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. 36

 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 Biological fixation

TechnicalDescription

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. 37

H2S Removal Method

TechnicalDescription

Contaminants Introducedto Biogasor Digestate

WasteDischarges

Activated Carbon

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.

No contaminants introduced.

Iftheprocessisregenerativethe desorbedgaswillbeventedout throughanabsorptionfilterofactive carbon,ironhydroxideorironoxide type(seenextitemsintable). Thedesorbedgasthatpasses throughthefilterconstitutesanair discharge. Regenerationoftheactivated carbonwillresultinairemissions howeverthisactivitywillmostlikely occuroffsiteataspecializedfacility. Activatedcarbonislistedasa DangerousGood.

No contaminants introduced.

No contaminants introduced.

Thisprocessisoftenregenerative, buteventuallythefiltermediawill havetobereplaced.Dependingon filtermediaused,thespentmedia mayconstituteahazardouswaste andmustbedisposedof accordingly. Note:FeSispyrophorriccan spontaneouslycombust. Scrubbingwatercontainingsodium sulphideorsodiumhydrogen sulphide. Causticsolutionsarefrequently dangerousgoods.Thespent materialmayormaynotbe.

Theprocessrequireslessscrubbing 38

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.

WasteDischarges

Couldresultindischargeof condensatewatertothesewer butnormallythecondensateis recycledbackintothedigester. Couldresultindischargeof condensatewatertothesewer butnormallythecondensateis recycledbackintothedigester. Spentrefrigerantcontaminated withanothersubstancemay constituteahazardouswaste andmustbedisposedof accordingly. 39

Refrigeration Heatexchangersareused Nocontaminants tocoolthebiogasto introduced. desireddewpointwhere watervapourcondenses. Biogascanbepressurized toachievefurtherdryness.

Absorption

Glycolorhygroscopicsalts Nocontaminants absorbwaterasbiogasis introduced. directedthroughthe dryingmedium.Drying mediumisregeneratedby dryingitathigh temperature. Silicageloraluminum oxideadsorbswateras biogasisdirectedthrough themedium.Drying mediumisregeneratedby dryingitathigh temperatureathigh pressure(otherwiseair needstobeinjectedfor regeneration). Nocontaminants introduced.

Processisregenerativebut eventuallythedryingmediawill havetobereplaced.Inthecase ofhygroscopicsaltsthiswill resultinanonhazardoussolid wastestream. Processisregenerativebut eventuallythedryingmediawill havetobereplaced,whichwill resultinanonhazardoussolid wastestream.

Adsorption

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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