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ScienceDirect
Energy Procedia 63 (2014) 7408 – 7420

GHGT-12

Life Cycle Assessment of Natural gas-based Chemical Looping

for Hydrogen Production

Letitia Petrescua*, Christoph R. Müllerb , Calin-Cristian Cormosa,

a
Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany Janos Street, RO-400028 Cluj -Napoca, Romania
b
Laboratory of Energy Science and Engineering, ETH Zurich, Leonhardstrasse 27, 8092 Zurich, Switzerland

Abstract

Hydrogen production from natural gas, combined with advanced CO 2 capture technologies, such as iron-based chemical looping
(CL), is considered in the present work. The processes are compared to the conventional base case, i.e. hydrogen production via
natural gas steam reforming (SR) without CO2 capture. The processes are simulated using commercial software (ChemCAD) and
evaluated from a technical point of view considering important key performance indicators such as hydrogen thermal output, net
electric power, carbon capture rate and specific CO2 emissions. The environmental evaluation is performed using Life Cycle
Analysis (LCA) with the following system boundaries considered: i) hydrogen production from natural gas coupled to CO2
capture technologies based on CL, ii) upstream processes such as: extraction and processing of natural gas, ilmenite and catalyst
production and iii) downstream processes such as: H2 and CO2 compression, transport and storage. The LCA assessment was
carried out using the GaBi6 software. Different environmental impact categories, following here the CML 2001 impact
assessment method, were calculated and used to determine the most suitable technology. Sensitivity analyses of the CO2
compression, transport and storage stages were performed in order to examine their effect on the environmental impact
categories.
© 2013The
© 2014 TheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd. Ltd.
This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of GHGT.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: "LCA; CCS; Chemical Looping; Natural gas"

* Corresponding author. Tel.: +4-026-459-3833; fax: +4-026-459-0818

E-mail address: letitiapetrescu@chem.ubbcluj.ro

1876-6102 © 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.777
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7409

1. Introduction

Hydrogen can play an important role as an energy carrier in a sustainable, reliable, and cost-effective energy
future [1]. Hydrogen is currently produced from a variety of primary sources such as natural gas, naphtha, heavy oil,
methanol, biomass, wastes, coal, solar, wind, and nuclear [2]. According to Muradov’s prediction prevision, fossil
fuels will remain the dominant source for hydrogen production over the next few decades [3]. Hydrogen production
from fossil fuels is a practical process, but the associated emission of large quantities of CO2 has to be reduced [4].
Combining hydrogen production based on fossil fuels with carbon capture and storage (CCS) is a major research
topic in the development of innovative energy conversion processes [5]. Natural gas is the dominating feedstock for
hydrogen production. The reason for this is that natural gas is abundant, available in most parts of the world, has the
highest hydrogen content of all fossil fuels, and is of low cost [6]. The dominant H2 production technology on a
large scale is the SR of natural gas, which is responsible for around 50% of the H2 produced worldwide [7]. Natural
gas reforming is a mature technology used in the refinery and chemical industries for large-scale H2 production [8].
Beside SR, there are also innovative methods for hydrogen production from natural gas e.g. hydrogen production
from natural gas combined with advanced CO2 capture technologies, such as CL. The CL technology for hydrogen
production uses oxygen carriers e.g. iron-based materials [5, 9]. The present paper deals with the natural gas
conversion based on CL process and on the natural gas SR combined with CL. Ilmenite is used as an oxygen carrier
in the CL processes. The focus of this paper lies on the environmental assessment of different hydrogen production
processes based on natural gas (using SR and/or CL technologies). As hydrogen gains popularity, the question
remains: how sustainable is the production of hydrogen? To measure sustainability, scientists commonly use Life
Cycle Assessment (LCA) - the internationally standardized method that quantifies the environmental impacts of a
product or service [10]. In this work the conventional SR and innovative CL methods for hydrogen production were
analyzed from a LCA point of view.

Nomenclature

ADP Abiotic Depletion Potential

AP Acidification Potential
BFW Boiler Feed Water
CL Chemical Looping
CCS Carbon Capture and Storage
EP Eutrophication Potential
FAETP Freshwater Aquatic Ecotoxicity Potential
GWP Global Warming Potential
HTP Human Toxicity Potential
HTS High Temperature Shift
LCA Life Cycle Analysis
LCI Life Cycle Inventory
LTS Low Temperature Shift
MAETP Marine Aquatic Ecotoxicity Potential
NG Natural Gas
ODP Ozone Layer Depletion Potential
POCP Photochemical Ozone Creation Potential
PSA Pressure Swing Absorption
PSRK Predictive Soave Redlich Kwong
SR Steam Reforming
SRK Soave Redlich Kwong
TEG Tri-ethylene-glycol
TETP Terrestric Ecotoxicity Potential
7410 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420

2. Plant configurations, simulation assumptions and technical key performance indicators

The three case studies investigated in the present paper are:

Case 1: Hydrogen production from natural gas using SR technology;
Case 2: Hydrogen production based on CL natural gas conversion;
Case 3: Hydrogen production based on SR combined with CL.

2.1 Description of Case 1: Hydrogen production from natural gas using SR technology

Hydrogen production via catalytic steam reforming of natural gas is a mature technology and is the means by
which most of hydrogen is made today [11]. Reforming is a catalytic operation, and the catalysts employed are
poisoned by even trace amounts of sulfur [12]. Thus, the natural gas is pre-treated in order to convert any sulphur
compounds to H2S [11]. Subsequently, H2S is adsorbed in a ZnO bed and reacts to form ZnS, which is removed as a
solid waste. After pretreatment, the natural gas together with steam are sent to the steam reformer. The reaction
taking place here is:

H2O + CH4 → CO + 3H2 (r1)

This is a highly endothermic reaction. In order to generate the heat required for the reforming reaction,
natural gas is burned with air in the furnace. The synthesis gas from the reformer is rich in H 2 and CO. After the
reformer, the gas mixture passes through a heat recovery step and is fed into a water-gas shift reactor to produce
additional H2 [6].The water gas shift (WGS) reaction:
CO + H2O → CO2 + H2 (r2)
can be used to increase the H2 content [12]. Normally, two WGS stages (HTS - high temperature shift and LTS - low
temperature shift) are used to reduce the CO content to a level of approximately 0.2-0.4 vol. The reaction is
exothermic and occurs at temperatures ranging from 200 to 400°C [6]. The two stages for CO conversion are
considered in the present study. The hydrogen obtained in the HTS and LTS steps is purified further using a pressure
swing absorption (PSA) unit. The H2 obtained in the process is compressed up to 60 bar. The process simplified
schema for Case 1 is presented in Fig. 1.

Fig. 1. Block diagram for Case 1: Hydrogen production from natural gas using SR (without CCS)

2.2 Description of Case 2: Hydrogen production based on chemical looping natural gas conversion

In this technology, natural gas together with the solid oxygen carrier (ilmenite) is sent to the fuel reactor.
The following reaction takes place at 750 - 900°C [13]:
4Fe2O3 +3CH4 → 8Fe+3CO2 + 6H2O (r3)
After water condensation and separation, the gaseous stream from the fuel reactor, is sent to the drying and
compression stage where CO2 is dried using Tri-ethylene-glycol (TEG) and compressed to 120 bar being ready for
storage. The solid stream containing the reduced metal is re-oxidized with steam to a metal oxide to close the redox
cycle. The steam reactor operates at 500 - 700°C [13]; the chemical reaction taking place is:
3Fe + 4H2O → Fe3O4 + 4H2 (r4)
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7411

The gaseous and solid streams are separated and the product of the process (H2) is compressed to 60 bar.
The solid coming from the steam reactor, i.e. Fe3O4 is transformed to Fe2O3 in the air reactor (combustor) as follows:
4Fe3O4 + O2 → 6Fe2O3 (r5)
This reactor operates at 950 - 1150°C [13]. The Fe2O3 is recycled back to the fuel reactor. A small amount
of solids (1%) is removed after oxygen carrier deactivation. The process simplified schema for Case 2 is presented
in Fig. 2.

Fig. 2 Block diagram for Case 2: Hydrogen production based on CL natural gas conversion

2.3 Description of Case 3: Hydrogen production based on steam reforming combined with chemical looping

The starting raw material for this technology is again natural gas. Sulfur is removed from the natural gas
(prior to the reformer). Subsequenty, process steam is added to methane, which is converted to H2, CO and CO2. The
gas is purified by CO2 removal in an iron-based CL process to produce a high quality H 2 product. The first part of
the process is simmilar to Case 1. Syngas from the natural gas SR together with the solid oxygen carrier (ilmenite)
are sent to the CL line. The reactions that occur in the CL section (fuel reactor, steam reactor, air reactor) are the
same as in Case 2 (r3, r4 and r5). The process simplified schema for Case 3 is presented in Fig. 3.
7412 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420

Fig. 3 Block diagram for Case 3: Hydrogen production based on SR combined with CL

2.4 Design assumption, process simulation and technical key performance indicators
The main design assumptions for the cases under investigation are presented in Table 1.

Table 1. Design Assumptions (Case 1-3)

Unit Operation Parameter Value
Natural gas desulphurization (Case 1- 3) Temperature (oC) 350
Adsorbent- ZnO
Natural gas reformer (Case 1) Pressure (bar) 30
Outlet temperature (oC) 900
HTS (Case 1) Temperature (oC) 430
Catalyst composition (% wt.)
Fe2O3 88
Cr2O3 9
CuO 3
CO Conversion (%) 70
LTS (Case 1) Temperature (oC) 275
Chemical Looping (Case 2-3) Catalyst composition- same as HTS
Chemical looping agent- Ilmenite
Fuel reactor parameters (bar/ oC) 30 / 700 - 750
Steam reactor parameters (bar/ oC) 28 / 700 - 800
Air reactor parameters (bar/ oC) 26 / 850 -1000
Pressure drop fuel and steam 1
reactors (bar)
Delivery pressure (bar) 60
H2 compression (Case 1-3) Compressor efficiency (%) 85
Delivery pressure (bar)
CO2 Drying and Compression (Case 2-3) 120
Compressor efficiency (%)
Solvent used for CO2 drying -TEG 85
'Tmin. (oC) 10
Heat exchangers (Case 1-3) 1-2
Pressure drop (% of the inlet pressure)

The above described processes were simulated using ChemCAD version 6.0.1 process simulator [14]. The
Soave Redlich Kwong (SRK) method was selected to model the thermodynamic properties for Case 1 and the
predictive Soave Redlich Kwong (PSRK) method was used for Case 2 and Case 3. The mass and energy balances
derived from the simulation were used to calculate key technical performance indicators. The key performance
indicators, their definition as well as their correspondent calculation formula, have been previously defined by
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7413

Cormos [15]. The obtained results are summarized in Table 2.

Table 2. Technical key performance indicators (KPI) for Case 1 - 3

KPI Units Case1 Case2 Case3
Natural gas flowrate kg/h 31371.58 30632.79 46219.51
Natural gas LHV MJ/kg 46.73 46.73 46.73
Thermal energy of the feedstock – LHV (A) MWth 407.26 397.66 600.01
Gross electric power output (B) MWe 17.02 17.53 68.41
Hydrogen output (C) MWth 300 300 300
Hydrogen compression MWe 4.18 3.97 4.33
Carbon capture & compression MWe - 1.98 1.88
Total ancillary power consumption (D) MWe 6.26 7.99 6.21
Net electric power output (E = B - D) MWe 10.76 9.54 62.2
Net electrical efficiency (E/A * 100) % 2.64 2.39 10.37
Hydrogen efficiency (C/A * 100) % 73.66 75.44 49.99
Cumulative energy efficiency % 76.30 77.83 60.37
Carbon capture rate % 0 99.25 68.5
CO2 specific emissions (hydrogen and power) kg/MWh 267.39 1.94 212.83

In terms of fuel consumption, the NG flow rate varies in the range 30-47 t/h, as shown in Table 2. The NG
flow rate is particularly high in Case 3, where additional quantities of NG are required to provide the heat for the
reforming reaction. The same situation occurs in Case 1. Regarding the ancillary power consumption of various
plant sub-systems two important aspects can be noticed: on the one hand, an increase power consumption in the
hydrogen compression sub-systems based on reforming technology (Case 1 and Case 3) and, on the other hand, a
higher power consumption for the CO2 compression sub-system for Case 2. The lowest ancillary power
consumption is registered in Case 3. The evaluated plant concepts generate 300 MWth of H2. The hydrogen
efficiency is around 75% for Case 1 and Case 2 and decreases significantly in the case of combining those two
technologies Case 3. Here, the hydrogen efficiency is around 50%. Besides H2, electric power is also generated in
the systems under investigation. The net electric power varies in the range 9–63 MWe and the net plant electrical
efficiency varies in the range 2–10.5%. The carbon capture rate is almost 100 %, i.e. 99.25% in Case 2, while, for
Case 3, it reaches only 68.5%. The capability of capture almost the total carbon content of the feedstock and lower
plant complexity streamlines the attractiveness of the direct chemical looping option (Case 2). The specific CO2
emissions of the evaluated plant concept with CCS (Case 2 and Case 3) are in the range of 2-213 kg/MWh. For
comparison, the case without CCS (Case 1) has specific CO2 emissions of about 268 kg/MWh.

3. Life Cycle Assessment (LCA)

LCA provides a comprehensive view of the environmental aspects of the product or process and it refers to
the major activities in the course of a product’s life from its manufacture, use, and maintenance, to its final disposal.
A “cradle-to-grave” approach was assumed for the three cases under investigation. “Cradle-to-grave” begins with
the gathering of raw materials to creating the product and ends at the point when all materials are returned to the
earth [16]. In order to deal with the complexity of LCA, the International Standards Organization (ISO) established
a methodological framework called ISO 14044 for performing LCA studies, which comprises four phases: Goal and
Scope, Life Cycle Inventory (LCI) analysis, Life Cycle Impact Assessment (LCIA) and Interpretation [17]. Those
steps are detailed in the next part.
7414 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420

3.1 Goal and scope of the study, system boundaries, limitations and LCA main assumptions

The primary goal of this study is to quantify and analyze the total environmental aspects of hydrogen
production from natural gas using SR and/or CL. For this aim, the following strategy is proposed: i) to provide a
detailed assessment of each pathway step, from raw materials extraction to H2 production, as well as, H2 and CO2
transport and storage; ii) to provide a comparison of the environmental efficiency of the processes under study. The
present LCA studies were conducted step by step, based on the energy and material consumption of each unit
process which derived from the ChemCAD process simulator. A requirement of the study is that the plants are self-
sufficient in all their utilities; this implies that electricity must be produced to drive the machinery.
The scope of the study includes the definition of the following characteristics: function of the system,
functional unit, geographical and temporal context, system boundaries, main assumptions and limitations. The
functions of the systems considered in the present study are: the production of 300 MWth of hydrogen as well as the
production of power (10.76 MW e for Case 1, 9.54 MWe for Case 2, 62.2 MWe for Case 3). The functional unit is
1MW of H2 and power produced. The plants are supposed to be located in Romania, Europe, in 2020, implying that
all technology configurations are subject to further technological improvement. The system boundaries include:
i) H2 production from natural gas conversion coupled to CO2 capture technologies based on CL;
ii) upstream processes such as: extraction and processing of natural gas, ilmenite and catalyst production;
iii) downstream processes such as: H2 and CO2 compression, transport and storage.
The following aspects are not covered in the present format of the study: 1) the construction of the
infrastructure (e.g. plant, pipelines, roads, railways); 2) the construction of trains and trucks used for transportation;
3) human activities as well as labour costs associated with the number of employees at each step. The main
assumptions made are detailed below.
The schema presented in Fig. 4 was considered for the natural gas supply chain for all cases.

Fig. 4 Natural gas supply chain (Cases 1 - 3)

Some fraction of the NG extracted was considered for the production of electricity required to power the
extraction stage. For the domestic extraction of 1 m3 of natural gas 0.02 m3 have been considered. A quantity of
0.016 m3 is requested to extract 1 m3 for imported natural gas [18]. The domestic natural gas is from Romania, the
imported natural gas comes from Russia. We assumed that 70% of the natural gas is domestic and 30% is imported.
It is further assumed that the gas was transported via a pipeline network. A distance of 300 km was considered from
the extraction site to the plant location for the domestic natural gas. A distance of 3000 km pipeline was considered
for the imported natural gas to the national pipeline. A quantity of 0.1% leakage was considered for domestic
transport; 0.2% for imported transport. The schema presented in Fig. 5 was considered for the ilmenite supply chain
(Cases 2-3).
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7415

Fig. 5. Ilmenite supply chain (Cases 2-3)

The quantities of water, electricity, diesel and explosives necessary to extract and concentrate one tone of
ilmenite are taken from literature [19]. The prepared ilmenite (extracted and concentrated) is transported by train
over a distance of 200 km.
For the present work it is assumed that H2 is delivered by pipeline. Hence, a high pressure is required to
ensure long distance transport from production sites to end-users with low energy consumption. Ideally, the pressure
should be equal to the distribution network pressure of 60-70 bar. One possibility for rapidly expanding the
hydrogen delivery infrastructure is to adapt part of the natural gas delivery infrastructure to accommodate hydrogen.
Converting natural gas pipelines to carry a blend of natural gas and hydrogen (up to about 20% hydrogen) may
require only modest modifications to the pipeline; converting existing natural gas pipelines to deliver pure hydrogen
may require more substantial modifications [20]. A percentage of 0.1% of the H2 produced in the plants is supposed
to be lost during transport. H2 is transported over a distance of 1000 km. The compressor stations are located every
100 km. The pressure drop is supposed to be 10 bar/100 km. The electricity necessary for compression was also
included in the analysis.
The CO2 transport and storage (Case 2-3) supply chain is presented in Fig. 6

Fig. 6. CO2 supply chain (Cases 2-3)

The CO2 captured from the processes is supplied to the transport chain at 120 bar and it is transported over
a distance of 800 km via pipelines in order to be stored in the sea (it is supposed to be stored in the Black Sea-depth
storage at 2000 m). Some data related to the transport are: the fugitive emissions through the pipeline are 2.32 t
CO2/km/year; the fugitive emissions through the compressors are 23.2 t CO2/MW/year; 40 MW contrigual
compressor and a pressure drop of 0.006 MP/km was considered; a distance of 100 km has been considered between
two compressor stations; the compression power is 111 kWh/ t CO2 (400 MJ/ t CO2); the injection power is 7 kWh/t
CO2; 0.1% CO2 is proposed to be considered as losses during the injection process [21].

3.2 Life Cycle Inventory (LCI) and Impact Assessment

The LCI correspondent to each step was performed taken into account the material and energy balances
derived from the process simulator and the assumptions presented previously. For example, the LCI table containing
the inputs and outputs for Case 2, for the hydrogen production step, is presented in Table 3.
7416 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420

Table 3. LCI for Case 2, hydrogen production step

Input Unit Value Output Unit Value
NG 30632.79 kg/h CO2 to storage 79285.77 kg/h
Ilmenite 571536.7 kg/h H2 9092 kg/h
Air 298606 kg/h Ilmenite removed:
BFW 145080 kg/h Ferric Oxide 3765.73 kg/h
TEG 2700 kg/h Titanium Dioxide 1883.71 kg/h
Power consumption 7.99 MWe Ilmenite recycled 565886.7 kg/h
Condensate 80664 kg/h
Exhaust Gas:
CO2 599.68 kg/h
N2 0.06 kg/h
H2O 36.03 kg/h
Exhaust Air:
N2 22903.99 kg/h
O2 2776.01 kg/h
Steam to CL 97281 kg/h
BFW 47799 kg/h
TEG 2700 kg/h
Hydrogen 300 MWth
Electricity 17.53 MWe

LCI for CO2 transport and storage for Case 2 is also presented (see Table 4).

Table 4. LCI for Case 2, CO2 transport and storage step

Input Unit Value Output Unit Value
CO2 from plant 79285.77 kg/h CO2 stored 77970.4 kg/h
Electricity for compressors 31615.32 MJ CO2 losses pipeline 247.47 kg/h
Electricity for injection 1964.84 MJ CO2 losses compressors 989.86 kg/h
Injection pressure 120 bar CO2 losses injection 78.05 kg/h
Pressure drop 48 bar
Pipeline distance 800 km
No. of compressor stations 8 -
Storage depth 2 km
Distance between 100 km
compression stations

An impact assessment was carried out in order to identify the environmantal impacts that arrise from the LCI.
The LCA software GaBi version 6.0 [22] was used to evaluate the environmental impacts of inventory aspects and to
create product assemblies and life cycles for the three cases under investigation. The CML 2001 method assessment,
developed by the Center of Environmental Science at Leiden University, was considered in the present study. The
description of the environmental indicators considered in the CML 2001 method are reported in the literature [17].
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7417

3.3 Results and discussions

Ten environmental impact categories were evaluated. The values of the environmental impact categories
for Cases 1-3 are reported in Table 5.

Table 5. LCA results (Case 1-3) according to CML 2001

KPI Units Case1 Case2 Case3
GWP kg CO2-Equiv./MW 701.13 240.09 494.25
AP kg SO2-Equiv./MW 0.34 2.25 2.28
EP kg Phosphate-Equiv./MW 0.01 0.15 0.16
-9 -8
ODP kg R11-Equiv./MW 5.58*10 4.72*10 4.79*10-8
-5 -4
ADP elements kg Sb-Equiv./MW 3.81*10 1.35*10 1.47*10-4
ADP fossil MJ/MW 4785.67 6679 8012.69
FAETP kg DCB-Equiv./MW 0.216 1.13 1.21
HTP kg DCB-Equiv./MW 1.79 14.78 14.98
PCOP kg Ethene-Equiv./MW 0.024 0.13 0.13
TEP kg DCB-Equiv./MW 0.072 1.72 1.75

There are large differences in terms of GWP between the cases with CCS (Case 2 and Case 3) and the case
without CCS (Case 1). Obviously, the case without CCS has the highest GWP caused by the CO2 released into the
atmosphere. The total GWP value for Case 1 is 701.13 kg CO2-Equiv./MW. From this value 301.06 kg CO2-
Equiv./MW comes from the H2 production process, 268.67 kg CO2-Equiv./MW comes from H2 transport process
and 131.14 kg CO2-Equiv./MW comes from the catalyst production process. Comparing the two cases with CCS, in
terms of GWP, it can be noticed that the GWP value in Case 3 is higher, i.e. more than double, than in Case 2.
Possible explanations for this behavior are: i) the exhaust stream coming out from the furnace emits 41268 kg/h of
CO2 in Case 3 vs. only 600 kg/h of CO2 are released in Case 2 and ii) the quantity of CO2 emitted during ilmenite
preparation is larger in Case 3 than in Case 2, i.e. 1683 kg vs. 1402 kg. The quantities of CO2 lost during the CO2
transport and storage step (via pipelines, compressors and injection) are the same for both cases. Regarding AP, the
best value is obtained in Case 1 (0.34 kg SO2-Equiv./MW). For this case 0.319 kg SO2-Equiv./MW comes from the
H2 production process and the rest, 0.022 kg SO2-Equiv./MW, comes from the H2 transport step. For Case 2, the
total value of AP is 2.25 kg SO2-Equiv./MW. The contributions of various steps to the AP value is as follows: 1.34
kg SO2-Equiv./MW comes from the H2 production process, 0.598 kg SO2-Equiv./MW is due to the ilmenite
production process, 0.286 kg SO2-Equiv./MW are due to CO2 transport and storage and 0.021 kg SO2-Equiv./MW
corresponds to the H2 transport. In Case 3, the total AP value is 2.28 kg SO2-Equiv./MW. The H2 production
process contributes 1.42 kg SO2-Equiv./MW to the total value, 0.598 kg SO2-Equiv./MW is due to the ilmenite
production process, 0.245 kg SO2-Equiv./MW comes from the CO2 transport and storage step and a small
contribution to the total value, i.e. 0.019 kg SO2-Equiv./MW, are due to H2 transport. The EP impact category has
the highest values in the CCS cases due to the ilmenite production process which generates around 83% of the EP.
Other impact categories such as ODP and ADP elements have low values in all three cases. ADP fossil has the
lowest impact in Case 1: 4785.67 MJ/MW. From this value 4772.12 MJ/MW is due to the SR process and only a
small part, equivalent to 12.56 MJ/MW, to the H2 transportation step. ADP fossil has the highest value in Case 3
(8012.69 MJ/MW ) because this case consumes the highest quantity of natural gas (see Table 2). The contribution of
different life cycle steps to the ADP fossil for Case 3 is: 7203 MJ/MW correspond to the H2 generation process, 640
MJ/MW is due to the ilmenite production, 158 MJ/MW is due to the CO2 transport and storage and 11.6 MJ/MW to
the H2 transport. The contribution of different life cycle steps to the total ADP fossil (6679 MJ/MW), for Case 2 is:
5841 MJ/MW corresponds to hydrogen production process, 640.43 MJ/MW is due to the ilmenite production,
184.14 MJ/MW is due to the CO2 transport and storage and 13.61 MJ/MW to the H2 transport. The best values of
the three impact indicators linked to the lethal concentration LC50, FAETP, HTP, TEP is obtained also in Case 1.
From Table 6 it can be noticed a higher human toxicity corresponding to the CCS cases compared to the base case.
7418 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420

PCOP impact category has almost the same value for Case 2 and Case 3, but this value is five times more than the
PCOP value of the base case (Case 1).
Starting from Spath and Mann definitions [11] two efficiencies and two ratios were adapted and calculated
for the hydrogen and power generation. The results obtained are presented in Table 6.

Table 6. Efficiencies and ratios (Case 1-3)

Calculation Units of Case 1 Case 2 Case 3
Formula measure
(a) Life Cycle LCE=(EH2+Ee-Eu- Ef)/Ef % -27.51 -38.82 - 53.57
Efficiency (LCE)

(b)External energy EEE=(EH2+Ee-Eu)/Ef % 72.49 61.18 46.33

efficiency (EEE)
(c) Net energy NER=(EH2+Ee)/Eff 0.76 0.77 0.6
ration

(d) External energy EER=(EH2+Ee)/(Eff- Ef)) 218.23 219.37 213.18

ratio

EH2 = Energy in the hydrogen; Eu = Energy consumed by all upstream processes required to operate the hydrogen plant
Ef = Energy contained in the natural gas fed to the hydrogen plant; Eff = Fossil fuel energy consumed within the system (e);
Ee= Electric power generation.
(a) Includes the energy consumed by all of the processes.
(b) Excludes the heating value for the natural gas feedstock from the life cycle efficiency formula.
(c) Illustrates how much energy is produced for each unit of fossil fuel energy consumed.
(d) Excludes the energy of the natural gas to the hydrogen plant.
(e) Includes the natural gas fed to the hydrogen plant since it is consumed within the boundaries of the system.

The energy in the natural gas is higher than the energy content of the hydrogen and power produced.
Therefore, the LCEs are negative. This reflects the fact that because natural gas is a non-renewable resource, more
energy is consumed by the system than it is produced. The best value for this indicator is obtained in Case 1. In
calculating the EEE, the energy content of the natural gas is not included, making the result of this measure positive
[11]. The best value for this indicator is again obtained in Case 1. The NER shows the quantity of energy produced
(hydrogen and power) when one energy unit of fossil fuel is consumed. The best value for NER is obtained in Case
2. EER shows the rate of energy consumption by the upstream process steps. Higher efficiencies and energy ratios
are desired for any process, not only in terms of economics, but in terms of reduced resources, emissions, wastes and
energy consumption [11]. The best value for EER is again obtained in Case 2.

3.5 Sensitivity analysis

A sensitivity analysis on the CO2 transport and storage step for Case 2 is reported in Table 7. The distance
from the sink to the storage site was modified from 400 to 1200 km in order to see the changes of this variable on
the CO2 losses (through pipeline, compressors and injection process) and, implicitly, the effect of this variable on
the total GWP.

Table 7. Sensitivity analysis for CO2 transport and storage step (Case 2)
Parameter 400 km 800 km 1200 km
CO2 input flowrate (kg/ h) 79285.77 79285.77 79285.77
CO2 losses pipeline (kg) 124 247.47 371.2
CO2 losses compressors (kg) 494.92 989.86 1484.76
CO2 losses injection (kg) 78.66 78.05 77.43
CO2 stored (kg) 78588.18 77970.4 77352.38
GWP (kg CO2-Equiv./MW) 238.08 240.09 242
 Letitia Petrescu et al. / Energy Procedia 63 (2014) 7408 – 7420 7419

The CO2 losses through the pipeline as well as the CO2 losses through compressors increase proportionally
with the pipeline length. There is a slight decrease in the CO2 loss during the injection process because less CO2 is
injected. The quantity of CO2 stored decreases with an increase in pipeline length. It can be also noticed, from
Table 8, that there is not a great modification on the total GWP (GWP generated by all the life cycle steps: NG
supply chain, hydrogen production process, hydrogen transport and CO 2 transport and storage step reported to one
MW of hydrogen and electricity produced) with the modification of the pipeline length.

4. Conclusions

Natural gas conversion based on CL process as well as the natural gas SR combined with CL using ilmenite
as the oxygen carrier were considered in the present study. These processes were compared to the conventional SR
process. The processes are evaluated, in the first instance, from a technical point of view considering some
important key performance indicators. Evaluated plant concepts generate 300 MWth of H2. The carbon capture rate
is almost 100% (99.25%) in Case 2, while for Case 3 it reaches only 68.5%. The capability of capturing almost the
entire carbon of the feedstock and lower plant complexity streamlines once more the attractiveness of the direct
chemical looping option (Case 2). The specific CO2 emissions of the evaluated plant concepts with CCS (Case 2
and Case 3) are in the range of 2-213 kg/MWh. For comparison, the case without CCS (Case 1) has specific CO2
emissions of about 268 kg/MWh.
The focus of the present work lies on an environmental evaluation of the processes using Life Cycle
Analysis (LCA). A “cradle-to-grave” approach was assumed for the three cases under study. The system boundaries
considered in the LCA include: i) hydrogen production from natural gas conversion coupled to CO2 capture
technologies based on CL; ii) upstream processes such as the extraction and processing of natural gas, ilmenite and
catalyst production; and iii) downstream processes such as H2 and CO2 compression, transport and storage. The LCA
assessment was carried out using the GaBi 6 software. Life Cycle Inventory (LCI) analysis, Life Cycle Impact
Assessment (LCIA) and Interpretation, the four steps of LCA are presented in detail. Ten environmental impact
categories, according to the CML 2001 impact assessment method, were defined, calculated and compared. The
most significant environmental impact categories are the GWP and ADP fossil. The best value for GWP is obtained
in Case 2, 240.04 kg CO2-Equiv./MW. ADP fossil has the lowest impact in Case 1: 4785.67 MJ/MW. A sensitivity
analysis on the CO2 transport and storage step, viz. on the pipeline length, and implicitly on the CO2 losses through
the pipeline, compressors and injection process, was also performed leading to the conclusion that such a
modification does not have a large contribution on the total GWP.

Acknowledgements

This work was supported by the Romanian – Swiss Research Programme, project no. IZERZO_141976/1:
"Advanced thermo-chemical looping cycles for the poly-generation of decarbonised energy vectors: material
synthesis and characterization, process modeling and life cycle analysis".

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