Chapter6:BiogasCleaning

Biogasiscomposedprimarilyofmethane(CH4),carbondioxide(CO2)andvariousothergases.
Typically,thecompositionofrawbiogasfromanaerobicdigestionis:

Methane

CH4 50%80%
Carbondioxide
CO2 20%50%
WaterVapour
H2O Saturated25%(mass)
Nitrogen

N2* 14%
Oxygen

O2* <1%
Hydrogensulphide H2S 505000ppm
Ammonia

NH3 0300ppm
Tracegasses
Siloxanesandhalogenatedhydrocarbonsinverylowconcentrations
Nongaseous
Particulateandoilinlowconcentrations
*OnlypresentifairisinjectedintothedigesterforH2Sreduction

Biogasfromonfarmanaerobicdigestionshouldnotcontainrelevantamountsofanythingthat
isnotpresentinthelistabove.Infact,eventhepotentialtracegassesshouldbeabsentfrom
farmbiogasduetothefeedstocksutilized,andthehydrogensulphideandammoniashouldbe
atthelowerendofthespectrumspresentedabove.

Sincetheprimaryobjectiveofanonfarmanaerobicdigestionsystemistoproducemethane,it
isdesirabletoremoveotherbiogascomponentsbecausetheyrepresentanenvironmental
hazard,aprocessingproblem,ordilutetheenergydensityofthebiogas.Thefollowingsections
presentvariouswaysofmanagingthenonmethanecomponentsofbiogas.Theremovalof
theseothercomponentsisbrokendownintotwosteps,biogascleaningandbiogasupgrading.
BiogascleaningreferstotheremovalofH2S,watervapour,NH3,particles,etc.,whereasbiogas
upgradinggenerallyreferstotheremovalofCO2.Allbiogasapplicationshavesomelevelof
biogascleaning,however,cogenerationrequiressignificantlyless.

6.1 RemovalofHydrogenSulphide(H2S)
H2Sispresentinbiogasresultingfromtheanaerobicdigestionoforganicmaterialcontaining
sulphur.Theconcentrationofthistoxicandcorrosivegasinrawbiogasmayvarygreatly
dependingonthenatureofthefeedstock.Concentrationsarereportedbetween505000
ppmforH2Sinrawbiogas.H2Sinbiogashastobereducedtolevelswhereitdoesnotharmthe
processdownstream.Downstreamconcernsrevolvearoundpublichealthandsafetyissues
suchashumantoxicityandcorrosiveeffectonmechanicalpartsandgaskets.Intermsof
equipmenttolerances,H2Sconcentrationshavetotypicallybereducedtobetween200500
ppmforcombustionofbiogasinaninternalcombustionengine(cogeneration)whileinjection
intothegridasupgradedbiomethane(naturalgasequivalent),wouldrequirereductiondown
tobelow4ppm.
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BarringstructuralfailuresordirectventingofrawbiogastotheatmospherenoH2Sshouldbe
dischargedfromanonfarmbiogassystem.Theonlyotherpathwayforbiogastoexitthe
systemisviacombustion(flare,boilerburnerorinternalcombustionengine)whichwilloxidize
H2StoSOx.

SeveralmethodsforreducingtheconcentrationofH2Scanbeappliedinanonfarmanaerobic
digestioncontext.Table5summarizesthedifferenttechnologiesandtheirwastedischarges.

Table 5: Summary of Typical H2S Removal Methods and their Waste Discharges

H2S
Removal
Method

TechnicalDescription

Biological
fixation

Airisventilatedintothegas
headspaceabovethe
digestingfeedstockinthe
digester.Thetargetis26%
airinthebiogas.Sulphur
oxidizingbacteriaconverts
H2Stoelementalsulphur(S)
andwater.

Iron
chloride
dosing

Liquidironchloridesolution
isinjecteddirectlyintothe
feedstockmixingtank.
Normaldosingis4g/liter
feedstock.H2Sisconverted
andcontainedinthe
feedstockasFe2(SO4)3.has
theaddedpositiveeffectof
reducingodour.
Water
CreateasolutionofH2Sin
scrubbing waterbyfeedingthebiogas
throughacounterflowof
water.Normallyonlyused
incombinationwithwater
scrubbingbiogasupgrading
technologies.

Contaminants
Introducedto
Biogasor
Digestate
Nitrogenis
introducedto
thebiogaswith
airinjection.
Excessairmay
drivetheH2S
oxidization
processto
produce
sulphuricacid
insteadof
elemental
sulphur.
Whilechloride
ionsare
introducedto
thesystem,they
remaininthe
digestatewhere
theycauseno
problem.
No
contaminants
introduced.

WasteDischarges

Nodirectdischarges.

Presenceofnitrogen(N2)inbiogas
resultsinNOxemissionswhen
combusted.

Sulphuricacidisfullybufferedinthe
digestateandisthereforenot
discharged.

Nodirectdischarges.

Addedchloridedoesnotresultin
chloriderelatedcombustion
discharges.

Scrubbingwaterisdischarged.

Theprocesscanbedesignedasa
regenerativeprocess,inwhichcase
scrubbingwaterdischargewouldbe
significantlyreduced.

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H2S
Removal
Method

Activated
Carbon

TechnicalDescription

Rawbiogasflowisled
throughanactivatedcarbon
filterimpregnatedwith
potassiumiodine(KI)or
sulphuricacid(H2SO4).This
methodisusuallyusedin
combinationwithand
subsequenttoventilationof
airintothebiogas(see
biologicalfixation).H2Sis
convertedtoelemental
sulphur(S)whichisreturned
todigester.
Iron
Biogasispassedthrougha
Hydroxide mediacomposedof
orOxide woodchipsandironoxideor
hydroxide.H2Sreactsto
formironsulphide.Less
commonmediaarerust
coatedsteelwoolor
pelletedredmud(aby
productofaluminum
production).
Sodium
BiogasbubbledinanNaOH
Hydroxide solutionformssodium
sulphideorsodium
hydrogensulphide.

Contaminants
Introducedto
Biogasor
Digestate

No
contaminants
introduced.

No
contaminants
introduced.

No
contaminants
introduced.

WasteDischarges

Iftheprocessisregenerativethe
desorbedgaswillbeventedout
throughanabsorptionfilterofactive
carbon,ironhydroxideorironoxide
type(seenextitemsintable).

Thedesorbedgasthatpasses
throughthefilterconstitutesanair
discharge.
Regenerationoftheactivated
carbonwillresultinairemissions
howeverthisactivitywillmostlikely
occuroffsiteataspecializedfacility.

Activatedcarbonislistedasa
DangerousGood.

Thisprocessisoftenregenerative,
buteventuallythefiltermediawill
havetobereplaced.Dependingon
filtermediaused,thespentmedia
mayconstituteahazardouswaste
andmustbedisposedof
accordingly.

Note:FeSispyrophorriccan
spontaneouslycombust.
Scrubbingwatercontainingsodium
sulphideorsodiumhydrogen
sulphide.

Causticsolutionsarefrequently
dangerousgoods.Thespent
materialmayormaynotbe.

Theprocessrequireslessscrubbing
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H2S
Removal
Method

TechnicalDescription

Contaminants
Introducedto
Biogasor
Digestate

WasteDischarges

agent(NaOHsolution)comparedto
purewaterscrubbingbutthe
processcannotbemade
regenerative.

6.2 WaterVapourRemoval
Biogasfromanaerobicdigestioniscommonlysaturatedwithwater.Mostbiogasutilization
processesrequirerelativelydrygas,sodryingisoftennecessary.Somecleaningandupgrading
techniques(e.g.,waterscrubbing),addwatervapourtoanonsaturatedbiogas.Nevertheless,
biogashastobedrypriortogridinjectionandfairlydrybeforecombustion.

Watervapourisaproblem,asitmaycondenseintowateroricewhenpassingfromhigh
pressuretolowerpressure.Thismayresultincorrosionissuesandthepressureregulator
clogginginthegasconveyancesystem.

Severalmethodsforreducingthepresenceofwatervapourcanbeappliedinanonfarm
anaerobicdigestioncontext.Table6summarizesthedifferenttechnologies.

Table 6: Summary of Water Vapour Removal Methods

Water
Vapour
Removal
Method
Passivegas
cooling

TechnicalDescription

Gasisleadunderground
forashortperiodoftime
tobecooled.Cooling
condenseswaterfromthe
gaswhichiscollected.

Contaminants
Introducedto
Biogasor
Digestate
Nocontaminants
introduced.

Refrigeration Heatexchangersareused Nocontaminants

tocoolthebiogasto
introduced.
desireddewpointwhere

watervapourcondenses.
Biogascanbepressurized
toachievefurtherdryness.

WasteDischarges

Couldresultindischargeof
condensatewatertothesewer
butnormallythecondensateis
recycledbackintothedigester.
Couldresultindischargeof
condensatewatertothesewer
butnormallythecondensateis
recycledbackintothedigester.

Spentrefrigerantcontaminated
withanothersubstancemay
constituteahazardouswaste
andmustbedisposedof
accordingly.
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Absorption

Glycolorhygroscopicsalts Nocontaminants
absorbwaterasbiogasis
introduced.
directedthroughthe
dryingmedium.Drying
mediumisregeneratedby
dryingitathigh
temperature.

Processisregenerativebut
eventuallythedryingmediawill
havetobereplaced.Inthecase
ofhygroscopicsaltsthiswill
resultinanonhazardoussolid
wastestream.

Adsorption

Silicageloraluminum
oxideadsorbswateras
biogasisdirectedthrough
themedium.Drying
mediumisregeneratedby
dryingitathigh
temperatureathigh
pressure(otherwiseair
needstobeinjectedfor
regeneration).

Processisregenerativebut
eventuallythedryingmediawill
havetobereplaced,whichwill
resultinanonhazardoussolid
wastestream.

Nocontaminants
introduced.

6.3 Ammonia
Apartfrombeingcorrosiveonmechanicalparts,thecombustionofammonia(NH3)asa
constituentofbiogasleadstotheformationofnitrogenoxides(NOx).However,sincethereis
verylittleNH3inbiogasderivedfromorganicfeedstock,itusuallystaysbelow1ppm.

Giventhatammoniaissolubleinwater,theconcentrationcanbefurtherreducedby
refrigeratedwatervapourremovalmethodsaswellasanywaterscrubbingtechnologywhere
thebiogasispassedthroughacounterflowofwater.Neitherofthesesystemsintroduces
contaminantsandonlynonregenerativewaterscrubbinggeneratesawastedischarge,e.g.,
scrubbingwatertosewer.

6.4 Particles
Somedustandoilparticlesfromthecompressorsmaybepresentinthegas.Theseparticles
havetobefilteredoutusing2to5mfiltersmadeofpaperorfabric,whichwillneedtobe
replacedatregularintervalsaspartofnormalmaintenance.Nocontaminantsareintroduced
butthereplacedfilterswillconstituteanonhazardoussolidwastedischarge.

6.5 Siloxanes
Siloxanescanbefoundincosmetics,deodorants,foodadditivesandsoaps.Thepresencein
biogascausesabrasivesiloxanedepositsonpistonsandcylinderheadswhichreduceenginelife
drastically.Theyaremainlyfoundinlandfillgasandwastewatertreatmentplantbiogasand
shouldnotbepresentinfarmbiogasfromtheacceptablefeedstockspresentedinthisguideline
40

(seeChapter11).Activatedcarbonfiltrationcanbeusedtoremovesiloxanesincaseswhere
theyarefoundtobepresent.Thiswouldnotintroducecontaminantsbutthefiltermediamay
constituteahazardoussolidwastedischargewhenreplaced.

6.6 Halogenatedhydrocarbons
Whenpresentinbiogas,halogensarecorrosivetomechanicalpartsandcanleadtothe
formationofdioxinsandfuransduringcombustion.Halogenatedhydrocarbonsandhigher
hydrocarbonsarepresentinbiogasfromlandfillsbutrarelyinbiogasfromsewagesludgeand
shouldnotbepresentinfarmbiogasfromacceptablefeedstocks(seeChapter11).Activated
carbonfiltrationcanbeusedtoremovehalogenatedhydrocarbonsincaseswheretheyare
foundtobepresent.Thiswouldnotintroducecontaminantsbutthefiltermediamay
constituteahazardouswastedischargewhenreplaced.

6.7 Oxygen
Oxygenisacommonbiogascontaminantinlandfillgasbutisnotfoundathighconcentrations
inbiogasfromanaerobicdigestionunlessintroducedthroughbiologicalfixationaspartofthe
H2Sremovalsystem.However,mostoftheoxygenisusedbythebiologicalprocessleaving
onlytracesofoxygenintheH2Sscrubbedbiogas.Thesignificanceofoxygenasabiogas
contaminantisnotrelatedtoenvironmentalorprocessimpactsbutratherithasadilution
effectonbiogasenergycontent.Nomethodsspecificallyaimedtoremoveoxygenarelikelyto
beemployedinanonfarmbiogasproductioncontext.However,oxygenispartiallyremoved
bythebiogasupgradingmethodsofmembraneseparationandlowpressurePSAthatare
explainedinChapter7.Nocontaminantsareintroducedandtheonlywastedischargesare
thoseassociatedwiththebiogasupgradingmethodsaspresentedinTable8.

6.8 Nitrogen
Sinceitisinert,theeffectofnitrogenonthefinaloutputisadilutionoftheenergycontentof
thebiogas.Landfillgascontainsalargeproportionofnitrogenbutitshouldbeabsentfrom
farmbiogasderivedfromacceptablefeedstocksaspresentedinChapter11ofthisguideline,
unlessH2Sabatementrequiresairinjection.At4%injectionofair,theoutputofnitrogen
wouldbe3.1%.Nitrogenisverydifficulttoremove.ThetwobiogasupgradingmethodsofPSA
andcryogenicsystemscanremovenitrogenbutitisgenerallytooexpensive.Asaresultthe
mostcommonwayofdealingwithnitrogeninbiogasistotrytolimitintroductionofitbefore
orduringbiogascleaningandtosimplyacceptwhatevertheresultingnitrogenlevelsareinthe
finalbiomethaneproduct.PresenceofnitrogeninthebiogasmayleadtoincreasedNOx
combustionemissions.

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Proponentsshouldidentifythefollowinginanapplication:

Expectedchemicalcompositionoftherawbiogas
Thebiogascleaningmethodsthatwillbeutilizedtoremovecontaminantsfromtheraw
biogas
Expecteddischargelevelsfromtheutilizedbiogascleaningmethods(usevendor
informationand/orrealdatafromthefacilitytoaddressallpotentialdischarges
mentionedinTable4andtextofChapter6).

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