficiency above 70%. Heat
steam to avoid waste problem. contained in hot gas and flue gas may be

115
used to produce steam and the fuel that can be used as soil abatement. The
drying. second side stream is the condensate
released during flue gas cooling. Flue gas
4. Results is the product of volatiles combustion in
The study shows that the KAJOT reactor excess of air and it does not contain
converts biomass to syngas with high organics so can be led to the public sewer.
purity. The tar content in the syngas does
not exceed 2 g/Nm3. Besides by lower tar 5. Conclusions
concentration the process is characterised The tests results show that the release of
by tars with low molecular weight. That volatiles from biomass prior to gasification
makes the tar dew point very low (below enables to produce syngas of high purity
0oC). in the wasteless process.
Table 1. Gas composition.
H2 %mol 25.09
CO %mol 19.40
CH4 %mol 2.14
CO2 %mol 13.66
N2 %mol 39.71
LHV kJ/Nm3 5,916
Table 2.Composition of tars analysed by
GC method.
Compound Concentration (mg/Nm3)
Benzene 1,560
Toulene 432
Ethylbenzene 41
2-ring 0

Low tar content and low tar molecular

weight make the syngas cleaning module
very simple. Two syngas cleaning lines are
configured for different application. The
syngas for gas engine is cooled to 40oC
downstream to the dedusting module. The
syngas dedicated to feed fuel cells (SOFC
type) is cooled to 400oC and desulfurized
with ZnO sorbent.
High electrical efficiency offered by end –
user unit combined with simplicity of
syngas cleaning module makes the
configurations based on KAJOT reactor
feasible.
The KAJOT process produces two side
streams. The bottom residue composed
mainly from ash with low carbon content

116
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

High-pressure anaerobic digestion up to 100 bar: the effects on biogas

production and upgrading
Wolfgang Merkle1, Simon Zielonka and Andreas Lemmer1
1 State Institute of Agricultural Engineering and Bioenergy, University of Hohenheim, Stuttgart, Germany

1. Introduction 2. Material and methods

Considering Germany’s energy supply, The present study researches an
there is a need to supplement the anaerobic digestion process at pressures
increasing share on volatile energy up to 100 bar, measuring the effect of
sources, such as wind and solar energy, by pressure on gas quality and production
expanding demand power generation and using three identical high-pressure batch
developing new energy storage concepts. reactors, each with a total volume of
Biomethane production, in this case, has 0.64 l. Three pressure levels (1 bar, 50 bar,
the potential to play a major role. As 100 bar absolute pressure) were tested at
biomethane gas can be fed directly into a temperature of 37°C (Figure 1).
the public natural gas grid, it thus utilizes a Each reactor was fed with a 0.5 l fluid with
large existing energy storage system. a COD concentration of 5.2 g COD/l. The
Biogas with a CH4 content of 55 to 65% is initial pressure levels were generated by
currently able to be fed into the grid. adding nitrogen. In addition to the specific
However, to achieve the same calorific methanogenic activity, which was
value as natural gas it must be purified, determined by the increase in pressure
and furthermore compressed to the caused by biogas production, alcohols,
required pressure level. The current alkaline buffer capacity, ammonium-
upgrading technologies, such as amine nitrogen, chemical oxygen demand (COD),
scrubbing, gas separation membranes, and volatile fatty acids were analysed. The
organic solvent scrubbing, pressure swing gas quality was calculated by subtracting
adsorption (PSA) and water scrubbing are the nitrogen content in the gas and setting
highly energy consuming and by that the other gas components to 100%.
expensive.
In a new, two-stage pressurized anaerobic
digestion process, methanogenic archaea
increase the pressure in the digester up to
100 bar auto generative, producing
biomethane of natural gas quality inside
the methane reactor, which can then be
fed directly into the grid.
Previous research in this area has achieved
CH4 contents of up to 87% at operating
pressures up to 10 bar in continuous
operation, and of up to 95% at pressures Figure 1. Three 0.64 l pressure batch
up to 90 bar in batch tests [1, 2]. digesters in water bath

117
3. Results and discussion 4. Conclusions
The analysis of the alcohols, alkaline By increasing the pressure in the 0.64 l
buffer capacity, ammonium-nitrogen and batch reactors, it is possible to achieve
volatile fatty acids clearly showed no higher methane contents above 86%. This
inhibition of the processes. Working with indicates that high-pressure anaerobic
lower initial pressures (1 bar) leads to a digestion at up to 100 bar may present an
faster and higher gas formation compared interesting alternative to commonly used
to higher pressures (50, 100 bar) biogas purification technologies. However,
(Figure 2). further research under continuous
conditions is needed.

5. References
[1] Lemmer, A., Chen, Y., Wonneberger, A.-
M., Graf, F., Reimert, R. 2015 Integration
of a water scrubbing technique and two-
stage pressurized anaerobic digestion in
one process. Energies ((2015), 2048-2065.
[2] J. Lindeboom, R. E., Fermoso, F. G.,
Weijma, J., Zagt, K., van Lier, J. B. 2011
Figure 2. Gas formation curves over time
Autogenerative high pressure digestion:
working with three different admission Anaerobic digestion and biogas upgrading
pressures (1, 50, 100 bar). in a single step reactor system. Water
Table 1 presents the gas quality and Science and technology 64 (3), 647-653.
specific methane yield of the three
different pressure levels. Despite the
increase of pressure, the CH4 content still
remains high, with only a small decrease
from 88% at 1 bar to 86.3% at 100 bar.
Table 1. Gas quality and specific methane
yield ± standard deviation working with
three different pressures (1 bar, 50 bar,
100 bar)
Initial mean mean mean specific
pressure calc. CH4 calc. CO2 methane
(bar) content content yield
(%) (%) (l/kg COD)
1 88.0 ± 1.5 12.0 ± 1.5 195 ± 8.4

50 87.8 ± 1.9 12.2 ± 1.9 175 ± 6.9

100 86.3 ± 0.7 13.7 ± 0.7 160 ± 12.1

One possible explanation for the low

specific methane yields is the
measurement only of the gas in the gas
phase and not the gas dissolved in liquid
phase under pressure.

118
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Pneumatic conveying of biocoal from hydrothermal carbonization: An

approach for small scale entrained-flow gasification
Ludwig Briesemeister1, Michael Kremling1, Matthias Gaderer2, Hartmut Spliethoff1,3
1 Institute for Energy Systems, Technical University Munich, 85748 Garching, Germany
2 Regenerative Energy Systems, Technical University Munich, 94315 Straubing, Germany
3 ZAE Bayern, 85748 Garching, Germany

1. Introduction is injected through a porous metal (FR4).

In a future energy system the utilization of Locally fluidized fuel is drawn off and
domestic biomasses and residues will play pushed through the pipe. Fig. 1 shows a
an important role. An enlarged potential simplified P&ID of the system.
of biogenic fuels can be accessed by pre- FQI
FQZ2
treating these materials in order to LS1
produce a high-quality fuel.
RVP2
A promising utilization path is the KL1 PIA-Z+
PZ1
gasification of biocoal made by PDI
hydrothermal carbonization (HTC) in an RVP1
PDZ1
entrained-flow gasifier [1][2]. Entrained- DV3
WIA+-
FR3 M1
flow gasification is typically applied at WZ1
PV1
large scale but it was shown that it can be
competitive at smaller scale as well [3].
Efficiency and quality of the process A1

depends heavily on the stability and

FR4
continuity of the media supply. Therefore
MV4
a reliable feeding system is required. DV2 VM FSA-
FS1
In this work a pneumatic conveying FR1
MV3 FR2 FR3
system is presented that is designed for a FQI DV1
FQZ1
pilot plant (100 kWth) gasifier [4]. The KH1
CP1
system is tested for its behaviour on MV2
LB2
PIA+
PZ2
different fuels and operation conditions.
Variation on fluidization gas was MV1
LB1
performed and the consumption of carrier
gas was measured. Figure 1. Simplified P&ID of the pneumatic
conveying system
2. Experimental set-up
The system basically consists of a pressure To avoid plugging additional gas is added
vessel that is connected to the gasifier via by a metal frit (FR1) and increases the flow
a conveyor pipe (CP1). A vacuum velocity. Interruption of conveying by
conveying system (LS1) is used to fill the plugging or instabilities is detected by a
vessel with fuel from a container. System microwave detector (FS1).
pressure is controlled by two regulating Current feed rate is determined by weight
valves. In the vessel bottom fluidizing gas measurement of the vessel and its time

119
derivation. Carrier gas is determined by the vessel. The system consists of a
balancing the nitrogen in- and outlet pneumatically lifted and lowered anchor
measured by mass flow meters. In Tab.1 above the fluidized bed to avoid
the basic design and operating parameters phenomena like channelling or formation
are summarized. of bridges.
Table 1. Design and operating parameters Solid-gas ratio was 10-30 kg/kg. Necessary
of the conveying system gas velocity for fluidization was in the
range of 2-4 cm/s and the conveying
Parameter Range velocity inside the pipe was 2-3 m/s.
in kg/h 5…25
Coal bulk density in kg/m³ 250…450 4. Conclusions
in barg 0…5 With the system presented in this work
in m³ 1 the concept of pneumatic conveying for
small-scale entrained-flow gasification
3. Experimental trials and results could be proven. Different fuels with
Experimental trials and feedstock typical particle size distributions for
Main purpose of the trials was to find entrained-flow processes could be
stable working points without fluctuation conveyed steadily.
of feed rate and to minimize the inert gas In particular the demonstration of the
consumption for transportation. The latter suitability for HTC coal as a rather new
can be evaluated by the solid-gas fuel type is of importance.
ration μ (1).
= (1) 5. References
[1] Briesemeister et al. Study of a
As feedstock two fossil coals and two HTC Decentralized Entrained-Flow Gasification
biocoals were tested with mean particle Plant in Combination with Biomass from
size as listed in Tab. 2. Hydrothermal Carbonization for CHP.
22nd European Biomass Conference and
Table 2. Mean particle size of fuels tested Exhibition, Hamburg (2014).
with the conveying system. [2] Tremel et al. Entrained flow gasification
Fuel HTC1 HTC2 Lign. Bitum. of biocoal from hydrothermal
D50 54 153 57 20 carbonization. In: Fuel 102, S. 396–403
(2012)
in μm
[3] Tremel et al. Performance of entrained
flow and fluidised bed biomass gasifiers
Trials were performed varying feed rates, on different scales. In: Energy Conversion
counter pressure, fluidization and and Management 69, S. 95–106 (2013)
additional gas. Two different conveyor [4] Kremling et al. High-Temperature
pipes (inner diameters of 6 and 8 mm) Biomass Gasification in an Entrained-Flow
were used with a pipeline length of 10 m. Reactor – Design and Engineering of a
Test Facility. 22nd European Biomass
Results Conference and Exhibition, Hamburg
With the current set up biocoal with a (2014).
mean particle size of 153 μm (HTC 2) could
not be conveyed. This is probably due to 6. Acknowledgement
the small pipe diameter attended by The financial support from Federal
plugging. Other fuels in Tab2. could be Ministry for Economic Affairs and Energy
steadily conveyed with additional support (FKZ: 03KB074B) is gratefully
of a mechanical loosening system inside acknowledged.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Establishment and Analysis of a two-stage Process for simultaneous

Production of Biohydrogen and Biomethane
Robert Manig1, Toni Raabe1, Ronny Erler1 and Hartmut Krause1
1 DBI – Gastechnologisches Institut gGmbH Freiberg, Halsbrücker Straße 34, 09599 Freiberg, Germany;

1. Introduction For cost reasons, a single-stage fermenta-

The increasing global demand for energy tion process is established in practice.
from fossil fuels is opposed by the short- However, a two-stage process, devided
age of resources. In addition, the envi- into two phases (Fig. 1), has certain ad-
ronment is polluted reinforced by the use vantages. The bacterial species prefer dif-
of fossil energy sources. A climate-friendly ferent requirements for environmental
energy source is hydrogen based on re- conditions (Table 1).
newable energy. A possibility to produce
biohydrogen is by using fermentation in a Table 1. Optimum process parameters for
two stage process [1-6]. a two-stage process [8]
parameter first phase second phase
2. Technology description mesophilic: 32 –
The fermentation process can be divided 42 °C
T 25 – 35 °C
into four biochemical phases (Fig. 1) [7, 8]. thermophilic: 50
These phases decomposition of complex – 58 °C
organic material are hydrolysis, the acido- pH-value 5,2 - 6,3 6,7 - 7,5
genesis (formation of CO2 and H2), aceto- C:N-ratio 10 - 45 20 - 30
genesis and methanogenesis, where me- nutrient
thane is formed. demand 500:15:5:3 600:15:5:3
C:N:P:S
trace ele- essential: Ni,
-
ments CO, Mo, Se

Based on these facts, a two-stage process

for combined production of biohydrogen
and methane was investigated.

3. Experimental investigation
The experimental investigations are car-
ried out on a pilot biogas plant (2 m³ fer-
menter volume) in the laboratory at DBI-
Gastechnologisches Institut gGmbH
Freiberg (Fig. 2).

Figure 1. Simplified scheme of biogas and

biohydrogen production

121
Figure 2. Pilot biogas plant with two fer-
Figure 3. Raw hydrolysis gas concentration
mentation plants
over time.
The fully automated pilot plant is
5. Conclusions
equipped with a data management and
In this study a continuous process with
recording system. The two-stage process
associated parameters for the simultane-
is analysed by different parameters, such a
ous production of biohydrogen and bio-
pH- and redox-value, temperature, pres-
methane was established. In an extensive
sure, gas-quality (CH4, CO2, H2, O2, H2S)
experimental program, the optimal pro-
and quantity.
cess parameters were determined and
validated in pilot biogas plant.
4. Results
In addition, the utilization pathways of
A continuous, long-term stable process
hydrogen (fuel cell) and methane (upgrad-
was established by the following parame-
ing and grid-injection) were shown.
ters (Table 2).
6. References
Table 2. Optimum process parameters.
[1] M. Cooney, N. Maynard, C. Cannizzaro, J.
parameter first phase second phase
Benemann, Bioresource technology 2007,
substrate carbohydrates hydrolysate
98 (14), 2641.
sewage sludge sewage sludge [2] H. Ding, J. Wang, International Journal of
inoculum
or digestate or digestate Hydrogen Energy 2008, 33 (23), 6993.
mesophilic: [3] D. Rechtenbach, Fermentative Erzeugung
T 60…80 °C
32…42 °C von Biowasserstoff aus biogenen Roh-
pH-value 5 – 5,5 6,5 – 7,5 und Feststoffen.Verlag Abfall aktuell,
retention Stuttgart, 2009.
4…8 d 20…40 d
time [4] F. Hawkes et al., International Journal of
Loading 5 kg/(m³·d) to be optimized Hydrogen Energy 2007, 32 (2), 172.
re- digestate from [5] N. Khanna, D. Das, WENE 2013, 2 (4), 401.
- [6] M. Krupp, R. Widmann, International
circulation second phase
nutrient 600:15:5:3 Journal of Hydrogen Energy 2009, 34 (10),
demand (1 wt% of sub- to be optimized
4509.
[7] Fachagentur Nachwachsende Rohstoffe
C:N:P:S strate)
e.V. (FNR): Leitfaden Biogas. 6. vollst.
übera. Auflage 2013.
The experiments ran stable for 6 months [8] P. Rabe, Untersuchungen zur Hydrolyse in
while hydrogen (up to 30 vol% in first Biogasanlagen. Präsentation zur Fachta-
stage, see Fig. 3) and methane gung „Biogas“, 2008.
(50…60 vol% in second stage) were con-
tinuously produced.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Medium-temperature Catalytic Tar Reforming of Biogenous Synthesis

Gas – Modeling and Sensitivity analysis
Michaela Fraubaum and Heimo Walter1
1 Institute for Energy Systems and Thermodynamics, Vienna University of Technology, Getreidemarkt 9,

1060 Vienna, Austria

1. Introduction mathematical models of the different gas

Tar removal is the major technical cleaning steps. Additionally a sensitivity
obstacle in the implementation of the analysis was performed to show the
gasification technology. The process influence of various operating parameters
presented in this study combines on the whole system and optimize the
pressurized allothermal gasification and a process.
novel catalytic gas cleaning process
operating in a considerably lower 2. Technology description
temperatures range than catalytic hot gas After gasification in the Agnion Heatpipe
cleaning methods. Medium temperature Reformer (HPR) [1] the syngas is cooled to
catalytic tar reforming is a promising 300°C. After passing a particle filter, H2S is
alternative to commercially available cold adsorbed on ZnO to avoid catalyst
gas scrubbing considering the high gas deactivation. In the next step steam
purity, the lower investment costs, the reforming of tars occurs simultaneously
increased fuel heat value and the with the methanation reaction and the
avoidance of waste water problems. In water gas shift reaction in a fixed bed
addition the process has less thermal reactor catalysed with a conventional Ni-
losses and allows simple and compact catalyst. The exothermic methanation
reactor design than hot catalytic tar reaction leads to a temperature rise in the
reforming, making it uniquely suitable for reactor, enabling the steam reforming of
decentralized small-scale gasification the tar components. Finally the SNG is
plants. cooled in a spray quench tower. A flow
In this study the overall process (including chart of the overall process is shown in
heat integration) was simulated using Figure 1.

Figure 1: Detailed flow sheet of the raw-SNG production process

123
3. Process modeling consumables decreases with low steam
The raw-SNG production process is excess ratio and high gasification pressure.
modeled and simulated in the commercial
process simulation software IPSEpro. 5. Conclusions
Mathematical models of the gas cleaning The results of this study clearly demon-
components are developed and imple- strate the potential of decentralized small-
mented into the IPSEpro Pyrolysis and scale SNG production by combination of
Gasification Process Library [2]. A special pressurised gasification and catalytic
focus lies on the combined tar reforming medium temperature gas cleaning. Due to
and methanation reactor, which is the combination of tar reforming and
modeled by applying mass and energy methanation in one reactor and the
balances, reaction kinetics and chemical reduced temperature, lower investment
equilibrium equations. costs in comparison with cold gas washing
and a simplification in the reactor design
4. Results compared with catalytic hot gas cleaning
To optimize the efficiency and minimize are expected.
the amount of consumables required for
the process, a sensitivity analysis is 6. References
performed, evaluating the influence of [1] G. Gallmetzer et al. The agnion Heatpipe-
steam excess ratio, gasification pressure Reformer operating experiences and
and the temperature of the SNG after the evaluation of fuel conversion and syngas
product gas cooling. The parameters cold composition, Biomass Conversion and
Biorefinery, 2 (2012)
gas efficiency (ratio of the chemical energy
[2] T. Pröll et al. Development and
content of the SNG compared to the
application of a simulation tool for
chemical energy in the fuel) and overall biomass gasification based processes,
thermal utilization rate (ratio of the International Journal of Chemical Reactor
chemical energy content of the SNG minus Engineering, 6 (2008)
the electric power consumption plus the
district heat compared to the chemical
energy in the fuel) are used to evaluate
the performance of the process.
The analysis shows that under optimized
process conditions a cold gas efficiency of
over 70% can be achieved. By using the
waste heat, the total efficiency for the
overall process can be increased to
approximately 90%. Moreover the
necessary amount of consumables like
catalyst and fresh water can be reduced
considerably by working under optimized
operating parameters. Results of the
sensitivity analysis show that steam excess
ratio and gasification pressure have the
strongest influence on the gasification and
the entire SNG process. The process
efficiency increases while the demand for

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Process for cost-effective Removal of Sulfur and Oxygen from

Biomethane on Iron Oxide Sorbents
Toni Raabe1, Sven Kureti2, Ronny Erler1 and Hartmut Krause1
1 DBI – Gastechnologisches Institut gGmbH Freiberg, Halsbrücker Straße 34, 09599 Freiberg, Germany;
2 Technische Universität Bergakademie Freiberg, Fuchsmühlenweg 9, 09599 Freiberg, Germany

1. Introduction Fe2S3 + 3/2 O2 Fe2O3 + 3/8 S8 (3)

One of the major issues of the energy Fe2S3 + 3/2 O2 + 3 H2O 2 Fe(OH)3 + 3/8 S8 (4)
industry is the integration of renewable Therefore, it is evident to combine both
energy sources into the energy supply steps for integrated desulfurization and
system, together with conventional fuels. removal of oxygen in biomethane facilities
In this concern, the injection and storage (Fig. 1).
biomethane

of biomethane in the natural gas grid is O2-free

currently considered as a promising

technology. In addition to the H2S-
removal
O2-
removal

desulfurization and carbon capture upon

the biogas purification, the removal of Biogas plant
CO2 - removal

residual oxygen is also required, especially

CO2-free gas /

in transnational natural gas grids or raw biogas

laden with O2

underground gas storage operators to

prevent corrosion respectively geo- Figure 1. Simultaneous removal of sulfur
chemical reactions. In gas grids with a high and oxygen during biogas purification
water content the negative influence of process [6].
oxygen is noticeable [1, 2]. Even at low
oxygen contents corrosion phenomena 3. Experimental investigation
and the formation of elemental sulfur in A screening of different commercial iron
pore and aquifer gas storage occur. oxides implying, different modifications
and particle size distributions, was carried
2. Technology description out. The physio-chemical characterization
Iron oxides and hydroxides, such as was performed using the following
ɲ-Fe2O3 or ɲ-FeOOH, are effective methods:
reagents for gas-phase desulfurization x Specific surface (BET,
from waste gas or biogas [3–5]. The N2-physisorption)
stoichiometry of the reactions of H2S with x Porosity, gross and pure density
iron oxides are summarized in the follow- (Hg-porosimetry)
ing equations. x Pore size distribution (Hg-
Fe2O3 + 3 H2S Fe2S3 + 3 H2O (1) porosimetry)
2 Fe(OH)3 + 3 H2S Fe2S3 + 6 H2O (2)
x Particle size distribution (laser
Regeneration of reaction sites is
diffraction)
accomplished by subsequent reaction with
x Number of acid sites (Ammonia-
oxygen resulting in the formation of iron
TPD)
oxides and elemental sulfur.
x pH-value

125
 x X-ray powder diffraction (XRD) interaction with ion pairs or defect sites
x Scanning Transmission Electron [7, 8]. Hydrogen sulfide is adsorbed on
Microscopy (STEM) metal oxide surface with participation of
Moreover, studies of break-through BASs and LASs [7]. In addition, a
behavior and loading in a fixed-bed transformation of Lewis in Brønsted acid
reactor were carried out. Studies on sites by adsorption of water or H2S on the
reaction mechanism of desulfurization on metal oxide is possible [7].
ɲ-Fe2O3 and ɲ-FeOOH as well as oxygen
removal on sulfidized ɲ-Fe2O3 / ɲ-FeOOH 5. Conclusions
were performed using Diffuse Reflectance The previous results have shown the
Infrared Fourier Transform Spectroscopy. promising potential of the combined
desulfurization and oxygen removal on
4. Results cheap and worldwide available iron
In Table 1 the results of the physio- oxides.
chemical characterization of the invest- Using physico-chemical characterization,
igated samples are shown. different iron oxide modifications were
studied and particularly important
Table 1. Results of physio-chemical
material values, especially specific surface,
characterization of the samples used.
number of Brønsted and Lewis acid sites
ɲ-Fe2O3 ɲ-FeOOH as well as pH-value, could be quantified.
Fe-content wt.% - 58.2 For further optimization of the iron oxide
Purity % 99.0 99.0 adsorbents studies on reaction
pH-value - - 8.5 mechanism of the process steps are of
ɸ - 0.78 0.78 crucial importance. This will be performed
PV,tot cm³/g 0.81 0.89
by Diffuse Reflectance Infrared Fourier
P%,Macro % 87.2 14.4
Transform Spectroscopy.
P%,Meso % 0 82.5
P%,Micro
% 12.8 3,1 6. References
(calculated)
[1] U. Gronemann, R. Forster, J. Wallbrecht,
SBET m²/g 19 102
H. Schlerkmann, gwf Gas|Erdgas 2010,
mol/
ndes,total 1.35 2.47 151 (4), 244.
m²
[2] Muschalle, M. Amro, Influence of oxygen
mol/
ndes,Brønsted 1.35 1.49 impurities on underground gas storage
m²
and surface equipment, DGMK research
mol/
ndes,Lewis 0 0.98 report, Vol. 753, DGMK, Hamburg 2013.
m²
[3] A. L. Kohl, F. C. Riesenfeld, Gas
Number 8.13E+1
m-2 1.50E+18 Purification, 2nd ed., Gulf Publishing
BAS/LAS 7 Company, Houston, Texas 1974.
Number 1.54E+1
g-1 1.51E+20 [4] G. Drautzburg, gwf Gas|Erdgas 1985, 126
BAS/LAS 9 (1), 36.
BAS – Brønsted acid sites, LAS – Lewis acid [5] J. E. Kattner, A. Samuels, R. P. Wendt,
sites: quantified by NH3-TPD Journal of Petroleum Technology 1988, 40
(09), 1237.
These results were correlated with data of [6] T. Raabe, R. Erler, H. Krause, gwf
break-through investigation to determine Gas|Erdgas 2013, 154 (11), 854.
structure-activity correlation. In literature [7] A. A. Davydov, Molecular spectroscopy of
the reaction of hydrogen sulfide with the oxide catalyst surfaces, Wiley-VCH,
surface of metal oxides, such as Al2O3, Chichester [u.a.] 2003.
MgO, SnO2 or ZnO, is described as an [8] A. Davydov, K. T. Chuang, A. R. Sanger, J.
Phys. Chem. B 1998, 102 (24), 4745.

126
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

High temperature biomass gasification in an entrained flow reactor –

Commissioning and first trials of a 100 kW test facility
Michael Kremling1, Ludwig Briesemeister1, Sebastian Fendt1, Matthias Gaderer2,
Hartmut Spliethoff13
1
Institute for Energy Systems, Technical University of Munich, 85747 Garching, Germany
2
Regenerative Energy Systems, Technical University of Munich, 94315 Straubing, Germany
3
ZAE Bayern, 85747 Garching, Germany

1. Introduction 2. Design of the test facility

The state of the art technology for The aim of this work is to investigate the
thermochemical conversion of biomass to high temperature gasification of pre-
gas is fluidized bed gasification. The treated biomass in an entrained flow
operation temperature of this process is gasifier. The focus lies on the optimization
limited to 950°C. This is why the of the cold gas efficiency and the gas
concentration of tars in the product gas is quality. Also the ash/slag behaviour inside
high and an aftertreatment system is the gasifier and the influence of the pre-
necessary. In a new approach an entrained treatment parameters on the gasification
flow gasifier – state of the art in industrial are of interest. For these experimental
coal gasification plants – is used for investigations a 100 kW lab-scale test
thermochemical conversion at high facility was designed, engineered and
temperatures (1,000°C – 1,500°C). Due to constructed. The gasifier is designed
the high operation temperature the industrial-like but still flexible in operation.
product gas is almost tar free and has only The main operating parameters are shown
a little CH4 content [1]. in table 1.
Table 1. Design and Operating Parameters
The product gas can be used directly for
of the test facility
power generation (e.g. CHP, micro gas
turbine, FC) or refined to SNG or BtL [2]. Operation mode: autothermal
Another part of the new approach is the Temperature: up to 1,500 °C
biomass pretreatment to make biomass Pressure: 0 to 5 barg
useable for energy supply which is not Fuel input: 100 kW
energetically used until now and does not Gasification agent: air, O2, H2O,
compete with agricultural food cultivation CO2
(e.g. straw, grass cut, agricultural Fuel feeding: pneumatically
residuals). Examples for pretreatment Operation without
technologies are hydrothermal carbon- fuel refilling: up to 10 h
ization or torrefaction.
The test facility consists of several
It is already theoretically shown that subsystems like pressure vessel with
entrained flow gasification of biomass can refractory, dosing system for biomass and
be competitive to fluidized bed reaction gases, burner unit, water quench,
gasification [3]. gas analysis, product gas flare and others.

127
Figure 1 shows a cross section view of the carry out with lignite. This fuel was used
gasifier. More details about design and because it was available at the site, the
engineering are described in [4]. behaviour is known and it has good
properties for pneumatically conveying.
biomass, The plant could be operated for almost 5
air, O2, H2O, CO2 hours without interruption. The
gasification agent was air, pressure was
burner unit camera
around 0.2 barg.

flame position 4. Outlook

In the next steps the operation with O2
multi layer refractory and pressure (up to 5 barg) has to be
tested. The design of different burners
continues. First significant results with
accesses for
measurement biomass are expected to be available until
technology the middle of 2015.

reaction chamber 5. References

[1] C. Higman; M. Burgt. Gasification (2008)
[2] M. Kaltschmitt; H. Hartmann; H.
water quench Hofbauer. Energie aus Biomasse (2009)
[3] A. Tremel; D. Becherer; S. Fendt; M.
Gaderer; H. Spliethoff. Performance of
entrained flow and fluidised bed biomass
CO, H2 gasifiers on different scale. in: Energy
(H2O, CO2, N2) Conversion and Management 69 (2013)
access for gas and 95-106
particle sampling
[4] M. Kremling; L. Briesemeister; H.
Figure 1. Cross section view of the gasifier Spliethoff; M. Gaderer. High-
Temperature Biomass Gasification in an
Entrained Flow Reactor, in: Proceedings
3. Commissioning
European Biomass Conference and
The test facility has an industrial PLC
Exhibition (2014)
(Simatic S7), which controls all systems of
the plant and logs the data.
6. Acknowledgment
After testing all sub systems separately
The financial support from Federal
the first heating up with a gas burner (84h
Ministry of Food and Agriculture of
with defined heating rates) was completed
Germany (FKZ: 2023911) is gratefully
successfully. Maximum temperature
acknowledged.
reached 1,500 °C.
The refractory contents electrical heaters
for heating up the walls of the reaction
chamber before starting the trials to reach
a self-ignition of the biomass. The first test
showed that the wall reached the
expected temperature of 950 °C after
36 h.
The first trials in the gasification mode
under realistic operation conditions were

128
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Biogas upgrading by electromethanogenesis using a microbial

electrolysis cell
Míriam Cerrillo1, Marc Viñas1 and August Bonmatí1
1 IRTA. GIRO Joint Research Unit IRTA-UPC. Torre Marimon, E-08140 Caldes de Montbui, Barcelona, Spain,

august.bonmati@irta.cat

1. Introduction 1) Directly (the electrons are taken directly

Bioelectrochemical systems (BES) use from the electrode and are used to reduce
microorganisms attached to one or both CO2 to methane).
electrode(s) to catalyse oxidation and/or
CO2 + 8 H+ + 8 e- Æ CH4 + 2 H2O
reduction reactions. A BES is called
Microbial Electrolysis Cell (MEC) when
2) Indirectly (through the intermediate
external energy is supplied to promote a
abiotic production of hydrogen in the
thermodynamic non spontaneous
cathodic compartment).
reaction. These systems have emerged as
a highly versatile technology that allows 2 H+ + 2 e- Æ H2
the coupling of wastewater treatment to CO2 + 4 H2 Æ CH4 + 2 H2O
the production of chemical compounds
and energy carriers. In the anode This process, called electromethano-
compartment of a MEC, oxidation genesis, could be applied for increasing
reactions take place, producing protons the methane content of the biogas
and electrons. The electrons are produced in anaerobic digestion plants.
conducted to the anode and flow through The aim of this study is to evaluate the
an external electrical circuit to the capability of a biocathode in a lab-scale
cathode, while the protons and the MEC to convert CO2 into CH4, as
cations migrate to the cathodic alternative technology for biogas
compartment through the cationic upgrading.
exchange membrane placed between both
compartments to maintain electro- 2. Technology description
neutrality. At the cathode, the protons The MEC consisted in a two chamber
and the electrons are used to produce reactor (500 mL of empty volume for each
methane from CO2. The cathode reaction compartment) equipped with a cation
is catalysed by electrochemical active exchange membrane between comp-
microorganisms, the hydrogenotrophic artments (Figure 1). Each chamber was
methanogens [1]. As the reaction is not filled with graphite granules to act as
thermodynamically favourable, external electrodes (anode and cathode). Both the
electric energy must be supplied. anode and cathode chambers were
Hydrogenotrohic methanogens can inoculated with biomass from the anode
catalyse methane production from CO2 in effluent of a mother MEC and the granular
a MEC by two mechanisms of extracellular sludge of an Upflow Anaerobic Sludge
electron transfer [1]: Blanket reactor, and were fed in
continuous with a synthetic solution of

129
acetate and bicarbonate, respectively. progressive enrichment of the biomass.
Both compartments were mixed by Further research is needed to achieve
recirculation. A potentiostat was used to higher methane productions, both by
fix the cathode at the desired potential (- applying lower potentials to the cathode
800 mV vs standard hydrogen electrode, [2] or by allowing a longer time for
SHE, in this study), with a three electrode increasing biomass density.
design, where the working electrode was 70 35

CH4 production (mL day-1)

connected to the cathode; the counting 60

Electron recovery (%)

30
electrode, to the anode; and the reference

Current (mA)
50 25
electrode, to an Ag/AgCl electrode 40 20
inserted in the cathode compartment 30 15
(+0.197 V vs SHE). In this manuscript all
20 10
voltages are reported with respect to SHE. Current
10 Methane production 5
Gas flow Electron recovery
Potentiostat meter 0 0
0 20 40 60 80 100
CH4
Time (d)
e-
Figure 2. Current, methane production,
and electron recovery in methane form.
CO2
Influent Influent
tank tank
4. Conclusions
Although in its early stage of
Reference
development, a MEC reactor with a great
Effluent electrode Effluent potential as a technology for biogas
Bioanode Biocathode
tank tank upgrading converting CO2 into additional
Cation Exchange biofuel is presented.
membrane

Figure 1. Scheme of the Microbial 5. Acknowledgments

electrolysis cell for methane production. This research was funded by the Spanish
Ministry of Economy and Competitiveness
3. Results (INIA project RTA2012-00096-00-00). Also
The MEC was operated during 95 days at a financial support was received by the
poised cathode potential of -800 mV. The Catalan Government (pre-doctoral
intensity produced by the MEC increased fellowship 2013FI_B 00014).
from around 15 mA to up to 60 mA in the
first 40 days of operation, and afterwards 6. References
[1] Cheng, S., Xing, D., Call, D.F., Logan, B.E.
was maintained in a range of 25-40 mA.
(2009). Direct biological conversion of
The methane production in the cathodic electrical current into methane by
chamber increased from 12 up to 22 mL electromethanogenesis. Environmental
day-1 (Figure 2). When the amount of Science & Technology, 43 (10), 3953–
electrons transferred from the anode to 3958.
the cathode is compared to the amount of
[2] Villano, M., Aulenta, F., Ciucci, C., Ferri, T.,
electrons recovered for the conversion of Giuliano, A., Majone, M. (2010).
CO2 to CH4 (taking into account that 8 mol Bioelectrochemical reduction of CO2 to
electrons are needed for every mole of CH4 via direct and indirect extracellular
CH4 produced), the efficiency increased electron transfer by a hydrogenophilic
from 15% in the first 45 days up to 30% at methanogenic culture. Bioresource
the end of the assay (day 95), showing a Technology, 101, 3085-3090.

130
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Renovagas project - getting synthetic natural gas from renewable

energy sources (RES)
Susana Pérez1 and Mónica Sanchez2
1 TECNALIA R&I, Energy and Environment Division, San Sebastian, SPAIN

2 CENTRO NACIONAL DEL HIDROGENO (CNH2), Technical and Research Department, Puertollano, SPAIN

1. Introduction Competitiveness (MINECO) in the frame of

While Renewable Energy sources (RES), the National Programme for Research
including solar photo-voltaic, Aimed at the Challenges of Society, has as
concentrated solar and wind make up an aim the development of a 15 kW
increasingly large fraction of energy supply demonstration plant for the production of
mix, the development of suitable energy Synthetic Natural Gas (SNG) from the
storage has lagged behind. The energy electrolytic production of hydrogen with
storage is nececesary to match supply and RES and CO2 (obtained from biogas)
demand of RES both, geographically and through a methanation process. By this
temporarily. One promising option for RE way, the SNG produced is fully renewable.
storage is the transformation of the Also, this SNG obtained should have an
electricity in a secondary chemical energy enough quality that permits its
carrier, such as hydrogen or carbon based introduction in the existing Spanish
fuel (e.g. methane). This is the Power-to natural gas grid infrastructure.
gas concept, P2G. Participants in RENOVAGAS project are
The main advantages of using methane as Enagás, FCC-Aqualia, Gas Natural Fenosa,
an option for storing renewable energy is Abengoa Hidrógeno, Consejo Superior de
their high energy density (3 times higher Investigaciones Científicas (CSIC), Centro
than hydrogen) and that it can be fed into Nacional del Hidrógeno (CNH2) and
the existing gas grid, taking advantage of Tecnalia R&I.
the vast storage capacity of the existing
gas network. Thus, the electricity grid will 3. Technical description
be integrated with the gas network The process to produce SNG from CO2 and
thereby resolving issues resulting from the H2 using renewable sources is a relatively
integration of Renewable Energy sources new concept, known as “Power-to-Gas”
into the existing electricity grid, including (P2G)”. This concept presents a new
imbalance of supply and demand and grid approach for storage of renewable energy
congestion. In addition, methane is a sources using the existing natural gas
valuable energy vector with applications in infrastructure and getting a bi-directional
the mobility secotr and the chemical link between the power and the gas grid.
industry.
The process involves two main steps:
2. RENOVAGAS project Firstly, fluctuating electricity from RES is
The RENOVAGAS project, funded by the used for the electrolytic generation of
Spanish Ministry of Economy and

131
 hydrogen, through the splitting of water - an advanced control system, for the
molecules: integration of the electrolyser with RES,
designed by CNH2.
H O O +H 'H0R=286 kJ/mol Finally, the subsequent developments
along the project will be integrated in a
Secondly, this renewable hydrogen is P2G demonstrator. This demonstrator will
converted to methane with CO2 in a be an installation of 15 kW that can
synthesis reactor, according to Sabatier produce up to 2 m3/h of SNG with a
reaction: quality that can be injected directly in the
Spanish gas infrastructure. The system
CO + 4H O + H 'H0R=-165 kJ/mol developed must be flexible, easily up
scalable and modular, in order to allow an
Although, the carbon dioxide required for adjustment to the specific condition, and
methanation can be provided from a will be tested in conjunction with a biogas
variety of sources, the use of CO2 from plant, which belongs to FCC-Aqualia
biogas directly, without previous Company to validate the performance in
separation, deserves special attention, real conditions.
because it allows the combination of the Therefore, based on the results of this
resources of biomass and electricity from project, it´s planned to scale up the
RES, increasing the coverage of fuels from system up to the order of megawatts,
biomass significantly. This is, precisely, the through the development of a 250 kW
main innovation of the RENOVAGAS pilot plant in a first stage and finally to
project. build a 5 MW infrastructure.
BIOGAS CH 4 +CO 2
4. Conclusions
Methanation CH 4 To the grid A demonstration plant for the production
of synthetic natural gas (SNG) from the
Electrolysis H2
electrolytic production of hydrogen with
renewable energy sources (RES) and
H 2O
biogas through a methanation process is
being carried out in the frame of the
Figure 1. Power to Gas system from RENOVAGAS project “Getting synthetic
biogas. natural gas from renewable energy
sources”. It is a unique demonstration
With the aim to improve the efficiency project in Spain, whose results will provide
and durability of the process, the main knowledge about the technical and
developments to carry out during the economic feasibility of the Power-to-gas
project are the followings: systems.
- a catalytic methanation reactor,
designed by Tecnalia R&I, in order to 5. Acknowledgements
improve the mass and heat transfer and to This work has been supported by the
run directly with biogas, at 300ºC and 25 Spanish Ministry of Economy and
bar Competitiveness (MINECO), in the frame
- new series of methanation catalyst, of the National Programme for Research
prepared by ICP-CSIC, based on Ni or Ru Aimed at the Challenges of Society under
supported on Al2O3 with high capacity and project RENOVAGAS with dossier number
resistance to the deactivation RTC-2014-2975-3.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

The effect of heat buffering on the performance of concentration

swing adsorption for the purpose of biogas upgrading
Carole Harrivelle1, Barna Heidel1, Günter Scheffknecht1
1 Department Fuels and Flue Gas Cleaning, Institute of Combustion and Power Plant Technology, Stuttgart
University, Pfaffenwaldring 23 D-70569 Stuttgart

1. Introduction the resin, while the desorption is

Commonly, biogas is converted into endothermic and requires heat supply.
electrical power in combined heat and Heat Air Heat
CH4
power plants directly at the location of the
biogas production. However, due to the
decentralized location, often a part of heat Adsorption Desorption
cannot be used adequately. Separating
carbon dioxide (CO2) from biogas allows
the injection of biomethane into the CH4 CO Air CO2
2
natural gas grid and to use it efficiently,
close to a heat sink. Currently, several Figure 1. Process scheme of concentration
techniques for upgrading biogas to swing adsorption
biomethane are used. However, the 3. Heat buffering
investment and operational costs of most The thermal buffering is achieved through
biogas upgrading systems allow an a water bath for the temperature
economic use only on large scale. At the regulation of the whole experiment and
Institute of Combustion and Power Plant the use of phase change material (PCM)
Technology (IFK), a novel technique for for heat storage.
biogas upgrading using a concentration In PCM, heat is stored and released when
swing adsorption of CO2 at polymeric the material is undergoing a phase change
resins is developed. such as solidification or melting. This
2. Technology description phase change allows heat storage at
In this process, the polymer resins have constant temperature, whereas in
the ability to adsorb CO2 from gases conventional heat storage the amount of
selectively. The resin is regenerated by energy stored depends on the heat
purging with air. By the use of 2 columns, capacity of the material and the
adsorption and desorption take place temperature difference between the
simultaneously in a continuously operated material and the surrounding.
process. A lab-scale and a technical-scale Furthermore, the use of PCM enables
plant were already operated successfully increased heat storage capacity.
with synthetic and real biogas. In order to 4. Experiments
further improve the process, additional Two columns are filled with a mixture of
research is carried out in the field of heat PCM and the polymer resin. The
management. As depicted in figure 1, the experiment is carried out at 40 °C. The
adsorption is an exothermic process phase change temperature of the PCM is
requiring the removal of excess heat from 50 °C. The air stream for the desorption is

133
varied from 0.5 L/min to 4 L/min. The 1,0
impact of PCM on the working capacity 0,8

[mol CO2 / kg resin]

Working Capacity
and on the temperature gap of the
0,6
continuously working biogas upgrading
process is investigated. 0,4
With PCM
5. Results and discussion 0,2
Without PCM
The results of the experiments are shown 0,0
in the following figures. In the presence of 0 1 2 3 4
PCM, the temperature gap between Air stream [L/min]
adsorption and desorption is reduced (see Figure 3. Working capacity of the process with
figure 2). For lower temperature during and without PCM
adsorption, more CO2 is adsorbed. 100%

Reduction of methane
Furthermore, higher temperature during 80%
desorption enhances the regeneration of
60%

loss [%]
the resin. As can be seen in figure 3, the
40%
resulting working capacity increases in the
presence of PCM significantly for all 20%
purging air flow rates. 0%
0,5 1 2 4
55 Air stream [L/min]
50 Figure 4. Reduction of methane loss through
Temperature [°C]

switching compared with the experiments

45 without PCM.
40 6. Conclusions
35 The results of this study show, that the
working capacity of the process is
30 increased by the combination of PCM and
0 1 2 3 4 polymer resin. The resulting decrease in
Air stream [L/min]
Tmax, with PCM switching frequency of the continuously
Tmax, without PCM operated process leads to increased
Tmin, with PCM efficiency and decreased methane loss.
Tmin, without PCM
7. Acknowledgement
Figure 2. Temperature range of experiments The results were obtained within the project
with and without PCM. “ABIoLa” (FKZ: 03SF0487A). The authors thank
At the end of each cycle, the columns are the consortium for the support and the
Federal Ministry of Education and Research
switched. Thus, gases still present in the
for the kind funding.
void volume of the column are mixed with
the new stream leading to loss of methane
and mixing of air and methane. Increasing
the working capacity of the process allows
longer cycle duration, hence leading to a
less frequent switching of the columns and 8. References
reduces the loss of methane with the [1] K. Raab et al., “Innovative CO2 separation
of biogas by polymer resins: Operation of
purging air by 30 to 40% (see figure 4). As
a continuous lab-scale plant”, Eng. Life
a result, by integration of PCM, the
Sci., 12, 2012, pp. 327–335, doi:
efficiency of the process is enhanced. 10.1002/elsc.201100066

134
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Syngas cleaning and upgrading for SNG production - experimental

results on tars, hydrocarbons and other impurities
Sebastian Fendt1, Felix Fischer1, Hartmut Spliethoff1,2
1 Institute for Energy Systems, Technische Universität München, 85748 Garching, Germany
2 ZAE Bayern, 85748 Garching, Germany

1. Introduction als and degradation effects have to be

Synthetic natural gas (SNG) can be pro- analysed before commercialisation.
duced by thermochemical gasification of
lignocellulosic biomass and subsequent 3. Test rig description and performed
catalytic syngas conversion. At the Insti- experiments
tute for Energy Systems, the complete The test rig consists of an allothermal flu-
process chain from biomass to raw-SNG is idised bed gasifier, a hot gas filter, a gas
built up in a small-scale demonstration cleaning and an upgrading unit (see Fig. 1).
test rig. It consists of an allothermal fluid-
ised bed gasifier, a hot gas cleaning unit
and a fixed bed methanation reactor. Ex-
tensive gas analysis methods are integrat-
ed for the permanent gas components as
well as minor substances (hydrocarbons,
tars, sulphur components). The test rig is
used to analyse the syngas cleaning stages
and to determine the influence on the
methanation reaction.

2. Technology description
Hot gas cleaning technology is not yet
state of the art, but compared to commer-
cially available technologies (e.g. gas
washing with solvents) it offers several
advantages. The main purpose is minimis-
ing energetic losses and hence increasing
the overall process efficiency. Ideally, the
temperature of the syngas is decreasing
from the gasifier to the methanation reac-
tor and no reheating is required. While Figure 1: Test rig for long-term investiga-
filtration systems for high temperatures tion of biogenic SNG production
are available, the required catalytic re-
forming and adsorption processes are sub- The gasifier can be run with different
ject of ongoing research. In particular the steam to biomass-ratios (S/B) at tempera-
long-term stability of the catalyst materi- tures up to 850°C. After passing a filtration
stage, the syngas is fed to a catalytic tar

135
reformation reactor operating at tempera-
tures above 800°C. The amount of tars can
be measured before and after the reactor
with SPA (Solid Phase Adsorption) analysis.
The formation and conversion of hydro-
carbons can be observed with a gas chro-
matograph using a flame ionisation detec-
tor (FID). In the following cleaning stages,
Figure 2: Chromatograms of hydrocarbon
chlorine and sulphur components are ad-
concentration before (top) and after tar
sorbed on Sodium aluminate and Zink ox-
reformer (bottom)
ide. H2S is measured online and additional
adsorptive measurements are carried out
Exemplary results of the tar reformation
for organic sulphur compounds. The
process can be seen in Figure 3.
methanation reaction takes place in a two-
zone, cooled (air or thermal oil) fixed bed
reactor at adjustable outlet temperatures
between 280 - 350°C. Pressures up to
5 bar can be reached.
Since the focus of the conducted experi-
ments is the analysis of the syngas clean-
ing steps, the gasification is kept at a con-
stant biomass input of approx. 1 kW, an
S/B-ratio of approx. 2 and temperatures of
810 - 820°C for a period of 100 hours (with
interruption). Temperatures and volume
flows in the gas cleaning and methanation
unit are varied only to some small extent.

4. Results
The conducted experiments show a nearly
constant formation of hydrocarbons dur- Figure 3: Chromatograms of tar concentra-
ing the gasification over the 100 hour pe- tion before (top) and after tar reformer
riod. Figure 2 shows exemplary chromato- (bottom)
grams of the hydrocarbon concentration
before and after tar reformation. It can be The amount of tars is significantly reduced
concluded that the hydrocarbons are al- during the reformation. Furthermore, the
most entirely decomposed during the tar influence of sulphur components on the
reformation. formation is analysed.

5. Conclusions
Experimental results show the efficiency
of the realised syngas cleaning regarding
tars and sulphur components during 100
hours. Long-term test in combination with
post-mortem catalyst analysis show the
degradation effects on the catalysts.

136
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Advanced concepts for integrated SNG production at pulp mills

Katja Kuparinen1, Esa Vakkilainen1, Jero Ahola1, and Pasi Vainikka2
1 LUT School of Energy Systems, Lappeenranta University of Technology, Lappeenranta, Finland
2 Technical Research Centre of Finland

1. Introduction following reaction (1). Methanation forms

Technically feasible and cost-efficient methane and water from hydrogen and
energy system based solely on renewable carbon dioxide following the Sabatier
energy is possible by using advanced reaction (2). Renewable CO2 for
methods for energy generation. At pulp methanation can be captured from the
mills, renewable gas production via pulp production process, for instance from
power-to-gas or biomass gasification lime kiln. For experiments of power-to-gas
integrated in the pulp production process process, an electrolysis testing equipment
can be a way to both reduce the amount has been obtained.
of fossil fuels used at the mill and provide
new business opportunities related to 2 H2O 2H2 + O2 (1)
renewable energy. Lime kiln is typically
the only user of fossil fuels at a modern 4H2 + CO2 CH4 + 2H2O (2)
pulp mill during normal operation process.
In addition to pulp production, pulp mills Gasification of biomass has been used in
typically produce heat and electricity using several pulp mills during the last decades.
residual biomass and black liquor. Residual Biogas has been fired in lime kiln alone or
biomass gasification in addition to or in in addition to traditional lime kiln fuels. At
spite of direct firing bring about new pulp mills, circulating fluidized bed
possibilities for fossil fuel replacement or gasifiers are typically used, and biomass
business. Electricity and heat are in many has been usually residual biomass from
cases used more than produced at the pulping process, such as bark.
modern pulp mills. As an alternative to
selling, excess electricity can be used to
produce oxygen and hydrogen from water
using electrolysis. Oxygen can be used in
the mill processes, where it is needed
anyway, and hydrogen can either be
combusted in lime kiln to replace fossil
fuels or refined further to methane or
other products.

2. Technology description
Alkaline electrolysis is currently the
commercially available electrolysis
method [1]. Electrolysis produces pure Figure 1. Electrolysis and methanation in
oxygen and hydrogen by splitting water pulp mill process

137
3. Integration in pulp mills 4. Results
Pulp and paper industry is an attractive At first, the benefits of the integration of
environment for integration due to ready electrolysis come from existing use of
infrastructure and existing use of oxygen oxygen and replacement of fossil fuel at
for delignification. The integration effect the mill. In the case of gasification, uses
has been estimated using MillFlow mass for residual biomass are often needed, as
and energy balances program [2]. well as solutions for CO2 emission
Hydrogen or methane can be used as lime reduction by replacing fossil fuels with
kiln fuel with little or no modifications to renewables.
the existing combustion process.
5. Conclusions
Lime kiln fuel replacement Neo Carbon Energy project is looking for
Fossil fuels used in lime kiln can be successful business cases within an energy
substituted using gas from renewable system based entirely on renewable
sources. Replacement with methane or energy. Pulp and paper sector with
hydrogen needs little or none existing infrastructure and supply chains is
modifications in burning equipment, while a potential part of this kind of energy
gasification gas requires significantly system, in the roles of user and producer
more. of renewable energy and added value
products.
Advanced opportunities
Existing natural gas network in developed 6. References
countries is an easy way to transport
methane and also limited amounts of [1] M. Lehner et al. Power-to-Gas:
hydrogen. Transport using BioLNG is Technology and Business Models. ISBN
another option. These gases, as well as 978-3-319-03995-4. Springer, Austria
(2014).
biogas from gasification, can also be
refined further to other products, such as
[2] M. Hamaguchi et al. Additional revenue
chemical or liquid transportation fuels. opportunities in pulp mills and their
This creates various possibilities for impacts on the kraft process. D.Sc. Thesis,
development of pulp mills towards Acta Universitatis Lappeenrantaensis 562,
modern bio-product mills (Figure 2). ISSN 1456-4491, Lappeenranta University
of Technology (2013).

Figure 2. Bio-product mill concept

138
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Off-Grid biomethane mobile solution - Investigation on upgrading &

storage mobile units and centralized injection facility
Dr. Laura Gil Carrera

Gas Networks Ireland, Gasworks Road, Cork, Ireland, laura.gilcarrera@gasnetworks.ie

1. Introduction evaluated for this purpose. The membrane

Research shows that the majority of plant has a capacity for raw biogas flow up
biogas sources are remote from the gas to 300 m3/h [2] and PSA from 50 - 200
grid (i.e. 36% off-grid farms and 21% off- m3/h [3]. Such technologies are mounted
grid landfill in Ireland), and thus on a trailer in a 20 ft container. Upgraded
represents both a challenge and an biogas is then compressed to a maximum
opportunity in getting to market/grid. To of 250 bars and stored in gas vessels on
overcome these issues and to sustainably the second truck within a container. The
produce, capture and utilize this gas, a standard gas storage containers are
centralized biomethane grid injection available in steel or in composite tanks.
facility with third party access has been The standard steel vessels have a total
proposed and further investigated. storage capacity of 2,500 Nm3 whereby
A centralized grid injection and a virtual the composite vessels have a total storage
pipeline transport solution (cleaning, volume of 5,200 Nm3 [4]. Such trucks
upgrading and storage mobile units) are would ideally run on biomethane, which
critical to the development of the wider could reduce fuel cost up to 40% [5].
green gas industry in countries where the Trucks deliver biomethane to centralized
physical or economic conditions deems gas injection facilities where the gas is
the installation of a real pipeline unfeas- then odourised and quality controlled
ible. In this paper technical and before being injected into the gas grid.
economical challenges of an aggregator
and centralized biomethane grid injection 3. Economical analysis
model are identified and discussed. The collected data has been used to
perform economical analysis for different
2. Technology description off-grid biomethane scenarios in an Irish
The following technical elements were context, focusing only on cleaning, storage
evaluated: a centralized injection point, mobile units and gas injection.
where the biomethane transported from Assumptions & Scenarios
each cluster is injected, and a mobile The grid injection facility is provided by
solution including cleaning/upgrading the gas network operator; however
technology and storage units. producers are responsible for gas
The mobile units consist of a cleaning and conditioning and an injection fee. Bio-
upgrading technology to remove mainly methane is injected into the high pressure
CO2 and H2S and other impurities which pipeline, therefore propane addition is not
also has a negative effect on equipment required.
[1]. Membrane and pressure swing Key variables for sensitivity analysis are
adsorption (PSA) for small scale were distances, consumption, compliance with

139
 the transport, environmental and security low capacity clusters. Regarding the
norms in addition to the biogas cost, storage, composite vessels were found to
investment and capacity factor. be the most cost-effective option.
Baseline scenario has a total raw biogas Although it requires a higher CAPEX, the
capacity of 275 m3/h – 16 GWh (5 small OPEX and availability for higher trans-
scale biogas plants), CH4 53-62%, low ported volume makes a difference in the
pressure biogas storage capacity 30-48 producers’ revenue and NPV analysis.
hours/site, distance between plants 30-60 Technical limitations regarding the storage
km, transportation and setting-up time 2 and pressure requirements might impact
hours. Such scenario was studied while the investment; alternatively delivering
varying the number of biogas plants from the biomethane into a filling station in-
3 to 5, the upgrading technology (memb- stead of centralized injection could reduce
rane/PSA) and transport capacity (2,500 operational cost avoiding additional comp-
m3/5,200 m3). Furthermore, it was comp- ression and storage. The economics of
ared with a decentralized plant (8 GWh). virtual pipeline are significantly influenced
by the distance and the biogas production
4. Results and storage capacity. Incentives may be
The study of the baseline scenario and its necessary for economic justification.
alternatives shows that a centralized
system is required to make the business 5. Conclusions
case for small scale producers. Clustering farms, landfills and wastewater
Table 1 shows a comparison of the capital treatment plants to facilitate use of a
(CAPEX) and operational cost (OPEX) [6] of mobile upgrading and storage system is
the most representative scenarios. imperative for achieving economies of
scale and make biogas market accessible
Decentralized Mobile Sol'n Mobile Sol'n
1 plant 5 plants 3 plants
for small scale producers. However,
Capacity - kWh
Capital
8,000,000
Φ
16,000,000
Φ
10,000,000
Φ
biomethane quality requirements for end
Storage raw biogas
Cleaning & Upgrading
40,000
520,000
360,000
1,005,000
275,000
520,000
use applications, technically demanding
Gas Conditioning - compression
Storage biomethane
252,000
220,000
405,000
220,000
308,000
220,000
mobile units, restrictive guidelines and
Trucks 110,000 220,000 220,000 high cost for grid injection are among the
Grid Connection Contrib' 342,000 342,000 342,000
Total Capital Investment 1,484,000 2,552,000 1,885,000 prevailing challenges.
Capital Investment/Site 1,484,000 510,400 628,333

Operating Cost / annum

Cleaning & Upgrading
Φ
20,000
Φ
30,000
Φ
30,000
6. References
Injection/Pressurization 50,000 50,000 50,000 [1] Eekelen, R. N., Wolters, M. 2011 Design,
Electricity 100,000 150,000 120,000
Labour 70,000 140,000 120,000 operation and maintenance of local
Insurance 100,000 120,000 110,000
Mobile - Transport 24,100 41,800 41,800 biogas networks. International Gas
Total Annual Opex 364,100 531,800 471,800 Research Conference, Seoul.
Annual Opex /Site 364,100 106,360 157,267
[2] Flesch, S. 2013 Biomethane calculator &
Table 1. Economic analysis. cooperative biogas to biomethane
developments. Biomethane Regions.
[3] NeoZeo AB & SIA “NeoZeo”
Membrane technology was chosen due to
[4] Luxfer, Gas Cylinders. Bulk gas transport
its higher upgrading capacity, since PSA (BGT) solutions, G-Stor Pro, 2015.
would be a limiting factor in the 5 plants [5] Baldwin, J. 2014 Biomethane to Grid UK
scenario. However, the higher investment Project Review. CNG Service Limited.
of such technology could affect the [6] Department of Energy & Climate Change
economical viability for clusters with (GB) Waste plant cost revenues -
capacity bellow 150 m3/h, therefore, PSA Renewable Heat Incentive Biomethane
may be the most feasible technology for Tariff Review.

140
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Offshore biomethane production: the new frontier of anaerobic

digestion in aquaculture and maritime operations
Mario A. Rosato1
1 Sustainable Technologies SL, Barcelona, Spain

1. Introduction dumping their garbage and sewage in the

Aquaculture is a fast growing industry, ocean, because the MARPOL directive
listed among the priorities of the EU for requires no treatment. Offshore digesters,
ensuring reliable food sources. At the moored in strategic points along sailing
same time, the impact of fish farms on the routes, could become the "fuelling
marine environment is high, both in terms stations" of sea, where ships would dump
of organic matter dispersed in the sea and their organic waste and refuel compressed
CO2 emissions from fishing vessels biomethane that can be easily co-fired in
operation. During the research project naval Diesel engines in order to save oil
H2Ocean, a novel type of digester and reduce CO2 emissions. Offshore
conceived for operation in offshore upgrading of the biogas presents some
environment was developed. It is peculiarities: environmental safety in case
characterized by combining the of wreckage and minimum energy and
advantages of both CSRT and PFR, using chemicals consumption are the main
the pitching movement of the moored technology selection parameters. The
digester to create a travelling wave that most suitable technology appears to be
provides thorough yet mild agitation of the simple biogas washing with a
the slurry. The potential of offshore scrubber, just with sea water. The highest
anaerobic digestion is huge, since the energy input is found to be the
aquaculture operation produces large compression of biomethane to 200 bar.
quantities of waste algal biomass and
furthermore, about 2% of the fish live 2. Technology description
weight usually dies of natural causes The floating digester is a combination of
before the harvest, with the dead fish plug flow and multistage CSRT, with the
representing an interesting substrate in peculiarity that the agitation system is
terms of biomethane productivity (600 powered by the waves’ energy. No more
Nm3/t VS, measured with an AMPTS II information about its internal construction
instrument in batch mode). The energy for details can be disclosed at this stage, since
the operation of fish farms is currently the concept is under patenting. The
provided by Diesel generators installed on external appearance is that of a
barges, so the installation of a digester catamaran.
nearby will enhance the reliability and This shape was chosen because it provides
general economy of the whole more stability and space for the
aquaculture system. On the other hand, installation of the CHP (combined heat
maritime traffic represents a big and power) generator, the emergency
environmental impact, with both torch, and the biogas purification and
passenger and commercial vessels compression units.

141
 Overall efficiency of the compressor = 85%
Sea water needed to wash the biogas =
2,617 m3/day
Energy required by the sea water pump =
95 kWh/day
Energy for aux. services = 205 kWh

4. Results
The study shows that, in the special case
Figure 1. Block diagram of a floating
of offshore biomethane production, 2.53
anaerobic digestion plant with water
Nm3 of CH4 must be produced from
scrubbing upgrade and compression of
organic waste in order to obtain 1 Nm3
biomethane
compressed @ 200 bar, ready for use as
fuel in ships. The resulting EROIE (energy
3. Mass and energy balances
return on invested energy) is 0.4.
Based on batch tests on different kinds of
marine biomass, the theoretical mass and
5. Conclusions
energy balances are the following:
Washing the biogas with sea water in
order to obtain biomethane is feasible,
Mass balance
since the energy consumption for
Daily input = 0.5 t/day dead fish + 1 t/day
pumping the seawater is less than 1% of
seaweeds + 2.7 t/day solid waste from
the LHV of the biomethane. Producing
ships + 10 m3/day wastewater = 2.5 t VS
electricity to compress the biomethane by
(total average).
means of a conventional CHP generator
Daily output of digester = 1,011 Nm3 CH4 +
leads to a very low EROIE because of the
544 Nm3 CO2 + 0.72 t VS (digestate)
conversion low efficiency. The alternatives
Daily output of biomethane @ 200 bar =
to improve the EROIE are either replacing
354 Nm3.
the CHP generator with a fuel cell
(technically not mature technology) or
Energy balance
compressing the biomethane by means of
65% of the biogas produced is employed
wind or wave power.
in the CHP generator to run the floating
anaerobic plant’s services, the
6. References
biomethane compressor and the biogas
[1] M. Rosato. Own research during H2Ocean
purification system. The waste heat can project (Not publishable till 2016 because
only be used to heat the digester. The of patent secrecy). www.h2ocean-
remaining 35% of the biogas is purified project.eu
and compressed as biomethane for
fuelling ships. [2] Z. Duana, R. Sunc. An improved model
Input: calculating CO2 solubility in pure water
0.66 * 1,011 Nm3 CH4 * 9.94 kWh/Nm3 * and aqueous NaCl solutions from 273 to
0.4 = 2,613 kWh (electric) 533 K and from 0 to 2000 bar. Chemical
0.5 * 1,011 Nm3 CH4 * 9.94 kWh/Nm3 * Geology 193 (2003) 257 – 271, Elsevier.
0.45 = 2,939 kWh (thermal)
[3] M. Mezzadri; E. Antonini; V.Francescato .
Output:
Purificazione e upgrading del biogas in
Energy to compress the biomethane to biometano. Veneto Agricoltura e AIEL
200 bar = 354 Nm3 * 20 MPa / 0.85 = (2010).
8,327 MJ = 2,313 kWh

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Analysis of power-to-gas technology with oxyfuel combustion

integration
Manuel Bailera1, Pilar Lisbona1, Luis M. Romeo1,2
1 Emission Reduction in Energy Systems Area, CIRCE, Zaragoza, 50018, Spain
2 Department of Mechanical Engineering, EINA, Universidad de Zaragoza, Zaragoza, 50018, Spain

1. Introduction Methanation
Nowadays energy storage has become a Three methanation adiabatic reactors with
critical issue for future society. Power-to- intermediate condensation stage achieve
gas (PtG) may store large amounts of methane molar fractions above 95% [3],
electrical energy in form of synthetic which is the technical condition for SNG
natural gas. A source of CO2 is needed and injection into pipeline network. Five
oxygen is produced as side-product. Both important parameters control the
issues can be solved by hybridizing PtG methanation process. Initial molar ratio
with oxyfuel combustion [1]. O2 could be H2/CO2 (3), and inlet temperature to
used for reducing electrical consumption reactors have been kept constant. A ratio
of the ASU, and CO2 would be supplied below 4 leads to C deposition [2] and
without energy penalty in its separation. given that oxygen would poison the
Carbon deposition inhibits catalysts and catalysts [3], a surplus of hydrogen is
must be controlled [3]. needed to eliminate the oxygen through a
controlled combustion, H2/CO2 = 4.075.
2. Plant description The flue gas flow sent to R1 is 3.8 kg/s and
The hybridized plant consists of an oxyfuel represents approximately 8.8% of the
combustion integrated with PtG plant to original flue gas from the boiler. The inlet
produce SNG through methanation [2], temperature to reactors is fixed by the
using flue gas and hydrogen generated by technical limitations of commercial
an electrolyser (Figure 1). Alkaline catalysts (190°C). The remaining variables
electrolyser size is 100 MW ( ), as a are the flow of condensed water (4), and
potential future scenario, which produces recirculations in R1 (5) and R3 (6), and
0.8 kg/s with 97.9 %vol. H2, with 80% . Recirculation controls temperature in
efficiency. Oxygen from electrolysis partly the reactors, changing equilibrium
provides the required comburent (1). constants and concentrations. While low
water content displaces equilibrium
towards methane production.

Oxyfuel combustion
A 151.8 MW oxyfuel plant with 17.0 kg/s
coal consumption and a 35.16% global
efficiency is considered. LHV of coal is 25.4
MJ/kg and its composition is shown in
Table 1. Once 67.3% of water and all
Figure 1. Oxyfuel plant hybridized with PtG sulphur compounds are eliminated, 80%

143
of flue gas is recycled to the boiler. ASU When exceeds , H2O and CO2 final
supplies O2 up to 15% excess with an content are reduced and changes in CH4
electric consumption of 180 kWh/tO2. Gas concentration are less pronounced. Also,
composition is shown in Table 1. auxiliary work decreases faster with .
Thus, an optimized operation point is
Table 1. Coal and flue gas composition.
= 87.3% and = 66.0%, with
Flue Gas
%
Coal
% Flue
after H2O
64.14% PtG efficiency. After H2O
mass vol Gas condensation, 1.37 kg/s of SNG are
removal
C 66.1 CO2 85.30 91.22 produced with a volumetric composition
H 3.6 CO 0.12 0.12 of 95.02% CH4, 2.29% H2, 1.16% CO2,
O 7.1 H2O 9.56 3.35
N 1.6 O2 3.18 3.41 1.00% N2 and 0.53% H2O. Additionaly, 61.7
S 0.6 SO2 0.06 0.00 MWth are available at 80-120°C, 14.2
M 8.6 NO 1.78 1.90 MWth at 149-190°C and 23.7 MWth at 224-
Z 12.4
359°C.
3. Results and discussion CO2 generated in the oxyfuel power plant
Results from Aspen Plus® simulations is diminished from 969.9 kgCO2/MWh to
reveal how oxyfuel plants may improve 940.8 kgCO2/MWh by means of PtG plant
efficiency with PtG technology integration. integration since part of the CO2 is reused.
ASU electrical consumption is decreased 851.1 kgCO2/MWh are directed to storage.
15.2% because O2 is also generated from
electrolyser. While compression work falls 4. Conclusions
8.2% since flue gas to compression is Oxyfuel combustion efficiency improves
reduced (2). Attending to the PtG plant, its about 3.1% when hybridized with PtG. It
efficiency mainly depends on the reduces ASU and compression electrical
composition of final gas (eq. 1). It will be demand and PtG achieves 64.14% global
maximized by maximizing H2 content efficiency, maximizing H2 final content
(minimum 95% CH4 in SNG). under methane constraint. A higher
recirculation in R1 than in R3, results in
·
= ( . 1) lower H2O and CO2 content which lead to
+ minor auxiliary power needs. A 8.8% of
An atmosphere with low water and high CO2 produced in combustion is reused in
methane content can lead to C deposition methanation, not emitted or compressed.
[2]. Figure 2 illustrates carbon formation
inside R3 which mainly depends on and 5. References
the temperature of condensation stage. [1] Zibell L. “Long-term electric energy
Over 47°C, C deposition is avoided in R3. storage using electrolysis + methanation”.
Siemens Technical Academy, Aveia
Consulting (2013).
[2] Gao J. “A thermodynamic analysis of
methanation reactions of carbon oxides
for the production of synthetic natural
gas”. RSC Advances, 2012, 2, 2358-2368
(2012).
[3] Agersborg J. “Integration of Power-to-Gas
in Gasendal and GoBiGas”. Master’s
Thesis within the Sustainable Energy
Systems programme, Chalmers University
Figure 2. Conditions of carbon deposition
of Technology (2013).

144
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Scrubber oil recovery in biomass gasification plants

Laura Malek1
1 Department of Chemical Engineering, Lund University, Lund, Sweden

1. Introduction order to mimic a spent scrubber liquid from

Tar scrubber liquid regeneration is an an actual gasification plant and ratio was
important step in lowering operation costs determined by analyzing the spent
in small scale biomass gasification plants. scrubber liquid from a small scale CHP
Although there are separation systems plant. The composition ratio is presented in
using stripper technology commercially Table 1.
available [1], these systems may be too Table 1. Weight ratio of components in
sophisticated and too expensive for small model spent scrubber liquid
scale combined heat and power (CHP)
plants. Component Amount (wt %)
Scrubber liquid 50 %
Aim Water 5%
This study examines the possibility to Wood tar 5%
regenerate spent scrubber liquid using a Sludge 40 %
centrifuge. Real tar/ash reject (sludge)
from a small scale CHP plant was used for 3. Separation procedure
the experiments. A selection of scrubber A small benchtop centrifuge was used to
liquids was tested on their ability to separate the model spent scrubber liquid
dissolve the sludge and were then samples. Centrifugation time and sample
centrifuged to determine the possibility of temperature was varied according to the
oil recovery. The effect of separation time experiment parameter matrix presented in
and sample temperature was studied. Table 2.
Table 2. Parameter matrix for separation
2. Scrubber liquids
experiments.
Seven different scrubber liquids were
selected for testing after reviewing Parameter Low Medium High
literature on tar and removal of volatile Temp. (°C) 50 70 90
organic compounds [2-4]: bio-diesel (RME), Time (min) 1.5 5 10
diesel, vegetable oil (rapeseed), linseed oil,
linoleic acid, motor oil (10-50W) and Twin samples were prepared for each
silicone oil. The silicone oil was disregarded parameter combination and each sample
after initial solubility testing of the sludge. weighed approximately 12 g.

Model spent scrubber liquid Grade of separation

For the experiments, model spent scrubber Separation efficiency was determined by
liquids consisting of scrubber liquid, sludge, weighing the top phases of the samples
water and commercial wood tar, were after centrifugation. Grade of separation
prepared. The composition was chosen in (GOS) is defined as:

145
 ܶ‫݁ݏ݄ܽ݌݌݋‬ሺ݃ሻ above 50 % at high centrifugation time and
‫ܱܵܩ‬Ψ ൌ
ܶ‫݈݁݌݉ܽݏ݈ܽݐ݋‬ሺ݃ሻ sample temperatures. This implies that the
lighter tars and oil residues previously
Considering the composition ratio of the
trapped in the sludge, together with the
model spent scrubber liquid, the desired
wood tar, have been separated from the
GOS is 50 %.
solid bottom phase and ended up in the top
phase. On the basis of these results, a
4. Results and discussion
scrubber liquid regeneration system using
Figure 1 shows the GOS for all scrubber
centrifugation could either allow a small
liquids. The best separation efficiency was
amount of solid particles to be recirculated
obtained for RME and diesel samples.
to the scrubber or bleed off excess
scrubber liquid to prevent accumulation in
60
the system.
55
GOS (%)

50 Top phase
Bottom phase 5. Conclusions
45 Of the evaluated scrubber liquids, RME and
40 diesel achieved the highest GOS. The GOS
is highly dependent on the centrifugation
E

oil

oil

oil
cid
se
RM

time and the sample temperature.

Die

tor

ed

ed
ic a

se

se
Mo

ole

Lin

pe

Regenerating spent scrubber liquids using

Lin

Ra

centrifugation has potential to significantly

Figure 1. GOS at 90°C and 10 minutes of lower operation costs in small scale CHP
centrifugation time for all scrubber liquids plants.
Top phases that were entirely free of solid
particles were only obtained for the RME 6. Acknowledgement
and diesel samples, and only at higher The received financial support by Meva
temperatures and longer separation times. Energy AB and the Swedish Energy Agency
Figure 2 shows GOS results for all the RME is greatly appreciated.
and diesel samples.
RME 50 °C
7. References
RME 70 °C
RME 90 °C
[1] H. Boerrigter et al. "OLGA" tar removal
65
Diesel 50 °C
Diesel 70 °C
technology. ECN-C-05-009, The Energy
60 Diesel 90 °C
research Centre of the Netherlands
GOS (%)

55 (2005).
50 [2] B. Ozturk, D. Yilmaz. Absorptive Removal
of Volatile Organic Compounds from Flue
45
Gas Streams. Process Safety and
40
Environmental Protection 84(5): 391–98
1.5 5 10 (2006)
Centrifugation time (min)
[3] T. Phuphuakrat et al. Absorptive Removal
Figure 2. GOS for RME and diesel samples. of Biomass Tar Using Water and Oily
Materials. Environmental Progress 20(1):
The high GOS values for the RME samples
27–35 (2011)
at low centrifugation time can be explained
[4] S. Majumdar et al. A Pilot-Scale
by the presence of solid particles in the top Demonstration of a Membrane-Based
phase. Values below 50 % indicate that Absorption- Stripping Process for Removal
scrubber liquid is trapped in the solid and Recovery of Volatile Organic
bottom phase of the samples. Both RME Compounds. Environmental Progress
and diesel samples reached GOS values 20(1): 27–35 (2001)

146
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Energy balance, mass balance analysis and econometric modelling of a

biological-fermentative power-to-gas process
Katharina Edelmann1, Sabine Schenk1, Hubert Röder1, Raimund Brotsack2, Wolfgang
Mayer3
1Straubing Center of Science, Schulgasse 16, 94315 Straubing; 2MicroPyros GmbH, Imhoffstraße 95, 94315

Straubing; 3University of Applied Science Kempten, Bahnhofstraße 61, 87435 Kempten

1. Introduction bundle. The main component of the pre-

The German energy transition aims to pilot plant is a 100 liter fermenter in which
realize an amount of renewable energies the methanation takes place.
in the final energy consumption until 2050 In order to gather the energy flows the
between 80 and 85 % [1]. A great share of power consumption is metered itemized
these renewable energies will be sources to every individual power consumer. Thus
that are supply-dependent as for example it is possible to make a statement about
wind energy and photovoltaics. The which system components are the main
renewable energies pose great challenges consumers. The results are used for
to the given grid infrastructure. identifying approaches to optimize the
Considering multiple studies [2, 3, 4] re- process considering the energy
garding the development of excess consumption.
capacities in the future energy system the The next step of development will be a
Power to Gas technology appears to pilot plant with a 1,000 liter fermenter
assume an important role in this system. (Figure 1). The energy flows shall be scaled
The Power to Gas technology enables an up by a computer model. The metered
upgrade of biogas to biomethane. In a first data serve as validation of the pre-pilot
step excess energy from the electricity plant.
grid can be used to produce hydrogen The upscale from the pilot plant to the
within an electrolysis process. In a second demonstration plant will be done with the
step carbon dioxide out of biogas and similar procedure. The simulated data will
hydrogen are transformed to biomethane be evaluated by the metered data from
microbiologically by the use of methane- the demonstration plant when it is
producing microorganisms (domain: constructed.
archaea).

2. Methodology
The basis for analyzing the energy flows is
to record the power consumption at a pre-
pilot plant. This plant is connected to a
sewage treatment plant that delivers
carbon dioxide as well as nutritional Figure 1. Plant size development
medium for the Power to gas process. In The calculated mass and energy flows are
this early stage of development the used as main input variables for the
needed hydrogen is supplied by a cylinder econometric model (Figure 2).

147
 4. Conclusions
A preliminary approach for the mass and
energy balance as well as for the
econometric analysis of the power to gas
process has been carried out. The ASPEN
software is considered to be an applicable
tool for the analysis of the power to gas
process. As well the plant design as
associated the mass and energy flows will
be optimized before the corresponding
development steps are realized.
Figure 2. Econometric Model Power to Gas For the retrograde econometric analysis
process the analysed price development
means high requirements for the
3. Results and Discussion effectiveness of the process regarding its
In order to improve the plant design and mass and energy balance and low specific
the input variables for the econometric upgrading costs are needed to be
model the methodology has to be competitive on the market.
adjusted. The software tool ASPEN will be
introduced. This allows simulating 5. References
different variants of the process (Figure 3). [1] Deutscher Bundestag, Drucksache
18/739, last accessed on 14.01.2015,
h p://dip21.bundestag.de/dip21/btd/18/
007/1800739.pdf.
[2] Nitsch, J.; Pregger, T.; Naegler, T. et al.
(2012): Langfristszenarien und Strategien
für den Ausbau der erneuerbaren
Energien in Deutschland bei
Berücksich gung der Entwicklung in
Europa und global. Schlussbericht BMU.
[3] Verband Der Elektrotechnik (Hg.) (2012):
Figure 3. Adjusted Methodology
Energiespeicher für die Energiewende.
Compared to North-America the European [4] Klaus, Thomas; Vollmer, Carla; Werner,
gas price is more than three times higher Kathrin et al. (2010): 2050: 100%. Ener-
and multiple studies on future gas prices gieziel 2050: 100% Strom aus erneu-
show the trend of an increasing gas price erbaren Quellen. Hg. v. Umweltbundes-
due to an increasing global demand amt.
[5] Prognos AG (Hg.) (2011): Energieszena-
(Figure 4).
rien 2011.
[6] Interna onal Energy Agency (2013):
World Energy Outlook 2013.
[7] DLR, Fraunhofer IWES, IfnE
(2012):Langfristszenarien und Strategien
für den Ausbau der erneuerbaren
Energien in Deutschland bei
Berücksich gung der Entwicklung in
Figure 4. Future Development of Natural Europa und global
Gas Prices [5, 6, 7]

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Catalytic decomposition of biogas: a novel approach for biogas

valorisation into syngas and bio-carbon nanofibers.
Saul de Llobet1, José Luis Pinilla1, Rafael Moliner1 and Isabel Suelves1
1 Instituto de Carboquímica (CSIC). C/ Miguel Luesma Castán 4 50018 Zaragoza, Spain.

1. Introduction the CDB process was analysed considering

Biogas is an energy source from which CH4 and CO2 conversions, catalyst stability
electricity and heat are produced by its and carbon production. Those studies
direct combustion. Nevertheless, the allowed us to select the optimum
exploitation of the biogas for different experimental conditions to simulate the
applications like the production of implementation of a CDB continuous
hydrogen, syngas, high added value process, which is in fact the purpose of
carbon materials or bio-methane appear this work.
as an interesting option. Particularly when
considering the renewable origin of the
source. In this context, the Catalytic
Decomposition of Biogas (CDB) to
simultaneously produce syngas (CO and H2
with smaller amounts of unconverted CH4
and CO2) and bio-carbon nanofibers
(BCNF) is a potential alternative to be Figure 1. Scheme of the CDB process
considered [1]. Syngas can be further
processed to produce chemicals, liquid 2. Experimental
fuels or hydrogen or be used as engine The Ni/Al2O3 catalyst was prepared by the
feedstock since it presents better highly economic fusion method [1]. To
combustion characteristics than biogas carry out the experiments, a synthetic
[2]. In turn, BCNF are high added value CH4:CO2 mixture with a volume ratio of
materials that depending on their 60:40 (v:v) was selected in order to mimic
structure and surface properties can be biogas composition. Catalytic experiments
employed in different applications. Among were carried out at 600 ºC and 30 LN·gcat-
them, BCNF thermally treated to produce 1 -1
·h in a fluidized bed reactor described
graphite nanofibers and their use as elsewhere [4]. In order to determine the
anode in rechargeable lithium-ion operating parameters for a CDB
batteries is of important relevance. Work continuous process, the following
carried out in this field lead to the considerations were stablished:
publication of a Spanish patent and a PCT - A start-up experiment was carried out in
application [3]. order to produce BCNF material to
In previous studies, synthetic biogas initiate the simulation.
mixtures were decomposed in a fixed bed - 3 experiments 4 hours long were carried
reactor varying the experimental out (batch operation).
conditions in the presence of different - The amount of carbon produce after
metal based catalysts. Their behaviour on each batch was withdrawn and the

149
 necessary fresh catalyst was added in experiment is also considered (Eprocess), the
order to keep constant the catalyst difference becomes higher (17%).
inventory (note: carbon material
Table 1. Gas fuel energetic values.
contains catalyst).
Biogas CDB
3. Results L.H.V. (kJ) 21492 20099
Catalyst activity Eprocess (kJ) - 2249
During the experiment, catalyst showed a Enet (kJ) 21492 17851
good performance. The average outlet %deviation - 17
gases concentration is included in Figure
2. Comparing the outlet gases However, the co-production of syngas,
concentration of the three cycles, less with better combustion properties than
than a 3% of standard deviation was raw biogas [2], and interesting carbon
observed highlighting the considerable materials (Figure 3) with potential
repetitiveness achieved. applications make up for the loss of L.H.V.

Figure 3. TEM micrographs of the BCNF

produced in the CDB.

Figure 2. Scheme of the continuous CDB 4. Conclusions

process. Based on the presented results, the
implementation of the continuous CDB
Mass and energy balances process in a fluidized bed reactor is
Mass and energy balances were carried feasible. The simultaneous production of
out in order to analyse the viability of the an interesting syngas and valuable BCNF
CDB process as compare with the make up for the loss of outlet gases L.H.V.
traditional biogas combustion. In both The CDB appears as an interesting process
cases, 1 m3 of biogas was used as basis of to valorise biogas.
calculation. According to mass balance, for
each m3 of biogas fed, 5.91 g of fresh 5. References
catalyst (NiO/Al2O3) need to be supplied [1] S. de Llobet et al. Int J Hydro Energy 37
and 72.9 g of carbonaceous material are (2012) 7067.
recovered (with a 6.8 wt.% of Ni/Al2O3 [2] S. de Llobet et al. Int J Hydro Energy 38
catalyst). (2013) 15084.
Energy balances were carried out [3] Method for preparing graphite nanofibres
from biogas. I. Camean, N. Cuesta, S. de
considering standard enthalpies of
Llobet, A.B. Garcia, R. Moliner, J.L. Pinilla,
formation and heat capacity values. The
A. Ramos, I. Suelves.
L.H.V. of the CDB outlet gases is lower n°: PCT/ES2014/070509 (23/06/2014).
than that of the raw biogas (Table 1). If [4] J.L. Pinilla et al. Int J Hydro Energy 32
the heat needed to carry out the (2007) 4821.

150
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Towards energy self-sufficiency at Murcia Este WWTP

Francisco J. Navarro1, M. Mar Castro2 and Teresa R. Serna3
1 EMUASA, Plaza Circular 9, 30008 Murcia, Spain
2
AQUATEC, Plaza de Cetina 6, 1º Entlo. 30001 Murcia, Spain
3 AQUAMBIENTE, Plaza de Cetina 6, 2º Entlo. 30001 Murcia, Spain

1. Introduction viability of different technologies for

Besides contributing to the achievement biogas valorization.
of the European Union (EU) goals on
mitigation of global warming, production
and use of biogas allow creating many
economic and environmental benefits in
the surrounding areas.
It is expected, as laid out in the PER 2011-
2020 [1], that during the next years its
production and the use will be promoted
by the Spanish government, establishing
the legal framework and the pricing Figure 1. Pilot plant for biogas treatment
policies as it is estimated that in 2020, at Murcia Este WWTP.
biomass, biogas and urban solid waste will For testing purposes a pilot plant (Figure
represent an energy production up to 1) was built in Murcia Este WWTP, with
12,000 GWh (2010, 4,228 GWh). capacity to treat up to 10 Nm3/h of raw
Aguas de Murcia was born in 1989 as a biogas, including biogas cleaning by gas-
joint venture service company, 51% liquid absorption (acid, oxidative and
owned by the City of Murcia, and 49% by caustic scrubbing) and polishing: cooling
Hidrogea. The company leads the water and solid-gas adsorption (activated
cycle in the municipality of Murcia. carbon).
Aguas de Murcia manages 15 wastewater
treatment plants (WWTP), of which only
Murcia Este WWTP has sludge
stabilization treatment by anaerobic
digestion (AD).
This WWTP treats urban wastewater of an
equivalent population of 960,000 inhab-eq
and the design flow is 100,000 m3/day.
There are three anaerobic digesters with a
total volume of 18,317 m3. Figure 2. View of the pilot plant, the pump
2. Technology description and a vehicle fuelled by biogas.
From 2004 to 2012, Aguas de Murcia has This plant was enlarged subsequently to
developed in Murcia Este WWTP several include an upgrading phase and, from
research projects aimed to evaluate, from 2007 to 2010, efforts were focused on
a technical and economic perspective, the assessing the technical feasibility of

151
obtaining automotive fuel (BIOEDAR) from problem in 2014 was installed a separator
the biogas (Figure 2). screen in the pipe feeding the digester.
From to 2009 to 2012, Aguas de Murcia 3. Results
has participated in the BIOCELL project Figure 3 shows the monthly evolution of
(www.life-biocell.eu/).This project aimed biogas production during 2012, 2013 and
to demonstrate the industrial feasibility of 2014. The results show that it has been
energy production on WWTP from biogas possible to increase a 2.03% the amount
via PEMFC and Solid Oxide Fuel Cell of biogas produced in 2014 regarding to
(SOFC), developing suitable tools for 2013, and a 14.56% regarding to 2012.
industrial implementation.
At industrial scale, in September 2012, a
biogas-fuelled Combined Heat and Power
(CHP) system was commissioned (1 MW),
expecting to supply 100% of thermal
requirements and 40% of power demand.
Since its construction were implemented Figure 3. Monthly biogas production [Nm3
in the WWTP several measures aimed to biogas].
increase the amount of biogas generated:
The improvements have allowed
(i) Digesters cleaning,
producing 2,863,480 Nm3 biogas in 2014,
After 10 years of operation the useful
generating 5,707,000 kWh, a 7.42% higher
volume of the digesters was nearly a 30%
than energy production recorded in 2013.
lower. The digesters cleaning has restored
the useful volume and allowed to improve Last year biogas valorization has avoided
sludge mixing. the emission of 2,055 tons CO2 and more
(ii) Thermal insulation than 37 tonnes of SO2.
The digesters and a substantial proportion 4. Conclusions
of pipes were outdoors, causing significant The commissioning of the CHP plant in
thermal losses. To avoid such losses, in 2012 aimed to cover 40% of the electricity
2013 the 3 digesters were insulated. demand and virtually 100% of the thermal
(iii) High efficiency heat exchangers. requirements of the WWTP. Currently
Temperature is a key factor for AD proper 100% of the thermal and 42% of power
operation. In 2013 high efficiency heat demand are satisfied.
exchangers were installed to increase the The results show that by applying good
yields of heat transfer. operating practices and innovative
(iv) Sludge pretreatment by hydrolysis technologies it is possible reduce the
Also in 2013 a pretreatment by electro- energetic dependence on WWTP and also
kinetic disintegration was installed. It reduce GHG emissions.
consists on the application of an internal 5. References
high voltage field to the sludge, increasing [1] Plan de Energías Renovables (PER) 2011-
the methane gas production and reducing 2020. Publicaciones del Instituto para la
the final sludge production. Diversificación y el Ahorro de la Energía
(v) Sludge screening. (IDAE). Available in: http://www.idae.es
(Last visit: 08/10/2014).
Blockages in the sludge line and the loss of
useful volume cause drops in the
production of biogas. To avoid this

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Potential candidates for improvement of anaerobic degradation of

lignocellulosic biomass
Orsolya Strang1, Norbert Ács1, Roland Wirth1, Gergely Maróti2, Zoltán Bagi1, Gábor
Rákhely1, Kornél L. Kovács1,3,4
1 Department of Biotechnology, University of Szeged, Szeged, Hungary
2Institute of Biochemistry, Biological Research Centre, Szeged, Hungary
3Department of Oral Biology and Experimental Dental Research, University of Szeged, Szeged, Hungary
4Institute of Biophysics, Biological Research Centre, Szeged, Hungary

1. Introduction microbe communities were marked as

Lignocellulosic materials have great AD1 and AD2.
potential to satisfy the increasing demand
of resource for energy production. 3. Substrate
Lignocellulose containing biomass has vast In subsequent experiments corn stover
amount on Earth but it is recalcitrant and was used as substrate. Corn stover is an
therefore not so efficiently can be used. agricultural residue produced in vast
Lignocellulose is composed of cellulose, amount annually, potentially a cheap
hemicellulose and lignin. For the utili- substrate for biogas plants to replace
zation of substrates having high cellulose more expensive maize silage. Corn stover
content, the biogas producing microbial has high organic dry matter content, i.e.
community should include cellulose 81- 92%. Dried corn stover was pre-
degradeing microbes, which can break treated mechanically by shreding to 2 mm
down cellulose to easily utilizable sugar particles. Mechanical pre-treatment
monomers [1]. increase the surface to bacterial access.

2. Adaptation and isolation 4. Effect of AD1 and AD2

Our first aim was to examine if it was The effect of AD1 and AD2 on the biogas
possible to adapt this natural consortium production were examined.
to cellulose-rich substrate. The exper-
iments were carried out under thermo- 300
philic conditions at 55°C. -cellulose was 250
Methane yield Nml

used as substrate and the control ferm- 200

entors received glucose as carbon and 150
energy source. After a successful adap- 100
tation samples were taken from the adap- 50
ted fermentors and were inoculated onto 0
cellulose containing media for the 0 10 20 30
isolation and cultivation of cellulose de- Time (days)
F-AD1 F-AD2 Control
grading microbes. From these experiments
two mixed cellulolytic cultures were Figure 1. Effect of AD1 and AD2 to the
obtained. These cellulose degrading biogas fermentation

153
Several experiments were carried out, and 6. Effect of the candidates
each showed elevated methane yield in In the subsequent experiments the effect
case of addition of AD1 and AD2 to the of these strains on the biogas production
fermenters (Figure 1.) from lignocellulosic substrates is
investigated with the aim of constructing a
5. Metagenome analysis defined cellulolytic consortium effective in
To know better the cellulose degradation the intensification of the thermophilic
and the composition of these mixed anaerobic biodegradation of
cultures, DNA was purified. After the initial lignocellulose-rich substrates. Preliminary
difficulties, adequate quality and quantity results show promising outcome, the
of DNA was achieved for metagenome addition of the four bacterial strains and
analysis. To the metagenom analysis an their mixture according to the
Ion Torrent Personal Genome Machine® metagenome data evaluation to the
was used. Next generation sequencing of biogas fermenters enhance the methane
the total DNA samples identified the main yield.
orders being Thermoanaerobacterales and
Clostridiales with 70% and 10% abundan- 7. References
ces, respectively Thermoanaerobacterium [1] Kornél L Kovács, N Ács, T Böjti, E Kovács,
thermosaccharolyticum, Caldanaerobacter O Strang, R Wirth, Z Bagi. Biogas
subterraneus, Thermoanaerobacter pseud- Producing Microbes and Biomolecules,
ethanolicus and Clostridium cellulolyticum Biofuels: From Microbes to Molecules.
248 p., London: Caister Academic Press,
were the predominant strains (Figure 2).
pp. 47-92. ISBN 978-1-908230-45-4
[2014].

Figure 2. Dominant strains are Thermoanaerobacterium thermosaccharolyticum, Caldanaerobacter

subterraneus, Thermoanaerobacter pseudethanolicus and Clostridium cellulolyticum

154
2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Leachate recirculation and its effect on enhancing LFG production, and

site stabilization, a modeling study
Belkacem Adouane1 , Abdelmalek Benkorichi2 , Amir Bareche1 and Abderraouf Haddad1
1Department of Material Sciences, Laboratory of Applied Energetic Physics(LPEA), University of Batna,

Batna 05000 Algeria

2 Ecole Nationale Polytechnique, Ave. Hacen Badi, El Harrach, Algiers 16000, Algeria

1. Introduction hydraulic conductivity of waste is much

Burying MSW (Municipal Solid Waste) in higher than the vertical conductivity, this
controlled landfills is one of the most means that we need to have thin layers of
common techniques used nowadays. The waste; moreover, we found out that the
micro-organisms take care of the bio- hydraulic conductivity of the clay is much
degradation of the waste, which will result lower than the one of sand, which leads to
in stabilizing the landfill and landfill gas suggest the replacement of the clay by the
(LFG) production. sand in order to accelerate the humidifi-
The normal time that a landfill takes cation of the MSW massif. Figure 1, at the
before it is stable, and therefore could be end of this paper, shows a schematic dia-
used for other ends, e.g. a recreation area, gram of a bioreactor.
is of the order of 20 to 30 years, which is
quite a long time. This time will result in 2. Technology description
high operating costs. HYDRUS-2D is an interface of SWMS-2D
One of the novel ideas to accelerate the code, which allows the simulation of two-
life time of an active landfill is to dimensional flows of water and solute
recirculate leachate in order to optimise transport in variably saturated porous
the inner humidity, which will result in incompressible medium, permanent or
maximising the LFG production and thus transient, for various time steps
reducing stabilisation time to almost the
half of the time without recirculation. 3. Results
In this poster, we will study the recircula- The study of 2D leachate recirculation
tion of leachate back to the landfill to form represents the influence of gravity and
what’s called a bio-reactor. The aim is to pressure potential on moisture transfer.
enhance the biodegradation of the MSW, Reinjection of leachate inside the landfill
which will result in high biogas production. cell from eight meters depth, appears to
The study is carried out using Hydrus 2D be an effective way to boost the kinetics
software, which models the landfill cell as of degradation and thus also the produc-
a porous media. Results showed how the tion of biogas.
re-injection of leachate is affecting moist-
ure, porosity and hydraulic conductivity; 4. Conclusions
parameters that affect significantly the Reinjection of leachate is required to
biogas production and thus the time ensure an optimal moisture level in the
needed to the settlement of the landfill. cell of a controlled landfill.
This study has showed that the horizontal

155
The gravity force and pressure potential [1] A. Bitar, Modélisation des écoulements en
have a significant effect on the moisture milieu en milieu poreux hétérogènes 2D
transfer. / 3D, avec couplages surface / souterrain
The horizontal hydraulic conductivity of et densitaires. Thèse doctorat, Institut
National Polytechnique de Toulouse,
the waste is greater than the vertical
2007.P.16-17
hydraulic conductivity, thus, we suggested
[2] J. imunek, M. Th. van Genuchten and M.
thin horizontal layers of waste in the cell. ejna the HYDRUS Software Package for
The hydraulic conductivity of the clay is Simulating the Two- and Three-
low compared to the hydraulic conduct- Dimensional Movement of Water, Heat,
ivity of the sand, so we suggest replacing and Multiple Solutes in Variably-
the clay with sand to accelerate the saturated Media, University of California
humidification within the waste massif. Riverside, 2006.P.51
Reinjection of leachate is an effective [3] G.Y.S. Chan, L.M. Chu, and M.H. Wong,
means to accelerate the degradation E ects of leachate recirculation on biogas
kinetics and therefore the production of Production from landfill co-disposal of
municipal solid waste, sewage sludge and
biogas.
Marine sediment, Department of Applied
Biology and Chemical Technology,
5. Prospects The Hong Kong Polytechnic University,
x Studying the problem in (3D). 2002.P.393-399
x Studying the effect of the thermal [4] État des connaissances techniques et
phenomena on humidity and the recommandations de mise en uvre
various hydraulic parameters of pour une gestion des installations de
the porous medium. stockage de déchets non dangereux en
x Experimental study of the effect of mode Bioréacteur.
Coordination technique : Isabelle HEBE -
pH and compaction
Département Gestion Optimisée des
x Study leachate flow taking into
Déchets–Direction Déchets et Sols –
account the changing nature of the ADEME Angers,12.2007.P.40
porous medium, i.e. the coupling
between biodegradation and
hydraulic behavior (liquid/gas).

6. References

Figure 1. Schematic diagram of a bioreactor

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Digesters Upflow Anaerobic Sludge Blanket Treating Brewery Effluent

Ederaldo Godoy Junior1,2, Ricardo Osmar de Jesus1, José Rui Camargo1,2, Jorge Yago
Oliveira1 and Pedro Henrique de Jesus1,3
1 University of Taubate, Taubaté, R. Daniel Danelli s/n, Zip 12044-660, Brazil
2
Scholarship and Innovative Productivity Extension – CNPq
3
Scholarship Master ITAIPU BINATIONAL - CIBIOGAS

1. Introduction Volume of 974 m3 and a treatment

The present work was a comparative study capacity of 120 m3/h. Fig. 1 illustrates the
of four systems of digesters upflow schematic and photo of the concrete with
anaerobic sludge blanket (UASB) operating HDPE film.
with brewery effluent in a hot climate Configuration UASB circular steel.
region, in Brazil. In this case, there was a The UASB circular steel was protected by
epoxy paint and anodic protection. This
UASB IC steel, cylindrical steel UASB, a
reactor follows the same principle of the
UASB rectangular concrete and high reactor concrete previously presented and
density polyethylene (HDPE) and also a has a volume of 2,000 m3 and a treatment
digester system consists of two UASB plug capacity of 210 m3/h.
flow in rotomolded HDPE. Configuration UASB IC steel
The biodigester UASB IC in AISI 304
2. Materials and Method
stainless steel has 20 meters height,
Characterization of the sludge
volume of 664 m3 and a treatment
The digesters were inoculated with
capacity of 250 m3/h. The IC consists of a
flocculent anaerobic sludge reactors of the
reactor, relatively large circular tank that
brewery. The wastewater used in the
contains two distinct zones for the
experiment was of the brewery, stabilized
biological conversion of the effluent: The
thermally and chemically at COD of 2,090
lower treatment zone contains granular
mg/l. The flocculent sludge volume index
sludge in fluidized or expanded form. This
was 20-40 ml/ g TSS. The presence of
zone of complete mixing is characterized
filamentous microorganisms interconnect-
by high speed upward flow of liquid. These
ed with archaea Methanothrix soehngenii
speeds are produced by the flow of
is predominant.
effluent fed plus the flow of internal
Characterization of affluent
recycle. The recycle flow is generated by
The research was conducted in sewage
the gas collected at the top of the first
treatment station of a brewery located in
separator installed in the central part of
Jacarei SP, Brazil, 567 meters in relation to
the reactor and the resulting effect "gas
sea level. The climate, according KOPPEN
lift”. Fig. 2 illustrates the schematic view
is characterized as humid subtropical
of the digester and UASB IC used in the
climate and an average temp. of 23°C.
experiment, and the UASB circular steel.
Configuration UASB rectangular concrete.
The rectangular UASB digester used was
constructed in reinforced concrete and
protected from the harsh environment of Fig. 1: Design and view the UASB digester system
the effluent through pockets HDPE. rectangular in concrete and HDPE.

157
 3. Results and Discussion
Table 1 shows the results of the
(a) (b) comparison between the systems.
Fig. 2. View of the biodigester system UASB circular
in steel(a) and view of the digester system UASC IC Table 1: Comparative characteristics of the
in stainless steel AISI 304 (b). parameters studied UASB reactors
Flow Flow Tem
COD COD Efficie
Configuration UASB Plug Flow Reactor
Capacity rate
3 3
HRT
Inlet Outlet
rate pera
ncy
(m ) (m /d) (h) biogas ture
Polyethylene rotomolded 3 (mg/l) (mg/l) 3 o %
(m /h) (Nm /d) ( C)
The biodigester UASB plug flow was made 3,120
UASB
2,000 9.52 2090 202 3,330.43 34 90.33
of rotomolded HDPE. Because the study Steel N°1 210

was conducted in a WWTP of a brewery, UASB

rectangular 2,880
the effluent already arrives with primary 974 8.12 2090 329 1,775 35 84.26
concrete 120
N°2
treatment. As the effluent passes through UASC IC
6,000
the blanket of sludge, anaerobic stainless 664
250
2.66 2090 420 3,507 33 79.90
steel N°3
microorganisms digest the organic matter, UASB
2
producing biogas on the surface of the Plug Flow 1 12 2090 418 1.17 34 80
0.0833
N°4
sludge granules increasing its fluctuation.
Depending on the upward speed of the As Table 3 shows, the analysis of the
flow, the blanket of sludge expands, and biogas generated in the reactors was
some of aerated sludge granules can be performed using the method of the gas
dragged toward the surface. In the
chromatograph according to DIN 51872.
separation zone of solid, liquid and gas
phases, by means of a helical phase Table 3: Comparative characteristics of biogas
separator zone, the flow is directed to the produced in UASB analyzed
output, the sludge granules are degassed, UASB
UASB
UASC IC
Para rectangular UASB Plug
causing them to return to the blanket of meter
Unit Steel
concrete
stainless steel
Flow
N°1 N°3
sludge, the biogas bubbles are directed to N°2
CO2 % 22,03 16,04 17,77 24,80
the bell collection. Then, the effluent CH4 % 75,18 81,10 79,44 72,33
passes through the other UASB arranged H2S % 0,03 0,048 0,03 0,048
N2 % 2,50 2,615 2,40 2,615
in series. Fig. 3 illustrates drawings and O2 % 0,261 0,205 0,262 0,205

view the UASB digester system Plug Flow

deployed. 5. Conclusions
It is noteworthy that the UASB rotational
molded plug flow, has a removal efficiency
of organic load very good, comparable to
the IC when operated with HRT of 2.66
Fig. 3: Schematic in section details of the system hours plus the cost of implementing the
digesters. And view of UASB system digesters plug system is much smaller than the UASB IC,
flow deployed in brewery in Jacareí SP Brazil.
as well as maintenance because the IC any
Parameters of evaluation for the maintenance in sludge digestion column is
efficiency of the system the highest, rather risky from the point of
To evaluate the efficiency of the systems safety, and in the case of plug flow UASB
the following parameters were analyzed: this height can be reduced to 6 meters.
COD; BOD; temperature; residence time;
With this, the plug flow UASB system has
system efficiency and determination of
proved to be more feasible when
amount of biogas.
compared to conventional models.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Experience of Aguas de Murcia on biogas valorization R&D projects

Teresa R. Serna1, M. Mar Castro2 and Francisco J. Navarro3
1 AQUAMBIENTE, Plaza de Cetina 6, 2º Entlo. 30001 Murcia, Spain
2
AQUATEC, Plaza de Cetina 6, 1º Entlo. 30001 Murcia, Spain
3 EMUASA, Plaza Circular 9, 30008 Murcia, Spain

1. Introduction For testing purposes a pilot plant (Figure

In the context of sustainable development 1) was built, with capacity to treat up to
and particularly in the case of Waste 10 Nm3/h of raw biogas, made up three
Water Treatment Plants (WWTP), energy main stages: gas-liquid absorption (acid,
must be considered not only in terms of oxidative and caustic scrubbing), cooling
consumption reduction, but also in terms and solid-gas adsorption (activated
of production and use of "green" energy. carbon)[1].
Aguas de Murcia was born in 1989 as a
joint venture service company, 51%
owned by the City of Murcia, and 49% by
Hidrogea. The company leads the water
cycle in the municipality of Murcia.
Aguas de Murcia manages 15 wastewater
treatment plants (WWTP), of which only
Murcia Este WWTP has sludge stabili-
zation treatment by anaerobic digestion. Figure 1. Pilot plant for biogas treatment.
This WWTP treats urban wastewater of an
equivalent population of 960,000 inhab-eq This plant was enlarged subsequently to
and the design flow is 100,000 m3/day. include an upgrading phase and, from
There are three anaerobic digesters with a 2007 to 2010, efforts were focused on
total volume of 18,317 m3. assessing the technical feasibility of
The company is aware that all its activities obtaining automotive fuel (BIOEDAR) from
should be done in a sustainable way and, the biogas (Figure 2). The project, called
for that reason, since 2004 has been AMEB, allowed obtaining, from clean
carrying out in Murcia Este WWTP several biogas, a methane (CH4) rich stream and a
research and development projects carbon dioxide (CO2) rich stream, through
focused on the valorization of biogas two different processes: (1) chemical
generated during the sludge treatment. absorption by amines [2] and (2) physical
2. Technology description absorption by high pressure water
From 2004 to 2006, Aguas de Murcia scrubbing. The CH4 rich stream was comp-
carried out the ABICEC project, aimed to ressed and stored into special cylinders
assess the technical feasibility of an and finally used as automotive fuel; the
integrated process to achieve sustainable CO2 rich stream was pumped to the
use of biogas generated in WWTP by WWTP head for pH regulation of input
selective removal of undesired comp- waste water.
ounds.

159
 6,790 ppm), and it has been proven that it
is feasible to obtain an adequate biogas
quality just cleaning it by caustic
scrubbing.
The experimentation with amines has
enabled to identify the most suitable
amine (MEA) and the concentration (20%),
as well as the temperature to set during
Figure 2. View of the pilot plant. the desorption process (98°), obtaining a
biogas stream with average CH4 contents
From 2007 to 2010 Aguas de Murcia up to 95%.By water scrubbing, the results
participated in the project SOSTAQUA: reached were not satisfactory.
Technological developments towards a With regards to SOSTAQUA, the catalyst
self-sustainable urban water cycle finally obtained allows reforming directly a
(www.sostaqua.com/), funded by the clean stream of CH4 and CO2, generating
CDTI. The company established an H2 and CO.
agreement with the Spanish National The BIOCELL project has enabled the
Research Council in order to develop a implementation of FC technology on
specific catalyst for biogas dry reforming. biogas field, although it is yet no ready
From to 2009 to 2012, Aguas de Murcia neither from a technical or an economical
has participated in the BIOCELL project viewpoint; hence industrial deployment is
(www.life-biocell.eu/), aimed to demon- expected for the medium term.
strate the industrial feasibility of energy 4. Conclusions
production on WWTP from biogas via The experience acquired during the
Proton Exchange Membrane Fuel Cells development of all these projects has
(PEMFC) and Solid Oxide Fuel Cell (SOFC), allowed to Aguas de Murcia to choose
developing suitable tools for industrial installing a Combined Heat and Power
implementation [3]. plant for real scale biogas valorization.
To carry out the experimental trials a pilot CHP seems to be nowadays the most
plant has been built (Figure 3), made up of mature and profitable technology to
three stages: (1) biogas pretreatment, (2) implement in big size WWTP.
fuel processor, consisting of three diff- 5. References
erent reactors (reforming, water gas shift [1] F. Osorio et al. Biogas Purification from
and carbon monoxide (CO) preferential Anaerobic Digestion in a Wastewater
oxidation) and (3) two PEMFC (MES S.A., Treatment Plant for Biofuel Production.
1.5 kWe). Renewable Energy 34 (2009).
[2] F. Osorio et al. Preliminary studies for
obtaining biofuel by absorption with
mono-ethanol-amine from a wastewater
treatment plant. Energy Sources, Part A:
Recovery, Utilization, and anaerobic
digestion biogas in Environmental Effects
(2011).
[3] M. Martín et al. Valorización del biogás de
Figure 3. View of the BIOCELL pilot plant. depuradora mediante pilas de
combustible. Proceedings CONAPPICE
3. Results Congreso Nacional Pilas de Combustible
ABICEC allowed characterizing in detail the (2012).
biogas, showing large H2S contents (579-

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Enzymatic upgrading of biogas and how renewable resources can be

integrated in the natural gas grid
Thomas Hernø1 and Henrik Rousing1
1 HMN Gashandel A/S, Gladsaxe Ringvej 11, DK 2860 Søborg, Denmark

1. Introduction (DK) and EUDP, the Danish Energy

HMN Gashandel A/S and five partners Technology Development and Demon-
have initiated a 3-year full scale demon- stration Program with a grant on approx.
stration project to show that ENZymatic 50% of the project budget.
UPgrading of biogas (ENZUP) is a more
energy- and cost-effective method for 2. Technology description
upgrading biogas to grid quality gas than Enzymatic upgrading technology
the commercial technologies in operation The biogas will be upgraded in a
today. The project addresses one of major commercial-scale (500 nm3/h biogas = 300
barrier for increased use of biogas in the nm3/h bio methane) demonstration plant
natural gas grid: the cost of upgrading the developed by Akermin in collaboration
biogas. with Novozymes. Akermin’s technology
Another demonstration project “Power- transforms enzymes into proprietary
to-Gas via Biological catalysis – Phase 2” industrial biocatalyst that can be readily
(BioCat), will be located beside the ENZUP incorporated into conventional chemical
biogas upgrading plant. absorption processes for Carbon Dioxide
Upgrading of biogas from waste water (CO2) removal. By addressing the key issue
treatment, agricultural and industrial of enzyme stability in harsh industrial
residues support the Danish national environments, Akermin’s approach to CO2
energy policy on using biogas produced on removal significantly reduces operating
residuals and waste instead of fresh crops. costs. Carbonic anhydrases (CAs) form a
The upgraded biogas will meet natural gas family of enzymes that are particularly
specifications and will be injected in the useful in biogas upgrading as they convert
natural gas grid, replacing fossil natural CO2 and water to bicarbonate. Akermin
gas and reduce Green House Gas uses developmental versions of recomb-
emissions to the atmosphere. inant, highly active and thermostable CAs
Lower cost for upgrading biogas will available from major enzyme suppliers.
accelerate the use of renewable biogas in The enzymes are manufactured using
the natural gas grid and supports Danish conventional fermentation processes.
gas utilities’ business strategies on
increasing the amount of green gases in
the natural gas grid. Akermin’s approach enables the use of
The EUR 5.5 million ENZUP project is non-volatile, carbonate-forming solvents,
funded by HMN Gashandel A/S (DK), which, without an enzyme, absorb CO2 at
Akermin Inc. (USA), Ammongas A/S (DK), a rate that is far too slow to have any
Novozymes A/S (DK), BIOFOS Spilde- practical application, but that otherwise
vandscenter Avedøre A/S (DK), DGC A/S have outstanding physical properties. By

161
addressing this key limitation, Akermin Synergy with BIOFOS & BioCat project
creates an environmentally friendly sol- The rejected CO2 from the ENZUP
ution for removing CO2 from biogas. upgrading plant will be used by the BioCat
plant to produce synthetic methane using
Biogas source and system hydrogen produced from excess
The ENZUP demonstration facility will be renewable electricity. Waste heat from
located at the BIOFOS Waste Water the ENZUP plant will be used in the
Treatment Plant (WWTP), near Copen- BIOFOS WWTP.
hagen, Denmark. The plant handles
around one third of Greater Copenhagen’s
waste water from residences and industry.
Today the biogas is used in a 1 MWe gas
engine, producing electricity and heat. In
the future the ENZUP upgrading plant will
use all the biogas available (today approx.
3.5 mill. nm3). BIOFOS has a strategy to
become CO2 neutral by 2025. The means
are electricity savings, waste water
process changes, utilisation of waste heat
from sludge incineration and increased
energy production from the ENZUP &
BioCat projects. The future biogas and bio
methane system is shown in figure 1.
Figure 1. Biogas & bio methane system
Natural gas grid injection
The upgraded biogas (app. 98% methane) 3. Results
will be injected in the natural gas The expected results of the demonstration
distribution grid. The bio methane quality of the biocatalyst upgrading process is a
will be checked in a receiving station with 27% reduction of power and heat cost.
gas chromatograph, temperature, dew The total cost advantage for ENZUP
point and gas amount are measured. Then demonstration plant is estimated to 6%.
the gas is odorized and transferred with a Total cost advantage for future upgrading
pressure of around 5.5 bar in a 1.8 km gas plant is estimated to 14%. Higher cost
pipe to a Meter and Regulator station. In advantage can be achieved if upgrading
this station the gas is injected in the 4 bar plant is up scaled.
grid and distributed to natural gas
costumers. 4. Conclusions
The heating value of the bio methane is When the ENZUP upgrading facility
around 10 kWh/nm3, approx. 10% lower commences in full operations end 2015,
than natural gas. One option is to increase this is expected to be the largest
heating value by adding propane, which is demonstration of a biocatalyst used to
adding a substantial cost to the gas. In this remove CO2 from an industrial gas stream
project the distribution company keeps anywhere in the world. BIOFOS Waste
track of the heating value in the Water Treatment Plant is turned into a
distribution system, so the heating value is full-scale demonstration centre for new
known for each customer and no propane technologies for Biogas Upgrading and
is needed. Power to Gas in 2016.

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2nd International Conference on Renewable Energy Gas Technology Barcelona, Spain 2015

Biogas as a component for Dual Fuel system of vehicle's Internal

combustion engines
Jamshid Inoyatkhodjaev 1
1 Department of Applied Mechanics, Tashkent Turin Polytechnic University, Tashkent, 100095, Uzbekistan

1. Introduction full diesel), PM reduction (depending on

In this paper a Dual Fuel system for vehicle application it is possible to reach a max
engines is described. As a result of the PM reduction of 35% compared to full
application the ecological and economy diesel), Smoke reduction (it is possible to
characteristics using biogas as one of the reach a reasonable smoke reduction of
components of a Dual Fuel system are 40%), Oxidation catalyst option for CH4
discussed. slip; Noise reduction.
In Uzbekistan, where increasing demand Economics: High economical saving
in oil, hard to cover by own resources and potential (Actual economical saving
a huge amount of natural gas (NG) depends on the substitution efficiency and
reserves, NG becomes more popular as an the difference in price between diesel and
alternative for gasoline in vehicles. gas); Small initial investment for system
As a gaseous fuel, NG is mostly used but implementation.
the perspective in biogas has recently Technical: Exploitation of all combustion
been observed. control inputs (injection quantity and
timing, air control, Exhaust Gas Recircula-
2. Technology description tion control, etcetera).
Dual Fuel conversion permits to exploit Additional integrated to Engine control
the advantages of NG to diesel engines unit another Control Unit can control fuel
with a simple conversion, without being supplying process as preferred by driver.
strictly conditioned by the availability of The software gives an opportunity to
an adequate network of gas filling choose different ratios of each fuel in the
stations, since the vehicle can always air-fuel mixture. Such variable character-
switch back to the original fuel. NG is istics give advantages not only for fuel
mixed with the air flow in the engine’s economy but also for engine control
intake manifold. Diesel injection is operations. [2]
reduced in quantity, and ignites the Setup of dedicated control strategies and
mixture of air and NG in the combustion procedure for calibration (on engine or
chamber. During operation the system vehicle): Base Fuel Control, Operating
provides and controls the injection of CNG Mode transitions, Drivability Calibration,
and Diesel oil in variable percentages Safety management, Emission Cycle
according to the engine Operating Point verification.
(Fig.1). [1] Integrated diagnostic functions, and
specific OBD (On-Board Diagnostics)
3. Advantages thresholds: Possibility to get information
Emissions: CO2 reduction (it is possible to from both control units.
reach a reduction 12-14 % compared to

163
 3
Chlorine + Cl+F mg/m <100
Fluorine
consistence
3
Ammonia NH3 mg/m <30
3
Dust mg/m <10
consistence
Particulate micron 3-10
dimensions
3
Oil vapors (>C5 mg/m <3000
<C10)
3
Oil vapors mg/m <250
(>C10)
3
Silicium Si mg/m <10
(organic)
Minimum mBar 20
pressure in
intake gas float
Gas pressure % +/-10
fluctuation

There are several methods to desulfurize

the gas fuel. One is chemical vapor
deposition or precipitation. Another solu-
tion is to add iron trichloride to the biogas
digester.
Figure 1. Fuel supply in a Dual Fuel system
5. Conclusions
4. Demands to Biogas
Biogas can be used as a component of a
Biogas may contain harmful components
Dual Fuel system for internal combustion
such as Sulfur, Ammonia, and Silicon
engines. The chemical treatment proced-
which should be removed from the fuel.
ures for the neutralization of some of the
The minimum characteristics of fuel gases
harmful components are not expensive
for Internal Combustion engines are
and could be executed under simple
shown in Table 1.
industrial conditions.
Dual Fuel has proven to be a viable and
Table 1. Characteristics of fuel gases for
reliable technology for use of CNG (or
ICE.
biogas) on old and current powertrains.
Characteristic Symbol Unit Limit However, as biogas has a higher octane
Caloricity Hu kWh/m
3
>4 number than NG the control unit should
(lowest) be calibrated according to that.
Hu Speed %/min <5
change 6. References
3
CO2/Hu CO2/Hu %/kWh/m <10
3
[1] P. Tubetti, D. Ceccarini. Overview of Dual
Sulfur S mg/m <2200 Fuel Technology and its field applications.
consistence ANGVA - 2013 Conference & Exhibition
3
H2S H2S %/m <0,15 paper. 27-29 Nov. 2013.
consistence
3 [2] R.Aliev, J. Inoyatkhodjaev. Features of
Chlorine Cl mg/m <100
consistence
vehicle mechatronics and its diagnostics.
Fluorine F mg/m
3
<50 Scientific Journal of Kyrgyz State technical
consistence University #2 (28). 2010.

164
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