Modelling of Material and Energy

Balance of Biogas Production Process

Mandy Gerber

2nd GERG Academic Network Event

Brussels, June 2010

Basics

Biogas Range Average

Process
Metabolic waste product Vol-% Vol-%
CH4 45 70 60
CO2 25 55 35
Production
H2Od
Degradation of organic matter (25C, 1 atm)
0 10 3.1

(protein, carbohydrate, fats) N2 0.01 5 1

in anaerobic environment O2 0.01 2 0.03
Natural process identical to H2 01 <1
swamp / marsh, cattle rumen, NH3 0.01 2.5* 0.7*

sewage sludge, dumps, rice field H2S 10 30,000* 500*

* in mg/m DVGW, 2005

Input material
Manure, energy crops, organic waste

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 2

Basics

IEKP of German government

Integrated energy and climate programme (measures to
increase energy efficiency and use of renewable energies)
Objective: replace 10% of gas supply by gas out of biomass
(60109 kWh biogas per year until 2020, 100109 kWh biogas per year until
2030)

Quality of biogas for feeding in gas distribution net

Raw biogas: HHV = 5.2 - 8.2 kWh/m, WS = 18.0 - 33.1 MJ/m
(average: HHV = 6.9 kWh/m, WS = 26.1 MJ/m)
Upgraded biogas: HHV = 10.8 kWh/m, WS = 51.3 MJ/m
Depending on net and biogas quality as exchange gas or
additional gas
(L-Gas: WS = 37.8 - 46.8 MJ/m, H-Gas: WS = 46.1 - 56.5 MJ/m,
HHV = 8.4 - 13.1 kWh/m)

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 3

Basics

Status biogas plants in Germany

30 of about 4500 biogas plants with feed in a gas distribution net
(about 2.6% of government goal)
To reach the goal of government: Construction of 100 120
biogas plants per year until 2020 will be needed
(700 Nm/h, 8000 operating hours)
1. modified 2. modiefied
EEG EEG EEG
1600
5000 1600
1400
4780
biogas plants 1400
1270
4000
installed power 4000 1200
number of biogas plants

power installed in MW
950 3711
1000
3000 2690

665 3280 800

2010
2000 1760
1608 600
1360
1043 400
850 247
1000
160 190
111 200
49 78

0 0
1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009*

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Basics

Typical biogas plant

Two-stages
Feed: energy crops and manure

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Modelling

Aspen Custom Modeller

Modelling
of important
plant
components

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Material Balance Fermenter 0.4
max = 0,4 d-1

-1
KS = 0,033 mmol/L

specific growth rate in d

0.3 KI = 0,667 mmol/L

Process parameter 0.2

Quality of input material 0.1 pH 6.0

pH 6.5
(organic components, complex organic pH 7.0
0.0
inhibitors, trace elements) 100% 0 20 40 60 80 100 120
substrate concentration in mmol/L

Quantity of input biodegradable organic

material
carbo-
proteins hydrate fats

21% 40% 5% 21%

(organic loading rate, Hydrolysis
(hydrolytic enzymes)
dilution)
amino acids, mono saccharide fatty acids

pH value / alkalinity / 46% 20% 34%

Acidogenesis
phase equilibrium (acidogentic microorganisms)
propionate, butyrate, etc
Temperature Acetogenesis
(acetogenic microorganisms)

Adaption of 35% 12% 23% 11% 8% 11%

microorganism
acetate H2, CO2

70% 30% Methanogenesis

(methanogenic microorganisms)

CH4, CO2

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 7

Material Balance Fermenter

Static models
Baserga
based on gas production
of organic components
Keymer & Schilcher
based on Baserga incl.
degradation coefficients
except KTBL and batch test
mostly used for facility design
qKoS = xCH qCH + xLip qLip + xProt qProt
derived from evaluating animal feed
qKoS = xi VQi qi
i

Boyle
based on elementary maximum of gas production as reference
composition state b c 3d e
CaH bOc Nd Se + a + + H2O
4 2 4 2
a b c 3d e
+ CH 4
2 8 4 8 4
a b c 3d e
+ + + + CO2 + d NH3 + e H2S
2 8 4 8 4

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 8

Material Balance Fermenter

Comparison to literature and laboratory

100
standardised gas production in %

80

60

40
CCM 2
CCM 3
20 inhibition

0
0 10 20 30 40 50 60
test duration in d

Cattle manure Corn silage CCM GPS

lab literature lab literature lab literature lab literature
Boyle -122.7 -186.7 -75.4 -48.7 -80.5 - -73.1 -82.1
Baserga 21.2 -1.4 -43.7 -21.8 -56.4 - -45.0 -52.5
K&S 21.2 -1.4 -3.1 12.6 -33.7 - 10.1 5.4
Deviation in % [100 (lN,exp/lit lN,calc) / lN,exp/lit] of specific gas production (lN/kgOM):

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 9

Material Balance Fermenter

Comparison to a large
scale biogas plant

Boyle Baserga K&S Praxis Boyle Baserga K&S

Gas production
in lN/kgOM 965 771 554 548 -76.0 -40.7 -1.1
in lN/kgOM 154 123 89 88 -76.0 -40.7 -1.1
CH4 Vol.-% 48.7 50.6 50.5 49.4 1.3 -2.5 -2.2
CO2 Vol.-% 45.3 46.1 46.2 47.3 4.1 2.6 2.3
H2S Vol.-% 0.1 - - 0.1 -44.2 - -
NH3 Vol.-% 2.5 - - - - - -
H2O Vol.-% 3.3 3.3 3.3 3.3 0.0 0.0 0.0

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 10

Material Balance Fermenter

Dynamic models
Andrews & Graef Hill & Barth ADM1
Degradation steps 1 2 19
Input material acetic acid organic matter, CH, XP, XL, MS, AA, AC,
acetic acid PR, BU, VA, LCFA, H2,
CH4, 7 MO, Comp, IN, IC ,
PI, SI
Gas CH4, CO2, H2O CH4, CO2, NH3, H2O CH4, CO2, H2, H2O
Temperature vapour pressure growth rate, vapour Henry coefficient, acid
pressure coefficient, vapour pressure
Gas solubility CO2 CO2, NH3 CH4, CO2, H2
Ionic equilibrium CO2, acetic acid, H2O CO2, acetic acid, H2O VOA, CO2, H2O, NH3
Inhibition substrate Substrate substrate, NH3, H2, pH
Complexity low medium high
Adapted to process stability, less less input, many output many input parameters,
input parameters parameters many dependencies
CH: carbohydrate, XP: protein, XL: lipid, MS: monosaccharide, AA: Amino Acid, LCFA: Long Chain Fatty Acid,
VA: Valeric Acid, BU: Butyric Acid, PR: Propionic Acid, AC: Acetic Acid, MO: Microorganism, Comp: Composites, PI: Particulate Inert,
SI: Soluble Inert, IN: Inorganic Nitrogen, IC: Inorganic Carbon, A-: Anions, C+: Cations

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 11

Material Balance Fermenter

Model of Andrews & Graef

Liquid phase
dcm,CO 2D ,1 V0
CO2 balance = ( cm,CO 2D ,0 cm,CO 2D ,1 ) + TG + RB + RC Biological phase
dt VL
dX1 V0
dcm,Z ,1 V0 organism balance = ( X 0 X1 ) + X1
netto cation balance = ( cm,Z ,0 cm,Z ,1 ) dt VL
dt VL
dcm,AC ,1 V0
V dc dc acetic acid balance = ( cm,AC ,0 cm,AC ,1 ) X1
chemical production rate RC = 0 ( cm,HCO 3,0 cm,HCO 3,1 ) + m,AC ,1 m,Z ,1 dt VL YX / S
VL dt dt
max
gas transfer rate (
TG = K LA,CO 2 cm,CO 2S cm,CO 2D ,1 ) growth rate
=
KS cm,HAc ,1
1+ +
dissolved CO2, cm,HAc ,1 KI
cm,CO 2S = K H ,CO 2 pCO 2
saturated biological production
RB = YCO 2 / X X1
carbonate cm,HCO 3,1 = cm,Z ,1 cm,AC ,1 rate CO2

cm,H + ,1 cm,AC ,1 Coefficients

unionised acetic acid cm,HAC ,1 =
K AC K a,AC 10-4,5 ionisation constant acetic acid at 38C
-6
KC cm,CO 2D ,1 K a,C 10 ionisation constant CO2 at 38C
hydrogen cm,H + ,1 =
cm,HCO 3,1 0,024272
K H ,CO 2 Henrys law constant CO2 at 38C
kmol/barm
pH value (
pH = log cm,H + ,1 ) K LA,CO 2 100 d-1 gas transfer rate
Gas phase KI 0,667 mol/m inhibition constant
biogas VBG = VCH 4 + VCO 2 KS 0,0333 mol/m saturation constant
VCO 2 = v m VL TG
-1
CO2 production max 0,04 d maximum growth rate

CH4 production VCH 4 = v m VL YCH 4 / X X1 YCO 2 / X 47 kmolCO2/kmolX Yield coefficient biomass to CO2

dpCO 2 V p YCH 4 / X 47 kmolCH4/kmolX Yield coefficient biomass to CH4

CO2 partial pressure = pT v m L TG CO 2 VBG
dt VG VG YX / AC 0,02 kmolX/kmolAC Yield coefficient acetic acid to biomass

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 12

 Material Balance Fermenter

Spontanously triplication of feeding

18 0.18
0.0045 1 to 3 l/day
1 to 2 l/day

microorganism concentration
16 0.16
0.0040

substrate concentration
gas production in l/day

14 0.0035 0.14
12 1 to 2 l/day
0.0030 0.12

in kmol/m

in kmol/m
10 0.0025 0.10
8 0.0020 0.08
6 0.0015 0.06 1 to 2 l/day
4 0.0010 0.04
2 0.0005 1 to 3 l/day 0.02
1 to 3 l/day
0 0.0000 0.00
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
test duration in d test duration in d
test duration in d

60 0.30 9.0 0.014

1 to 2 l/day 8.0 1 to 2
0.25 0.012
50

concentration HCO3
7.0
growth rate in 1/day
methane in vol.-%

1 to 2 l/day 0.010
40 0.20 6.0

in kmol/m
5.0 0.008
1 to 3

pH
30 0.15
4.0 0.006
20 0.10 3.0
0.004
2.0
10 0.05 0.002
1.0
1 to 3 l/day 1 to 3 l/day
0 0.00 0.0 0.000
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
test duration in d test duration in d test duration in d

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Summary

Conclusion
Tool to design and optimise biogas plants
Investigation of process failures and reaction rates possible

Outlook
More data needed for validation, especially for dynamic models
expand simulation for modeling of gas treatment

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 14

 Thank you
for your attention!

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 15

Energy Balance Fermenter
Danish Agricultural
fermenter fermenter
Number of mixer 1 3
Danish Fermenter
Power 18.9 kW 38.3 kW
454 kWh/d 77 kWh/d
Energy Demand
(24 h/d) (2 h/d)
Agricultural Fermenter
Feed: manure and corn silage (1:1), 3.65 kgOM/(md),
volume 3000 m, retention time 74d, temperature 38C

PMix = Ne n 3 dR5

Power demand mixer

Danish fermenter: one central, slow ongoing agitator
Agricultural fermenter: one or more submersible, fast ongoing
motor-driven agitators
Calculation by Newton-Number (geometry, agitator speed, flow,
density / viscosity - composition)
Mandy Gerber | 2nd GERG Academic Network Event | June 2010 16
Energy Balance Fermenter
Danish Agricultural
fermenter fermenter
Heat Demand 90.3 kW 38.3 kW

H BG
2167 kWh/d 2936 kWh/d

H Feed: manure and corn silage (1:1), 3.65 kgOM/(md),
SUB

H volume 3.000 m, retention time 74d, temperature
DIG
fermenter 38C, input material 20C, ambient 15C, wind
  speed 5 m/s
Q Heiz Q Loss PDiss
tRe f  ,t
HBG BG

 ,t
H tRe f
SUB SUB

tRe f  ,t
HDIG DIG
Heat demand Reaktion

Heat loss via roof, wall and ground (heat transfer coefficient of
every layer depending on temperature, wind speed, geometry,
fluid properties)
Dissipation Mixer
Enthalpy balance fr heat of reaction and temperature difference
substrate / biogas (heating value, evaporation, heat capacity)

Mandy Gerber | 2nd GERG Academic Network Event | June 2010 17