Anaerobic digestion fundamentals II

Thermodynamics

Dr Yue Zhang

Lecture 2, Monday 12th August 2013 1

Course RE1: Biogas Technology for Renewable Energy Production and Environmental Benefit, the 23rd Jyväskylä Summer School, August 2013
AD process consideration
• Kinetics (rate)
• Thermodynamics (extent)

0.300
extent

Methane production
CH4 production (STP m3 kg-1 VS)

0.250

0.200

0.150

cattle slurry
0.100

0.050

0.000
0 20 40 60 80 100 120 140 Time
Time (days)

Question:
• Is there an upper limit on specific methane/biogas production?
2
Contents
• Biomass energy
 Photosynthesis
Sun Bioenergy
 Calorific value and bomb calorimeter

Methane
Biomass
(biogas)

• Estimation of theoretical maximum methane production

 Elemental analysis and Buswell equation
 Biochemical composition approach
 Chemical oxygen demand (COD) approach

• Energy flow and mass flow in AD process

3
Biomass energy and calorific value

4
Biomass energy
• Photosynthesis: metabolic synthesis of complex organic
material using CO2, H2O, inorganic salts, and energy from the
solar radiation

6CO2 + 6H2O + sunlight = C6H12O6 + 6O2

Glucose

• Chemically-stored energy: chemical bonds

• Energy transferred and utilised through chemical and biological
processes

5
Bond energy
Approximate bond energies at 298 K (kcal mol-1)

Note: these bond energies are not perfect for

any one molecule, but are the best average
values for a great number of molecules with the
same kind of bond.

Source: http://www.chem.ox.ac.uk/ 6
Energy units
• Calorie
 The original scientific unit in which changes in energy were measured
 One calorie (symbol: cal) is defined as the heat energy required to raise
the temperature of 1 g of water by 1 °C
 The name ‘calorie’ is used for another unit of energy: large calorie or
dietary calorie (symbol: Cal, equiv: kcal)

• Joule
 A derived unit of energy in the International System of Units

𝐽 =𝑁∙𝑚 =𝑊∙𝑠 =𝐶∙𝑉

 One joule (symbol: J) can be defined as:

 The work done in applying a force of 1 N through a distance of 1 m;
 The work required to produce 1 W of power for 1 s;
 The work required to move an electric charge of 1 C through an electrical
potential difference of 1 V. 7
Energy units
• Conversion between different energy units
 1 cal = 4.187 J
 1 J = 1 W·s
 1 kWh = 3600 kW·s = 3600 kJ = 3.6 MJ
 1 kJ = 1×103 J; 1 MJ = 1×106 J; 1 GJ = 1×109 J; 1 TJ = 1×1012 J; PJ, EJ, ZJ, YJ

• Energy content of biomass

Biomass Starch Protein Lipid

Gross calorific value (MJ kg-1) 16.6 22.4 37.3

Biomass Starch Protein Lipid

CH4 yield (N m3 kg-1) 0.415 0.496 1.014

8
Calorific value (heat of combustion)
• It is the measure of the energy that is chemically available in the
substance per unit mass (Units: energy per unit mass, mole or
volume e.g. MJ kg-1).
• It is usually determined as heat released upon combustion with
oxygen under standard conditions, and measured using a bomb
calorimeter.
• The energy recovered by bomb calorimeter is the theoretical
maximum bioenergy we can obtained from any biomass.

9
Bomb Calorimetry - Procedure

Ignition coil

The ‘bomb’ sample

10
Bomb Calorimetry - Procedure

Compressed oxygen

~ 10 bar

Ignition coil

The ‘bomb’

11
Bomb Calorimetry - Procedure
Thermometer

Stirrer

Insulated
water bath ~ 10 bar

Ignition coil

The ‘bomb’

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Bomb Calorimetry - Procedure
Thermometer
We measure increase
in temperature
Stirrer
- +
Insulated
water bath ~ 10 bar

Ignition coil

The ‘bomb’

13
The Bomb Calorimeter
• Temperature increase is used to
calculate the energy released
• Other data needed;
• Heat capacity of the system
including the water, bomb,
coil etc.
• Amount of energy input by
the ignition coil
• The sample weight added
• Modern bomb calorimeters do this
for us!

Source: http://chemistry.umeche.maine.edu 14
The Bomb Calorimeter

15
Calorific value: gross vs net

Net calorific value

Gross calorific value

Heat of Condensation

Source: http://www.chem.ox.ac.uk/

16
Calorific value: gross (HHV) vs net (LHV)
• In calorimeter, water vapour formed during the combustion
condenses at the end of the measurement, and the latent heat
of water condensation contributes to the heat value.
• Calorimeter measures the gross calorific value (GCV) or higher
heating value (HHV).
• The latent heat of the water vapour formed using combustion,
however, usually cannot be recovered in most thermal
processes in bioenergy production. In this case, the net calorific
value (NCV) or lower heating value (LHV) should be used to
express the amount of energy available.
• HHV > LHV in the context of bioenergy production

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Calorific value: HHV, LHV, water
• Water produced during the combustion
 C6H12O6 + 6O2 = 6CO2 + 6H2O
 2H2 + O2 = 2H2O
• Water also present in the biomass as moisture

Moisture
driven off

Oven, 105°C
FM ODM
usually overnight lost on
Furnace, 550°C
DM ignition
2 hrs

Ash
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Calorific value: HHV, LHV, water

When NO moisture present in biomass, for 1 kg of dried biomass:

CV:
HoC • Heat energy generated during the
combustion of organic matter in biomass

HHV
• Determined using bomb calorimeter using
ODM Combustion dried material
LHV HHV
Water generated
• Leave steam turbine as water vapour

LHV
• Energy available for capture in steam
turbine
Ash

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Calorific value: HHV, LHV, water

When moisture present in biomass, for 1 kg of moist biomass

HoC HoC
LHV of
LHV HHV biomass
ODM of Hvap of
ODM moisture
Ash Combustion

Moisture Hvap of
moisture
Energy consumed
Heat of evaporation
(=heat of condensation):
energy needed to
evaporate the moisture
in the biomass
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Example – HHV & LHV of moist starch
Calculate the LHV for two samples of starch (C6H10O5)n containing
10 and 80% moisture by weight respectively. HHV of starch is 16.6
MJ kg-1 and Heat of Condensation of water to 55°C is 2.445 kJ kg-1
1. Write equation for combustion of starch
C6H10O5 + 6O2 → 6CO2 + 5H2O
2. Calculate the LHV of dry starch
a. 1 mole starch (monomer) produces 5 moles of water
b. Molecular weight of starch monomer is 162, water is 18
c. 162 kg starch produces 5 × 18 = 90 kg water
d. 1 kg starch produces 90/162 = 0.556 kg water
e. LHV dry starch =
16.6 MJ kg-1starch – (0.556 kgwater kg-1starch × 2.445 MJ kg-1water ) = 15.2 MJ kg-1
3. LHV (10% moisture) = 15.3 × 0.9 –2.445 × 0.1= 13.5 MJ kg-1fresh matter

4. LHV (80% moisture) = 15.3 × 0.2 –2.445 × 0.8 = 1.09 MJ kg-1fresh matter
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Example – HHV & LHV of moist starch
LHV of wet starch at different moist content

16.0

12.0
LHV (MJ kg-1)

8.0

4.0

0.0

-4.0
0 20 40 60 80 100

Moisture content (% FM)

Moisture content of the biomass has a significant impact on the conversion process
• Thermochemical conversion processes require a low moisture content biomass, or there will be
a negative impact on the overall energy balance
• Biochemical conversion processes can utilise a high moisture content biomass
22
Empirical equation for HHV of biomass
• HHV of a biomass is related to it elemental composition (DuLong equation)
• Many improvements have been made, including
HHV = (34.1C + 102H - 9.85O + 6.3N + 19.1S) / 100
where elements C, H, O, N and S are expressed as mass fraction of biomass on
a organic dry matter basis (% ODM)
(Source: International Flame Research Foundation Online Combustion Handbook ISSN 1607-9116: Method from Combustion File 24)

• Elemental composition of biomass

Elemental composition (% ODM) HHV HoC of water LHV
Biomass
C H O N S (MJ kg-1 ODM) (MJ kg-1 ODM) (MJ kg-1 ODM)

starch 44.4 6.2 49.4 - - 16.6 1.4 15.2

protein 53.1 6.2 28.3 12.4 - 22.4 1.4 21.0
lipid 77.4 11.8 10.9 - - 37.3 2.6 34.7
References on elemental composition:
Angelidaki I. and Ellegaard L. (2004) Codigestion of manure and organic wastes in centralized biogas plants, Applied Biochemistry and Biotechnology, 109(1-3), 95-105.

• On a ODM basis
 HHV is positively related to the contents of C and H, and negatively related to that of O
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 The difference between HHV and LHV depends on the content of H
HHV and LHV of biomass
• Most biomass contains water which needs to be accounted for
when calculating the HHV and LHV in addition to the water
produced by the chemical reaction.

• This allows us to predict the most suitable type of processing

 LHV gives some indication of the energy that can be extracted from the
biomass in a thermal process (e.g. combustion). May not be exact e.g.
where heat is recovered by condensation of exhaust.
 HHV gives the maximum energy that could be extracted from the biomass
by any process.

• Where HHV>>LHV the material is probably better suited for an non-

thermal process (e.g. anaerobic digestion, bioethanol), where
HHV≈LHV is often feasible to thermal process.

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Use of calorific value in AD studies
• The HHV is the maximum amount of energy contained in the
chemical structure of the material
• The HHV will always be higher than can be obtained in terms of
‘energy product’ from a biological system as ‘energy’ is
consumed in the catabolic and anabolic metabolic pathways
• Energy loss during the biochemical reactions in the form of heat
• Part of biomass is difficult to digest
• It provides however a performance benchmark for AD systems

25
 Estimation of theoretical
maximum methane production

26
Anaerobic digestion process

Biomass Biogas
ODM CH4 + CO2

Digestate
ODM

27
Energy value of biogas

Oxidised carbon –
CO2 no energy value

Reduced carbon –
energy value:
CH4
HHV: ~55 MJ kg-1 or 40 MJ m-3
LHV: ~50 MJ kg-1 or 36 MJ m-3
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Theoretical maximum methane production (1)
- Calorific value of biomass

Biomass Biogas
ODM CH4 + CO2

Digestate
ODM

29
Theoretical maximum methane production (2)
- Buswell equation
• Buswell equation provides stoichiometric calculation on the
products from the anaerobic breakdown of a generic organic
material of chemical composition CcHhOoNnSs.
CcHhOoNnSs + 1/4(4c - h - 2o +3n + 2s)H2O
= 1/8(4c + h - 2o -3n - 2s)CH4 + 1/8(4c - h + 2o +3n + 2s)CO2
+ nNH3 + sH2S
where molecular formula subscriptions, c, h, o, n and s, represent the molar
proportion of mass fraction of elements C, H, O, N and S in the organic fraction
of biomass
Reference:
Symons, G. E. and A. M. Buswell (1933) The methane fermentation of carbohydrates. Journal of the American Chemical Society 55(5): 2028-2036.
Buswell, A. M. and H. F. Mueller (1952) Mechanism of methane fermentation. Industrial and Engineering Chemistry 44(3): 550-552.

30
Theoretical maximum methane production (2)
- Buswell equation
• Buswell equation
CcHhOoNnSs + 1/4(4c - h - 2o +3n + 2s)H2O
= 1/8(4c + h - 2o -3n - 2s)CH4 + 1/8(4c - h + 2o +3n + 2s)CO2 + nNH3 + sH2S

• Elemental composition of biomass

Elemental composition (% ODM) H2O consumed CH4 produced (m3 CO2 produced (m3
Biomass
C H O N S (kg kg-1 biomass) kg-1 biomass) kg-1 biomass)

Starch (C6H10O5)n 44.4 6.2 49.4 - - 0.11 0.415 0.415

Protein C5H7NO2 53.1 6.2 28.3 12.4 - 0.48 0.496 0.496
Lipid C57H104O6 77.4 11.8 10.9 - - 0.57 1.014 0.431
References on elemental composition:
Angelidaki I. and Ellegaard L. (2004) Codigestion of manure and organic wastes in centralized biogas plants, Applied Biochemistry and Biotechnology, 109(1-3), 95-105.

• On a ODM basis
 Methane production is positively related to the contents of C and H, and
negatively related to that of O 31
Theoretical maximum methane production (2)
- Buswell equation
• Elemental analysis (ultimate analysis)
O
C H N
S CO2, H2O, N2, SO2
He

O2

CO2, H2O, N2+NOx, SO2 O2

FlashEA 1112 32
Theoretical maximum methane production (2)
- Buswell equation
• The Buswell equation is used to estimate the theoretical maximum
CH4 production (as it assumes 100% organic biomass breakdown)
and related CH4 and CO2 proportion, as well as H2S and NH3
production.
• CH4 calculated using Buswell equation is always higher than can be
obtained in AD process as small portion of biomass is consumed in
the anabolic metabolic pathways and therefore converted to
microorganisms
• Part of biomass is difficult to digest
• It provides however another performance benchmark for AD
systems

33
Theoretical maximum methane production (3)
- Biochemical composition
• Biochemical composition is also a set of key parameters used to
describe biomass and choose (biochemical) process for biofuel
production
• Organic dry matter (in plant biomass) includes
 Simple sugars
 Starch Carbohydrates
 Cellulose
 Hemicellulose Lignocellulose, or fibre
 Lignin
 Lipid (fat & oil)
 Protein

• Effective component(s) & Conversion efficiency?

34
Theoretical maximum methane production (3)
- Biochemical composition
• Simple sugars
• Starch
• Cellulose
• Hemicellulose Biogas production via
anaerobic digestion
• Lignin
• Lipid
• Protein

Lignin
Source: Wikipedia

35
Theoretical maximum methane production (4)
- Chemical oxygen demand
• Chemical oxygen demand (COD) is commonly used in the
water and wastewater industry to measure the organic
strength of influent and effluent
• COD test is a wet chemistry analysis using strong oxidising
reagent under acidic condition and high temperature
• The strength is expressed in ‘oxygen equivalents’ i.e. the
amount of O2 required to oxidise the organic carbon to CO2
• The real advantage of the COD test is: when we measure the
amount of oxygen consumed by a sample, we are in essence
measuring the electrons transferred from the organic
compounds to the terminal electron acceptor, i.e. O2

36
Theoretical maximum methane production (4)
- Chemical oxygen demand
• Generally speaking, anaerobic conversion of complex organic
material into biogas can be regarded as a disproportionate
reaction of organic carbon: one stoichiometric portion of
organic carbon is oxidised to CO2, and the rest portion of
carbon is reduced to CH4
• During anaerobic digestion process, electrons flow from
oxidised carbon to reduced carbon, rather than captured by
external electron acceptors
• Electron balance of anaerobic digestion
COD of biomass = COD of CH4

37
Theoretical maximum methane production (4)
- Chemical oxygen demand
• COD of biomass = COD of CH4 produced
• Example: 1 mole of glucose C6H12O6
 COD of glucose = 192 g O2
C6H12O6 + 6O2 = 6CO2 + 6H2O
 Biochemical CH4 potential of glucose = 3 mole CH4 mol-1 glucose
C6H12O6 = 3CH4 + 3CO2
 COD of CH4 = 64 g O2 mol-1 CH4
CH4 + 2O2 = CO2 + 2H2O
 Total COD of CH4 produced from 1 mole of glucose = 3 × 64 = 192 g O2
 COD of glucose = COD of CH4 produced

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Theoretical maximum methane production (4)
- Chemical oxygen demand
• One mole of methane requires 2 moles of oxygen to oxidise it to
CO2 and water, so each gram of methane produced corresponds to
the removal of 4 grams of COD
CH4 + 2O2 = CO2 + 2H2O
16 64
• 1 g of CH4 produced corresponds to the removal of 4 g of COD
• 1 kg of COD removal is equivalent to 250 g of CH4
• 250 g of CH4
 250/16 = 15.62 moles of CH4
 15.62 × 22.4 = 350 STP litres of CH4 = 0.35 STP m3 of CH4
• At standard temperature and pressure 1 kg of COD removed will
yield 0.35 m3 of CH4

39
Anaerobic digestion practice
• Part of feed material is difficult to digest
• Another part of feed material is converted to microorganisms
• A third part of feed material is forced out of digester before
getting a chance to be digested
• Only a proportion of the feed material is converted to biogas.
This proportion is variable according to the characteristics of
feed material as well as reactor operating conditions, typically:
 Food waste 85%
 Maize silage 80%
 Biodegradable municipal waste 70%

40
Energy flow and mass flow in AD

Biogas
feedstock CH4 + CO2

Undigested biomass Stabilised waste

Microbial biomass Digestate Biofertiliser

41
How much energy can we get from AD?
• Up to 75~85% conversion of
organic fraction into biogas
• It has a methane content of 50-
60% (but will depend on
substrate)
• Biogas typically has a thermal
value of about 22 MJ m-3
• The thermal value of methane is
36 MJ m-3

42
Uses of biogas
Biogas
60% CH4 Boiler Heat 85%
40% CO2
Losses 15%
Electricity 35%

Biogas CHP Heat 50%

Losses 15%

Biomethane
Biogas Upgrade
CO2, H2S, H2O

Question: 1m3 of biogas (60% of methane) => ??? kWh of electricity in CHP unit?
43
Energy flow and mass flow in AD
1 2 3 4 5 6 7 8 9 10
Waste
input Proportion Proportion Proportion Proportion CH4 carbon Energy value
(tonnes) dry solids fixed carbon Fixed C (kg) converted to CH4 (kg) CH4 (kg) CH4 (Nm3 ) (MJ)
1.00 0.35 0.40 140.0 0.70 0.55 53.9 71.9 100.6 3622

Pasteurisation
1 2 3 4 5 6 7 8 9 10

Pasteurisatio Pasteurisation
Waste ratio of Make-up Input Pasteurisatio Temp n energy energy Heat energy
input make-up water temperature n temperature difference Thermal requirement requirement available from
(tonnes) water (tonnes) (oC) (oC) (oC) efficiency (MJ) (KWh) gas (MJ)
1.00 5 5.0 20 70 50 0.8 1568 435.4 3622

Digestion
1 Tonnes of wet waste (can be per unit of time e.g. per hour, day, year)
2 Dry weight of the waste (105 oC to constant weight)
3 This is the total carbon content derived from elemental or proximate analyisis. A value of 0.4 is fairly typical for MSW.
4 Calculates the available carbon (kg) that could theoretically find its way to methane or carbon dioxide.
5 This is the factor reflecting the conversion of fixed carbon in the digester (equivalent to the volatile solids destruction). Typical figures 0.3 for
6 Methane content of biogas
7 Calculates the weight of carbon going to methane
8 Calculates the weight of methane produced
9 Calculates the volume of methane at STP
10 Calculates the energy value of the methane @ 35.82 MJ per Nm3
11-13 calculates the volume of carbon dioxide
14 Calculates the total biogas volume at STP
44
15 Electrical conversion efficiency
Summary
• Biomass energy

• Estimation of theoretical maximum methane production

 Calorific value
 Elemental analysis and Buswell equation
 Biochemical composition approach
 Chemical oxygen demand approach

• Energy flow and mass flow in AD process

 Extent of digestion process (conversion efficiency)

45