BIOGAS PRINCIPLES

BIOGAS PRINCIPLES

SHORTINTRODUCTION

MUCHEKlranlagenbauGmbH Trifte85 32657Lemgo Germany Fon+495261770800 Fax+4952617708050 Mailinfo@mucheka.de www.mucheka.de

21.11.2008

BIOGAS PRINCIPLES

Overview
degradationpathways specificgasyield effectoftemperature buffersystem kinetics dissociation inhibition digestercontrol

degradationpathways
Threesubstances carbohydrates willalwaysproduce

proteins

fats BIOGAS lesssuitable: cellulose

unsuitable:

lignin

degradationpathways
Degradationpathwayswithtimeaxis CH4 +CO2 +H2O
seconds tominutes

Methanogenesis CO2 +H2 acetate

minutes tohours

Acetogenesis

CO2 +H2
minutes todays

acetate

propionate

butyrate

valeriate

ethanol

Acidogenesis monomer carbohydrates aminoacids long chain fatty acids

hours todays

Hydrolysis

polymerscarbonhydrates

fat

protein

anorganicsubstance

Pindetal:MonitoringandControlaofAnaerobicReactors2003

degradationpathways
degradationofstarch
decompositionbyamylase
(C6 H10O5 ) n +
decomposition by amylase

starch amylose ~27% amylopectin ~73%

n n Amylase H 2O C12 H 22O11 2 2

maltose
decomposition by maltase

decompositionbymaltase(glucosidase)
C12 H 22O11 + H 2O 2C6 H12O6
Glu cos idase

glucose aceticacid methane carbondioxide biogas

degradationpathways
degradationofcarbohydrates C6H12O6 + 4 H2O 2 CH3COO + 2 H2CO3 + 2 H+ + 4 H2

glucose maltose glucose exoenzyme H2 exoenzyme glucose

Bacteriawhichareinvolved intheanaerobicdegradation ofcarbohydrates: SaccharolyticalClostridia Clostridiumbutyricum Clostridiumacetobutylicum Clostridiumcellulosaedissolvens

pHoptimum 5.3 6.7

bacteria

aceticacid

degradationpathways

Lipaseproducingbacteria: Pseudomonascepacia Pseudomonasfluorescens Pseudomonasspecies

lipids
hydrolysis by lipase

degradationoflipids stoichiometry
C55 H104 O6 + 26 H2O 39 CH4 + 16 CO2

fattyacids
oxidation

glycerin
fermentation

aceticacid hydrogen carbondioxide biogas methane

degradationpathways
degradationofproteins stoichiometry
C13H25O7N3S1 +9H2O 6.5CH4 +3.5CO2 +H2S+3NH4+ +3HCO3 Bacteriawhichareinvolvedintheanaerobic fermentationofaminoacids: aminoacids Alanin Arganin bacteria Clostridiumpropionicium Clostridiumspp. Streptococcusspp. Clostridium

proteins
hydrolysis by proteases

oligopeptide
decompositio nby peptidase

dipeptide,aminoacids
deamination

Glutamat tetanomorphium Glycin Peptostreptococcusmicros Lysin Clostridiumsticklandii

Gerardi2003

aceticacid methane

ammonia

partofthereaction:deamination

carbondioxide biogas

pHoptimum 7.0

G0 = - 77,8 kJ / reaction

methanogenesis
reductionofcarbondioxide G0= 135.6kJ
CH4 CO2
CO2 + 4 H2 CH4 + 2 H2O

CH3COOH CH3COO +H
aceticacid undissociated aceticacid dissociated =acetate

H2O

H2

decarboxylationofaceticacid G0 = 31kJ
CH4 CO2

CH3COOH CH4 + CO2

receptionofaceticacidbymethanebacteria onlyinundissociatedform
pHoptimum 6.8 7.5

CH3COOH

CH3COO

H+

specificgasyield

substance

gasyield m/kg

methane content %byvolume 50 65 71

carbohydrates proteins lipids

0.830 0.610 1.430

sewagesludge primarysludge secondarysludge

gasyield m/kgTOS 0.500 0.400

TOS=totalorganicsolids

substrates
CompositionofVariousSubstrates(%ofDryMatter)

Component Volatilesolids Lipids Cellulose Hemicellulose CrudeProtein Ash

Primary Secondary Municipal Meatpacking Cattle manure waste sludge sludge Refuse 75.0 10.3 32.2 2.5 19.0 25.0 70.0 5.8 9.7 53.7 21.0 82.1 6.4 35.0 16.5 5.8 17.9 92.0 54.6 28.7 8.0 72.0 3.5 17.0 19.0 19.0 28.0

Chicken manure 76.0 1.5 28.3 11.9 28.8 24.0

Pavlostathis/GiraldoGomez1991

CODbalance
CODbiogas CODinfluent CODeffluent

DIGESTER

calculationCODofmethane

CH4 +2O2 CO2 +2H2O

1molCH4 16.04gCH4 22.4lCH4 CODCH4 =2molO2 =2*31.99gO2 =2*31.99gO2 =16.04/2*31.99 =0.25gCH4 =0.350NlCH4 10%oftheCODboundedasbacteria 0.350Nl 0.0525Nl=0.315NlCH4 mCH4 /kgCODreduced 0.315m/kgCSB
ATVFA7.5:TechnologischeBeurteilungzuranaerobenAbwasserbehandlung,KA40(1993)S.217223

effectoftemperature
OptimalgrowthtemperatureandoptimalpHofsomemethaneproducingbacteria
Genus Methanobacterium Methanobrivibacter Methanosphaera Methanothermus Methanococcus Temperaturerange C 37 45 37 40 35 40 83 88 35 40 65 91 Methanocorpusculum Methanoculleus Methanogenium Methanoplanus Methanospirillum Methanococcoides Methanohalobium Methanolobus Methanosarcina 30 40 35 40 20 40 30 40 35 40 30 35 50 55 35 40 30 40 50 55 Methanothrix 35 50 7.1 7.8 7.0 7.5 7.0 7.5 6.5 7.5 6.5 6.8 7.0 6.8 6.5 pH

MichaelH.Gerardi:TheMicrobiologyofAnaerobicDigesters,2003

effectoftemperature
TemperatureRangeforMethaneProductionfor MunicipialAnaerobicDigester Temperature[C] 35 32 34 21 31 <21 MethaneProduction Optimum Minimum Little,digestergoingsour Nil,digesterissour

MichaelH.Gerardi:TheMicrobiologyofAnaerobicDigesters,2003

Comparison of Mesophilic and Thermophilic Digesters

Feature Loading rates Destruction of pathogens Sensitivity of toxicants Operational costs Temperature control Mesophilic Digester Lower Lower Lower Lower Lessdifficult Thermophilic Digester Higher Higher Higher Higher Moredifficult

MichaelH.Gerardi:TheMicrobiologyofAnaerobicDigesters,2003

buffersystem
pH>6.7 [NH4+]=[HCO3]+[CH3COO] [CH3COO]=~0 [NH4+]=[HCO3] carbonicacidbufferHCO3/CO2 influence pH6.0 6.6 ammoniabufferNH3/NH4+ influence pH7.7

CO2Gas CH4

H2S

C13H25O7N3S1 +9H2O 6.5CH4 +3.5CO2 +H2S +3NH4+ +3HCO3 proteindegradation CO2 +H2O H2CO3 H+ +HCO3

carbonicacidbuffer NH3 +H2O NH3 +CO2 +H2O NH4+ +OH NH4+ +HCO3

ammoniabuffer

Theconcentrationofammoniaislimitedbythecarbonateconcentration

kinetics

definition
limitiation theoptimumconcentrationsarenotreached inhibition exceedingoftheoptimumconcentrations substratesurplusblocking substratesarepresentintoohighconcentrationsanddamage thecellorligateanenzymatthewrongposition nutrientexhaustion limitationbyexhaustionofnutrients

rateofgrowth relative

Theblockingoftheanaerobicgenerationofmethaneis causedbyexceedingoftheoptimumconcentrations

limitation

inhibition

concentration

dissociationaceticacid CH3COOH CH3COO +H+

undissociated acetic acid depends on pH-value
30 28 26 24 22 mg CH3COOH / l 20 18 16 14 12 10 8 6 4 2 0 6,5 6,6 6,7 6,8 6,9 7,0 7,1 7,2 7,3 7,4 7,5 7,6 7,7 7,8 7,9 8,0 pH-value
Mol.% 50 100 90 80 70 60

dissociationaceticacid

pK =4,76 pK=4.76

500

1.000

1.500

2.500

5.000

mg CH3COOH / l

40 30 20 10 0 1 2 3 4 5 6 7 8 9 pH 10 11 12 13 14

acetate

aceticacid

inhibition
1 I= S 1+ I KI
I =inhibitionfunction SI =concentrationoftheinhibitioncomponent KI =inhibitionconstant(50%inhibition) [] [mg/l] [mg/l]

inhibition=100 (I*100)[%]
pH NH4 kg/m 7.0 7.1 7.2 1.020 1.284 1.616 2.035 2.562 3.225 4.060 5.112 6.435 8.101 10.199 NH3 kg/m 0.005 0.008 0.013 0.020 0.032 0.051 0.081 0.129 0.205 0.324 0.514

InhibitionoftheanaerobicdigestionbyammoniaNH3
60 50 40 30 20 10 0 0 50 100 ammonia[mg/l] 150 200 250

inhibition[%]

KI =210mg/l
ammonia

7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0

HendersonHasselbalchequation

WiththeHendersonHasselbalchenequatationarelationbetweenthe dissociationconstant,theconcentrationsandthepHvaluecouldbebuilt:

[c ] pH = pK + log [c ]
A HA

Becausetheammoniumcontentinthedigestedsludgeisproportionaltothe hydrogencarbonatecontent[NH4+]=[HCO3 ],theammoniumcontentcouldbe definedfromtheCO2contentofthegas

pH = pKs,C

[HCO ] = pK + log [CO ]

3 2

s,N

[NH ] + log [NH ]

3 + 4

temperaturedependencyofpKs,N
p Ks,N = A + B C*T T

HendersonHasselbalchequation

ThedegreeofCO2saturationcanbecalculatedwiththe HenrycoefficientandtheCO2partialpressureas:

[CO ] = K
2

H ,CO2

* pCO2 = K H ,CO2 *( p p H2O ) * cCO2

Ifthephvalueisknown,theNH4+ andtheNH3content couldbedefinedbychangingtheterm:

+ NH 4 NH 3 pH = 6,31 + log = 8,95 + log + CO2 NH 4

+ log NH 4 = pH 6,31 + log CO2

+ log NH 3 = pH 8,95 + log NH 4

digestercontrol

OK

substrateaddition weighingmass more substrateaddition <reference

gasproduction

stop substrateaddition OK noneedforaction

controlspezificgasproduction

measure:pHvalue

< reference
measure:CO2concentration measure:aceticacidconcentration measure:propionicacidconcentration

gasquality

OK

noneedforaction

noheat

> reference

temperature

OK

noneedforaction

<reference
toheat

OK

calculationundissociatedacid calculationundissociatedammonia

<reference