M argaret a PERSSON Owe JNSSON Art hur WELLINGER Biogas Upgrading IEABioenergy Content Biogas Upgrading AUTHORS M argaret a PERSSON and Owe JNSSON Swedi sh Gas Cent er (SGC) Scheel egat an 3, 212 28 M al m, Schweden Art hur WELLINGER Nova Energi e GmbH Cht el st rasse 21 8355 Aadorf , Swi t zerl and IM PRESSUM Graphi c Desi gn: Susanne AUER, Vi enna Phot os court esy of t he Swedi sh Gas Cent er and Nova Energi e GmbH December 2006 Task 37- EnergyfromBiogas andLandfill Gas BY THE END OF 2006 THE FOLLOWING NATIONS WERE M EM BERS OF TASK 37: Aust ri a Rudol f BRAUN, braun@i f a-t ul l n.ac.at Denmark Jens Bo HOLM -NIELSEN, j hn@bi o.sdu.dk Teodori t a AL SEADI, t as@bi o.sdu.dk EC Davi d BAXTER, davi d.baxt er@j rc.nl Fi nl and M art t i JORM ANAINNEN, mart t i .j ormanai nnen@kol umbus.f i Jukka RINTALA, j ri nt al a@j yu.f i Germany Pet er WEILAND, pet er.wei l and@f al .de Sweden Owe JNSSON, owe.j onsson@sgc.se M argari t a PERSSON, margaret a.persson@sgc.se Swi t zerl and Art hur WELLINGER (Task Leader), art hur.wel l i nger@novaenergi e.ch The Net herl ands M at hi eu DUM ONT, m.dumont @ sent ernovem.nl UK Chri s M ALTIN, mpcs@organi c-power.co.uk ACKNOWLEDGEM ENT The brochure was wri t t en i n cl ose co-operat i on wi t h t he Ci t y of St ockhol m whose cont ri but i on i s acknowl edged. Part of t he work was enabl ed t hrough f undi ng f rom t he EU Bi ogasM ax proj ect by t he EU commi ssi on. Content Introduction 4 Biogas Composition 5 Typi cal cont ami nant s i n bi ogas 7 National gas standards 8 Sweden 8 Swi t zerl and 9 Germany 9 France 10 Gas Utilisation 11 Product i on of heat 11 Power generat i on/ Combi ned Heat and Power (CHP) 12 Bi ogas i nj ect i on i nt o t he gas gri d 16 Gas upgradingtechnologies 16 Carbon di oxi de removal 17 Removal of hydrogen sul phi de 21 Removal of t race gases 23 Cost for upgrading 25 Casestudies 26 Inj ect i on of upgraded bi ogas (Hardenberg The Net herl ands) 26 M anure and wast e become vehi cl e f uel (Ki rst i anst ad Sweden) 27 Usi ng bi ogas i n vehi cl es and apart ment s (St ockhol m Sweden) 28 M arquet t e Sewage t reat ment pl ant , Li l l e France 29 Gri d i nj ect i on of upgraded bi ogas f rom OFM SW (Jona Swi t zerl and) 29 Further reading 31 3 2 had increased by almost 25% from the1990 level.It is expected that 90% of theincrea- seis attributableto thetransport sector. Alternativefuels might help considerably to reduceemissions.This has been recog- nised by a number of governments which brought forward programs and legislations. A new biofuel directive(2003/30/EC) from theEuropean Commission was approved in 2003. This directivesets targets for theEuropean Union to gradually replacefossil fuels by biofuels. Thepresent targets are2% biofuels by theyear 2005 and 5,75% bio- fuels by theyear 2010.In particular,biogas as a fuel could bring substantial reductions in greenhouse gases, particles and nitrogen oxide emissions, when replacing fossil fuels,likediesel or petrol. In 2003, theEuropean Parliament adopted theDirective2003/55/EC, giving com- mon rules for thenatural gas market but also for biogas and other gases from biomass in so far such gases can technically and safely beinjected into,and transported through thenatural gas system. Biogas Composition Biogas produced in AD-plants or landfill sites is primarily composed of methane (CH4) and carbon dioxide(CO2) with smaller amounts of hydrogen sulphide(H2S) and ammonia (NH3). Traceamounts of hydrogen (H2), nitrogen (N2), saturated or halogenated carbohydrates and oxygen (O2) areoccasionally present in thebiogas. Usually, thegas is saturated with water vapour and may contain dust particles and organic silicon compounds (e.g siloxanes). Typical compositions of different kinds of biogas and natural gas areshown in thetablebelow. Theraw gas is in all cases satura- ted with moisture. Introduction During anaerobic digestion, i.e. degradation in the absence of oxygen, organic material is decomposed by bacteria forming digestate, an excellent fertilizer, and bio- gas,a mixtureof carbon dioxideand methane.Anaerobic digestion (AD) has been suc- cessfully applied in recycling of biowasteand agricultural wastes, industrial wastewa- ter treatment,stabilisation of sewagesludgeand landfill management. Today, farm-based manurefacilities areperhaps themost common useof AD- technology. By theend of 2005 17 million family-sized low-technology digesters were used in China to providebiogas for cooking and lighting. Therearenow over 3500 farm-based digesters operating in Europeand North America.Thousands of digesters help to anaerobically stabiliseand thicken sewagesludgebeforeit is used on agricultu- ral land,dried and incinerated or landfilled.Morethan 2 000 high-rateanaerobic dige- sters are operated world-wide to treat organic polluted process waste water from beverage,food,meat,pulp and paper and milk industries. Gas recovery from landfills has becomea standard technology in most of theindu- strialised countries for energy recovery, environmental and safety reasons. Increasin- gly thegas is used in combined heat and power (CHP) engines or as a supplement to natural gas. Therearemorethan 250 plants operating or under construction using theorganic fraction of sourceseparated municipal solid waste(MSW) to producea high quality compost or mechanically separated MSW to stabilisetheorganic fraction beforeland- filling.Thetotal installed capacity is closeto ten million tonnes. Theproduct of anaerobic digestion is a gas containing primarily methaneand car- bon dioxide, commonly called biogas. In small-scaleinstallations, worldwide, thegas is primarily utilised for lighting and cooking. In larger units thegas can beused for co- generation (generation of heat and electricity),asvehiclefuel or asfuel in industrial processes. Thetotal European biogas production was in 2004 estimated to 50 TWh. This was a 43% increasefrom 2002.Morethan 55% of thebiogas production comes from land- fills and sewagesludgetreatment but this is expected to changesincedeposition of organic material in landfills has to bereduced and is even banned in European coun- tries. Instead biological treatment or incineration of organic material is steadily incre- asing. A study (From biogas to energy: a European overview, 2001) performed by Solagro, predicts a production of 210 TWh by theyear 2020. This can becompared to thetotal world gasolineproduction that in 2004 was 11000 TWh. Themajority of thecountries that participated at theconferenceof Kyoto and followers haverati- fied theindividual goals for thereduction of CO2 set for each country. Transport is thesector wherethe highest increaseoccurs.TheEuropean Commission predicts a 50% increasein theemissions of green- house gases in the transport sector from 1990 to 2010. In year 2000 the greenhouse gas emissions 4 Biogas Upgrading Introduction Biogas Composition Biogas Upgrading 5 CO2-emi ssi ons i n some coun- t ri es and regi ons i n t he worl d. (Source: Annual Energy Revi ew 2005, Energy Inf orma- t i on Admi ni st rat i on. www.ei a.doe.gov) CO2-emissions inselectedcountries Kompogas pl ant i n Oet wi l , Swi t zerl and Typical contaminants inbiogas Landfill gas may contain morethan 500 different contaminants such as halogena- ted hydrocarbons,higher hydrocarbons and aromatic compounds.Landfill gas and gas from digestion of sewagesludgemay also contain siloxanes that may causeseverepro- blems in downstream utilisation. Sulphur gases Biogas and, especially, landfill gas can contain a variety of sulphur compounds, such as sulphides,disulphides and thiols.Especially oxidized sulphur compounds (sul- phateand sulphite) arecorrosivein thepresenceof water. It has to beremoved in order to avoid corrosion in compressors, gas storagetanks and engines. Themain sulphur compound in biogas is hydrogen sulphide. It is reacti- vewith most metals and thereactivity is enhanced by concentration and pressure, the presenceof water and elevated temperatures. Halogenatedcompounds Halogenated compounds (e.g. carbon tetrachloride, chlorobenzene, chloroform and trifluoromethane) areoften present in landfill gas, however, only rarely in biogas from digestion of sewagesludgeor organic waste. Halogens areoxidized during thecombustion process. Thecombustion products arecorrosive,especially in thepresenceof water and can causecorrosion in downstre- am pipes and applications.They can also initiatetheformation of PCDDs and PCDFs (dioxines and furans) if thecombustion conditions (temperatureand time) arefavou- rable. Most halogenated species in landfill gas aretheresult of direct volatilisation from solid wastecomponents and their presencedepends on vapour pressurerelationships under landfill conditions.Themost common fluorinated contaminants arethechloro- fluorocarbons (CFCs), which were widely used as refrigerants, propellants, and in insulating foams until their usewas forbidden or reduced in thelate1980s.Themost abundant CFCs in landfill gas areCFC-12 (dichlorodifluoromethane) and CFC-11 (trichlorofluoromethane). Theseappear to persist at low concentrations in landfills dueto their slow volatilisation from old waste. Siloxanes Siloxanes arevolatilesilicones bonded by organic radi- cals. They occur in landfill gas and gas from digestion of sewagesludge.Theseoriginatefrom different kinds of consu- mer products (e.g.shampoo,detergents and cosmetics.) Siloxanes areconverted during combustion to inorganic siliceous deposits in downstream applications.Theamount of silica has to bereduced to a minimum, especially in engine applications. Siliceous deposits on valves, cylinder walls and liners arethecauseof extensivedamageby erosion or block- age. Onevery important factor in gas utilisation is thegas Wobbeindex. This is deter- mined by theequation below. Theheating valueof biogas is determined mainly by themethanecontent in the gas. Thehigher heating valuegives theenergy that is released when onenormal cubic meter (nm 3 ) of biogas is combusted and thewater vapour formed in thecombustion is condensed. Thelower heating valueshows theenergy formed when thewater vapour is still not condensed. Just as thereis a lower and higher heating valuethereis also a lower and higher Wobbeindex. Relativedensity is thequotient of gas and air density. Themethanenumber is a parameter that describes thegas resistanceto knocking when used in a combustion engine. Methanehas per definition a methanenumber of 100 and H2 a methanenumber of zero. CO2 increases themethanenumber becauseit is a non combustiblegas with a high knocking resistance. Upgraded biogas therefore has a methanenumber higher than 100. 6 Biogas Upgrading Biogas Composition Biogas Composition Biogas Upgrading 7 Compositionandparameters of gas fromdifferent sources PARAMETER UNIT LANDFILL BIOGAS NORTHSEA DUTCH GAS FROM AD NATURAL GAS NATURAL GAS Lower heat i ng val ue M J/ nm 3 16 23 40 31,6 kWh/ nm 3 4,4 6,5 11 8,8 M J/ kg 12,3 20,2 47 38 Densi t y kg/ nm 3 1,3 1,2 0,84 0,8 Hi gher Wobbe i ndex M J/ nm 3 18 27 55 43,7 M et hane number > 130 >135 70 M et hane vol -% 45 63 87 81 M et hane, vari at i on vol -% 3565 5370 Hi gher hydrocarbons vol -% 0 0 12 3,5 Hydrogen vol -% 03 0 0 Carbon oxi de vol -% 0 0 0 0 Carbon di oxi de vol -% 40 47 1,2 1 Carbon di oxi de, vari at i on vol -% 1550 3047 Ni t rogen vol -% 15 0,2 0,3 14 Ni t rogen, vari at i on vol -% 540 - Oxygen vol -% 1 0 0 0 Oxygen, vari at i on vol -% 05 Hydrogen sul phi de ppm < 100 < 1000 1,5 Hydrogen sul phi de, vari at i on ppm 0100 010000 12 Ammoni a ppm 5 <100 0 Tot al chl ori ne (as Cl
) mg/ nm 3 20200 05 0 Si l oxane deposi t s at t he cyl i nder of a CHP engi ne definition of theresistanceto knocking of fuels. TheSwedish standard is also applied when injecting biogas into thenatural gas grid.Additional demands concerning hea- ting valuearecovered by addition of propaneto thegas. Switzerland Biogas is injected into thenatural gas grid at several locations in Switzerland. Two different qualities areallowed in theSwiss regulations (G13): gas for limited injection and gas for unlimited injection. Therestrictions for gas for unlimited injection areof coursemoreseverethan therestrictions for limited injection. Germany Germany has a standard for biogas injection (G262) that has been elaborated in co- operation between theGerman Water and Gas Association and theGerman Biogas Association. Thestandard is based on theGerman standard for natural gas, DVGW G260.Themain requirements in thestandard arestated below (for injection into natu- ral gas grids with high heating value). TheGerman standards allow injection of two types of gas,gas for limited injection and gas for unlimited injection.Unlimited injection of upgraded biogas in H-gas grids is possible if the cited concentrations are maintained. The German standard also Silicon compounds may also reach thelubrication oil requiring morefrequent oil changes. Theincreased useof cosmetics and other silicon containing products means that morefrequent siloxanemonitoring in thefuel gas is required. Thereis though no standard method for siloxanemonitoring and discrepancies exist between results with different measuring methods. Ammonia High concentrations of ammonia area problem for gas engines,and areoften limi- ted by manufacturers of gas engines. Normally up to 100 mg/nm 3 ammonia can be accepted.Thecombustion of ammonia leads to theformation of nitrous oxide(NOx). Dust andparticles All biogas plants must beequipped with somekind of filter or/and cyclonefor reduction of theamounts of particles in thegas. Filters not only removeparticulates but also reducethecontent of droplets of water or oil.Filters with a 2 5 micron mesh sizearenormally regarded as appropriatefor most downstream applications. National gas standards Biogas can either beused directly on thesitewhereit is generated or distributed to external customers via separatepipelines.After proper upgrading it might befed into thedistribution grid for natural gas. Thederegulation of thenatural gas market in Europehas opened thepossibility to find new customers for upgraded biogas via the gas grid. Thereis no international technical standard for biogas injection but somecoun- tries havedeveloped national standards and procedures for biogas injection.MARCO- GAZ, thetechnical association of theEuropean Natural Gas Industry has adopted a recommendation concerning technical and gas quality requirements for delivery of non-conventional gases e.g biogas into gas networks. Therecommendation will be official in 2007. Injecting biogas into thegas grid sometimes raiseconcerns about therisk of trans- mitting diseasevia thegas.TheSwedish Instituteof Infectious DiseaseControl,Natio- nal Veterinary Instituteand theSwedish University of Agricultural Sciencehaveevalu- ated this risk (Identification of themicrobiological community in biogas systems and evaluation of microbial risk from gas usage, ELSEVIER, 2006). Thestudy concluded that therisk of spreading diseasevia biogas was judged to bevery low; thenumber of micro organisms found in biogas was equal to thelevel found in natural gas. Sweden In 1999 Sweden has developed a national standard for biogas as vehiclefuel on request of the Swedish vehicle manufacturers as a design basis for fuel- and enginesystems. The main parameters of thestandard aredescribed in thetablebelow. Motor octanenumber is a 8 Biogas Upgrading National gas standards National gas standards Biogas Upgrading 9 Swiss national standardfor unlimitedgas injection PARAMETER UNIT DEMANDIN STANDARD M et hane cont ent Vol -% >96 > Gas rel at i ve humi di t y phi <60% Dust - Techni cal l y f ree CO2 vol -% <6 O2 vol -% <0,5 H2 vol -% <5 H2S mg/ nm 3 <5 S mg/ nm 3 <30 Swedishnational standardfor biomethane PARAMETER UNIT DEMANDIN STANDARD Lower Wobbe i ndex M J/ nm 3 43,9 47,3 1 M ON (mot or oct ane number) - >130 (cal cul at ed accordi ng t o ISO 15403) Wat er dew poi nt C <t 2 -5 CO2+O2+N2 vol -% <5 O2 vol -% <1 Tot al sul phur mg/ nm 3 <23 NH3 mg/ nm 3 20 1 Corresponds t o 95 99% met hane 2 t = ambi ent t emperat ure Swiss national standardfor limitedgas injection PARAMETER UNIT DEMANDIN STANDARD M et hane cont ent Vol -% >50 > Gas rel at i ve humi di t y phi <60% Dust - Techni cal l y f ree CO2 vol -% <6 O2 vol -% <0,5 H2 vol -% <5 H2S mg/ nm 3 <5 S (wi t hout odourat i on) mg/ nm 3 <30 Gas i nj ect i on i nt o t he nat ural gas gri d i n Samst agern, Swi t zerl and Gas buses i n t he ci t y: l ow emi ssi ons and l ow noi se. Gas Utilisation Gas is an excellent fuel for a largenumber of applications and can also beused as raw material for theproduction of chemicals.Biogas can beused in moreor less all the applications that aredeveloped for natural gas.For someof theapplications thebiogas may haveto beupgraded. Injection of biogas into thenatural gas grid will result in an improved security of supply. This is important sincedependenceon imported natural gas is increasing and only 2/3 of theEuropean gas consumption is covered by gas from theEC.Thebenefits of gas as a fuel haveresulted in increased use.Natural gas accounts for 25% of thetotal energy consumption in theEU25 countries (2005, www.bp.com). Additional amounts of natural gas will haveto beimported to Europealready before 2010. Estimates by Eurogas indicatethat natural gas import to the(former) EU15 has to beincreased by 190 Mtoebeforetheyear 2020.Theincreased demand will of cour- sealso bereflected by increasing gas prices. Therearefour basic ways biogas can beutilised: Production of heat and steam Electricity production/ co-generation Vehiclefuel Production of chemicals Themain utilisation of biogas is governed by national frameworks likethetax system, subsidies, availability of gas and heat grids.Worldwide, biogas is mainly used for electricity production whereas in Sweden and in Switzerland a growing portion of thebiogas is used in thetransport sector. Themajor driver defining theway of biogas utilisation is thecompensation of the energy, i.e. electricity or (upgraded) biogas. Most of the European countries have increased feed-in tariffs for electricity. Front runners areGermany and Austria with feed-in tariffs for biogas up to 21.5 cents per kWh. Sweden on theother hand has a history of low electricity prices compared to the rest of Europe.It has thereforebecomethemarket leader for biogas as vehiclefuel.The rateof growth has been rapid,for example25% between 2004 and 2005.Thedevelop- ment has been driven by several factors including tax exemption, government invest- ment programme,reduction on valuation tax and freeparking in several cities. Themost common applications for biogas areheating and power generation.Using biogas as vehiclefuel and injecting thegas into thegas grid areapplications that reach moreand moreinterest. Productionof heat Themost common useof biogas from small-scaleplants in developing countries is for cooking and lighting. Conventional gas burners and gas lamps can easily beadju- sted to biogas by changing theair to gas ratio.In moreindustrialized countries boilers requires thebiogas producer to present at safety data sheet that describes any health hazards in connection to thehandling of thebiogas. France Gaz deFrancehas in 2004 produced a defacto standard for gas injection into the national gas grid. Thestandard has morestrict limits on oxygen than theother stan- dards and also comprises a number of limits for heavy metals and halogens. 10 Biogas Upgrading National gas standards Gas Utilisation Biogas Upgrading 11 Requirements for gas injectionaccordingtoGermanstandardG260/G262 PARAMETER UNIT DEMANDIN STANDARD Hi gher Wobbe i ndex M J/ nm 3 46,1 56,5 3 i n H gas 4 gri ds 37,8 46,8 5 i n L gas 6 gri ds Rel at i ve densi t y - 0,55 0,75 Dust - Techni cal l y f ree Wat er dew poi nt C <t 7 CO2 vol -% <6 O2 vol -% <3 (i n dry di st ri but i on gri ds) S mg/ nm 3 <30 Frenchnational regulationfor gas injection PARAMETER UNIT DEMANDIN STANDARD Hi gher heat i ng val ue M J/ nm 3 H gas: 38,52 t o 46,08 L gas: 34,2 t o 37,8 Hi gher Wobbe i ndex M J/ nm 3 H gas: 48,24 t o 56,52 L gas: 42,48 t o 46,8 Hydrocarbon dew poi nt C < -5 f rom 1 t o 80 bar Wat er dew poi nt C < -5 at M OP downst ream f rom i nj ect i on poi nt (Gergwat er correl at i on) CO2 vol -% < 2 Dust mg/ nm 3 < 5 Tot al sul phur mg/ nm 3 < 100 i nst ant cont ent < 75 annual average O2 ppmv < 100 Hg mg/ nm 3 < 10 (Nat ural gas) < 50 (Li quef i ed Nat ural Gas) Cl mg/ nm 3 < 1 F mg/ nm 3 < 10 H2 % < 6 CO % < 2 3 Corresponds t o >97,5% met hane 4 hi gh heat i ng val ue gas 5 Corresponds t o 87 98,5% met hane 6 l ow heat i ng val ue gas 7 t = ground t emperat ure Internal combustion Themost common technology for power generation is internal combustion.Engi- nes areavailablein sizes from a few kilowatts up to several megawatts.Gas engines can either beSI-engines (spark ignition) or dual fuel engines. Dual fuel engines with injection of diesel (10% and up) or sometimes plant oil are very popular in smaller scales becausethey havegood electric efficiencies up to guar- anteed 43%. On theother hand they havehigher emissions unless they usea SNCR catalyst. Another advantageis theeasy start-up of thebiogas plant becauseheat and electricity can beproduced from scratch by using diesel only. SI-engines areequipped with normal ignition systems and a gas/air mixing system that provides a combustiblemixtureto theengine. SI-engines can either bestoichio- metric or lean-burn engines. Thestoichiometric engines operatewithout air excess and can thereby also usea three-way catalyst that is common in light duty vehicles. Lean burn engines aremorecommon in larger sizes and generally havea higher effi- ciency. Gas turbines Gas turbines arean established technology in sizes above800 kW. In recent years also small scaleengines, so called micro-turbines in therangeof 25 to 100kW have been successfully introduced in biogas applications.They haveefficiencies comparable to small SI-engines with low emissions and allow recovery of low pressuresteam which is interesting for industrial applications.Maintenancecost arevery low. Fuel cells Fuel cells havea potential to becomethesmall scalepower plant of thefuture.Fuel cell technology is 160 years old, which is moreor less thesameageas thecombustion engineand theStirling engine. Nevertheless, widespread commercial useis yet to be achieved. Fuel cells havea potential to reach very high efficiencies (>60%) and low emissions.Special interest for stationary biogas application is focussed on hot fuel cells operating at temperatures above800C particularly becausetheCO2 does not inhibit theelectrochemical process, but rather serves as an electron carrier. Two types of fuel cells arein an advanced stageof development:thesolid oxidefuel cell (SOFC) for small applications of a few kW and themolten carbonatefuel cells (MCFC) operating in the rangeof 250kW and up. arepresent only in a small number of plants wherebiogas is used as fuel only without additional CHP. In a number of industrial applications biogas is used for steam pro- duction. Burning biogas in a boiler is an established and reliabletechnology. Low demands areset on thebiogas quality for this application.Pressureusually has to bearound 8 to 25 mbar. Furthermoreit is recommended to reducethelevel of hydrogen sulphideto below 1 000 ppm,this allows to maintain thedew point around 150 C. Power generation/ CombinedHeat andPower (CHP) Biogas is theideal fuel for generation of electric power or combined heat and power. A number of different tech- nologies are available and applied. 12 Biogas Upgrading Gas Utilisation Gas Utilisation Biogas Upgrading 13 FEATURE PETROL ENGINE DIESEL DIESEL MICRO SI ENGINE J ET ENGINE TURBINE IGNITION SI Ef f i ci ency [%] 2429 3038 3542 2629 M ai nt enance cost Hi gh Hi gh M edi um Low Invest ment cost Low M edi um (hi gh) M edi um Hi gh Power [kW] 530 30200 >200 <100 Li f espan Low M edi um Hi gh Hi gh Bi ogas can be used f or generat i on of el ect ri ci t y i n a number of di f f erent t echnol ogi es. Larger CHPs (> 200kW) usual l y are pure gas engi nes wi t h spark i gni t i on BIOGAS Desulfurisation Desulfurisation Gas treatment Gas treatment Reforming Compression Boiler CHP Fuell cell Pressuretank Heat Power Heat Power Heat Fuel Bi ogas can be used i n al l nat ural gas appl i ances provi ded t hat upgradi ng of t he gas qual i t y i s carri ed out . Besidethecloseto 100% CO2 reduction,puregas engines with catalytic converters demonstratefar better emission values than themost modern diesel engines (Euro IV or V) tested according theEuropean Transient Cycle(ETC) or theEnhanced Environ- mental friendly Vehicle(EEV) standard at theEMPA,Switzerland (Tableabove). Stoichiometric gas engines with an air-to-fuel ratio of 1 (=1) demonstratea bet- ter emission pattern than lean engines.However,both arefar better than dual fuel engi- nes although at a reduced efficiency. Thebench tests areconfirmed by real tests in Braunschweig. Thenumber of biogas and natural gas filling stations is still insufficient in Europeand elsewhe- rein theworld. However, thesituation is impro- ving enormously. The number of pumping sta- tions has multiplied over thelast few years.At the end of 2005 therewere1600 pumping stations in Europe. By theend of 2006 Germany should have 1000 stations in operation, Switzerland 100 and Austria morethan 50. Gas vehicles Biogas can beupgraded to natural gas quality and used in thesamevehicles that usenatu- ral gas (NGVs). At the end of 2005 there were more than 5 million NGVs in the world. Public transport vehicles driven on gas such as buses and waste trucks areincreasing consider- ably.In total 210000 heavy duty vehicles are operated, thereof 70000 buses and 140000 trucks. A number of European cities are exchanging their buses with biogas driven engi- nes. Six of them teamed in theBiogasMax EC project to shareand document their experience. Most of thegas driven personal cars areconverted vehicles that havebeen retro-fit- ted with a gas tank in theluggagecompartment and a gas supply system in addition to thenormal liquid fuel system. Dedicated gas vehicles can beoptimized for better efficiency and also allow for moreconvenient placement of thegas cylinders without losing luggagespace. Gas is stored at 200 to 250 bars in pressurevessels madefrom steel or aluminium composite materials. Today morethan 50 manufacturers worldwideoffer a rangeof 250 models of com- muter, light and heavy duty vehicles. Gas vehicles havesubstantial advantages over vehicles equipped with petrol or diesel engines.Carbon dioxideemission is reduced by morethan 95%. Depending on how theelectricity for upgrading and compressing of thegas is produced,thereduction might beas high as 99%.In both leading biogas fuel countries, Sweden and Switzerland, electricity is almost freeof CO2 becauseit is pro- duced by hydro or nuclear power. Emissions of particles and soot arealso drastically reduced,even compared with modern diesel engines equipped with particlefilters.The emissions of NOx and Non Methane Hydrocarbons (NMHC) are also drastically reduced. Heavy duty vehicles arenormally converted to run on methanegas only but in somecases also dual fuel engines havebeen used.Thedual fuel enginestill has theori- ginal diesel injection system and gas is ignited by injection of a small amount of diesel oil.Theenginenormally idles on diesel oil. Dual fuel engines normally requireless enginedevelopment and maintain thesame driveability as a diesel vehicle.However emission values arenot as good as for thecor- responding dedicated gas vehicleand theenginetechnology remains a compromise between spark ignition and diesel engine. 14 Biogas Upgrading Gas Utilisation Gas Utilisation Biogas Upgrading ENGINE TYPE CO HC NMHC NOX PARTICLES EFFICIENCY G/KWH % ETC Euro III 5.45 1.50 0.70 5.00 0.16 39.7 ETC Euro IV 4.00 1.10 0.55 3.50 0.03 39.2 ETC Euro V 4.00 1.10 0.55 2.00 0.03 38.1 EEV Euro V 3.00 0.66 0.40 2.00 0.02 Euro II Gas wi t h di esel i nj . 3.00 5.20 0.80 7.50 0.004 38.7 Gas =1 wi t h 3-way cat . 2.30 0.03 0.01 0.40 0.004 32.5 Gas l ean eng. wi t h oxi -cat . 0.04 0.42 0.02 1.70 0.004 30.0 In an i ncreasi ng number of European ci t i es, l i ke i n Bern, al l t own buses run on bi ogas. Repl aci ng di esel buses wi t h gas buses can subst ant i al l y reduce t he NOx emi ssi ons as shown by t hi s st udy of emi ssi ons f rom CNG and di esel buses. (Court esy VTT Fi nl and) LB: l ean-burn (combust i on), EEV: enhanced envi ronment al l y f ri end- l y vehi cl e, LM : l ean-mi x (combust i on), SM : st oi chi omet ri c, OC: oxi dat i on cat al yst , CRT: cont i nuousl y regenerat i ng t rap (part i cl e f i l t er) Emi ssi ons and ef f i ci enci es of modern heavy dut y engi nes operat ed wi t h di esel or gas or i n a dual f uel mode (Source: Chri st i an Bach, EM PA Swi t zerl and) Abbrevi at i ons: CO = Carbon monoxi de, ETC= European Transi ent Cycl e; HC = Hydrocarbons, NM HC = Non met hane hydrocarbons. 15 M ore t han 30 model s of NGVs are on t he market 16 Biogas Upgrading Gas upgradingtechnologies Gas upgradingtechnologies Biogas Upgrading Biogas injectionintothegas grid Biogas can beinjected and distributed through thenatural gas grid sincebiogas like natural gas mainly consists of methane. Thereareseveral incentives for using thegas grid for distribution of biogas. One important advantageis that thegrid connects theproduction sitewith moredensely populated areas which enables thegas to reach new customers. It is also possibleto increasetheproduction at a remotesiteand still use100% of thegas. Furthermore injecting biogas into thegas grid improves thelocal security of supply. This is an important factor sincemost of thecountries consumemoregas than they produce. As previously listed somecountries likeSweden, Switzerland, Germany and Fran- cehavea standard for injecting biogas into thenatural gas grid. Thestandards have been set to avoid contamination of thegas grid or end use.Demands on Wobbeindex havebeen set to avoid influenceon gas measurements and end use. In thestandards therearelimits on certain components for instancesulphur, oxy- gen,particles and water dew point.Thesedemands arein most cases possibleto achie- vewith existing upgrading processes. In somecases landfill gas can bedifficult to upgradeto sufficient quality dueto largecontent of nitrogen. Gas upgrading technologies Therearethreemajor reasons for gas cleaning: fulfil therequirements of gas appliances (gas engines,boilers,fuel cells,vehicles etc.) increasetheheating valueof thegas standardisation of thegas Thegas quality requirements depend strongly on theutilisation Utilisation in stationary gas engines is a typical casewhereonly contaminants have to beremoved from thebiogas.Most manufacturers of gas engines set maximum limits of hydrogen sulphide,halogenated hydrocarbons and siloxanes in biogas.When using biogas for vehiclefuel all contaminants as well as carbon dioxideneed to beremoved to reach a sufficient gas quality. Thereareseveral technologies availablefor removing contaminants from biogas and upgrading thegas to vehiclefuel or natural gas quality. Carbondioxideremoval Beforeusing biogas as vehiclefuel thelevel of carbon dioxideis reduced in thegas. It would betechnically possibleto run a vehicleon biogas without removing thecar- bon dioxideif theenginewould bespecially adjusted to it,but thereareseveral reasons why carbon dioxidemust beremoved. Removing carbon dioxideincreases theheating valueof thegas resulting in an increased driving distancefor a specific gas storagevolume.It also leads to a consistent gas quality between different biogas plants and a similar quality to natural gas. Beforeadding biogas into thenatural gas grid it is also common to removecarbon dioxidein order to reach therequired Wobbeindex of thegas.When removing carbon dioxidefrom thegas stream small amounts of methanearealso removed. It is impor- tant to keep thesemethanelosses low for both economical as well as environmental reasons sincemethaneis a greenhousegas 21 times stronger than CO2. Thereareseveral different commercial methods for reducing carbon dioxide.Most common areabsorption or adsorption processes. Other techniques that areused are membraneseparation and cryogenic separation. Oneinteresting method under deve- lopment is process internal upgrading. Absorption Carbon dioxide and hydrogen sulphide can be removed from biogas through absorption processes. Thedifferent binding forces of themorepolar CO2 or H2S and thenon-polar methaneareused to separatethesecompounds. APPLICATION H2S CO2 H2O Gas heat er (boi l er) <1000 ppm no no Ki t chen st ove yes no no St at i onary engi ne (CHP) < 1000 ppm no no condensat i on Vehi cl e f uel yes yes yes Nat ural gas gri d yes yes yes PRINCIPLE NAME TYPE OF PRE TREATMENT WORKING REGENERATION PRESSURE (BAR) Adsorpt i on Pressure Swi ng Vacuum Wat er vapour, 47 Adsorpt i on (PSA) H2S Absorpt i on Wat er None/ Ai r None 710 st ri ppi ng Pol yet hyl ene gl ycol Ai r st ri ppi ng Wat er vapour, 710 H2S M ono et hanol ami ne Heat i ng H2S at mospheri c (M EA) Requi rement s t o remove gaseous component s depend on t he bi ogas ut i l i zat i on. General dat a f or absorpt i on and adsorpt i on processes. 17 18 Biogas Upgrading Gas upgradingtechnologies Gas upgradingtechnologies Biogas Upgrading Water scrubbing Water is themost common solvent in which casetheprocess is called water scrub- bing.Biogas is compressed and fed into thebottom of a column whereit meets a coun- ter flow of water. Thecolumn is filled with packings to createa largesurfacebetween gas and liquid. Carbon dioxideas well as hydrogen sulphidearemoresolublein water than methane.Thebiogas which is brought out of thetop of thecolumn is enriched in methaneand saturated with water. To reducethewater vapour thebiogas needs to be dried. TheCO2-enriched water is brought to a flash tank wherethepressureis reduced and most of thecarbon dioxideis released. Sometimes theprocess is enhanced by air stripping or by vacuum.Air stripping brings oxygen into thesystem which is a problem when thegas is used as fuel or when it is fed into thegrid.Thegas released in theflash tank is recirculated to theinlet of thecompressor. Theprocess can usefresh water all thetime.This is most common at sewagetreatment plants wherepurified water is avai- lable. Hydrogen sulphidewhich is released to theair creates an emission problem. Someof thesulphur is accumulated in thewater and can causeproblems with fouling and plugging of pipework after sometimeof operation. It is thereforerecommended that hydrogen sulphideis separated beforehand. Plugging in theabsorption column dueto organic growth can bean issueat these plants and thereforeit is recommended to install automatic washing equipment for the column. Organic solvents Instead of water an organic solvent likepolyethyleneglycol can beused for the absorption of carbon dioxide.Selexoland Genosorbaretradenames for thechemi- cals.In this solvent,likein water,carbon dioxideand hydrogen sulphidearemoresolu- blethan methaneand theprocess proceeds in thesameway as water scrubbing with regeneration. Themain differenceto water is that carbon dioxideand hydrogen sul- phidearefar moresolublein organic solvents than in water. Hence, a smaller upgra- ding plant can bebuilt for thesamegas capacity.In theprocess also water and haloge- nated hydrocarbons, which can occur in landfill gas, areseparated. However a lot of energy is needed to regeneratetheorganic solvent from hydrogen sulphideand there- foreit is often better to separatethehydrogen sulphideprior to theabsorption. Other organic solvents that can beused arealkanol amines likemono ethanol ami- ne (MEA) or di-methyl ethanol amine (DMEA).The chemical is regenerated in a reverted chemical reaction usually driven by heat and/or vacuum. In a typical MEA process hydrogen sulphide is removed before the biogas enters the bottom of the absorption column. Thegas meets a counter-flow of liquid and thecarbon dioxide reacts with thechemical at low pressure. Sincethereaction is selectivealmost all car- bon dioxideand very littlemethaneis removed. Thegas is compressed and dried and can then beused for vehicles or distributed into thegas grid. Thechemical is regene- rated through heating with steam which has thedisadvantageof being energy consu- ming. PressureSwingAdsorption Adsorption of carbon dioxideon an material likeactivated carbon or molecular sieves can be used to separate carbon dioxide from the biogas. The selectivity of adsorption can beachieved with different mesh sizes. This method is named Pressure Swing Adsorption, PSA, sincetheadsorption takes placeat elevated pressureand the material is regenerated through reducing thepressureand subsequent application of a light vacuum. Theprocess requires dry gas.Water vapour is usually condensed in a cooler.Hydro- gen sulphideneeds to bepre-separated beforethegas is fed into thebottom of the adsorption vessel. This is doneby an additional tank with activated carbon. Usually when its surfaceis saturated with hydrogen sulphide,thematerial is exchanged.Adding air to thebiogas stream can extend thelifetimeof thesulphideremoval unit however, it bares therisk that therearetraces of oxygen also in theupgraded biogas. In thepressurized vessels carbon dioxideis adsorbed.Thegas leaving thetop of the vessel is enriched with methane.When thematerial in thevessel is saturated, biogas is led to a new vessel. Thereareseveral (most often four) vessels linked together to crea- tea continuous operation and to reducetheenergy need for gas compression.Regene- ration of thesaturated vessel is achieved through stepwisedepressurisation. First the pressureis reduced through linking thevessel with an already regenerated vessel.Then thepressureis reduced to almost atmospheric pressure. Thegas released in this step contains significant amounts of methaneand is thereforerecycled to thegas inlet. 19 Carbon di oxi de has a hi gher sol ubi l i t y i n wat er t han met hane. Thi s permi t s separat i on of t he t wo component s i n an absorpt i on col umn. Wat er wash i s one of t he most common t echni ques f or separat i ng carbon di oxi de f rom bi ogas. 20 Biogas Upgrading Gas upgradingtechnologies Gas upgradingtechnologies Biogas Upgrading Finally thevessel is completely evacuated with a vacuum pump.Thegas that leaves the vessel in this step mainly consists of carbon dioxidewhich is in onesystem (Carbo- tech) released to theatmosphere.In another system (Questair/Verdesis) it is burned in a flox burner designed for low caloriegases. In thefirst system moreupgraded biogas is produced whereas thesecond system needs less absorber surfaceand has no metha- neslip to theatmosphere. Membraneseparation Therearedifferent processes with membraneseparation. Either it is a separation with a gas phaseon both sides of themembraneor it is a gas-liquid absorption which means that a liquid absorbs thecarbon dioxidediffusing through themembrane. The liquid can bean amineand thesystem has high selectivity compared to solid mem- brane systems. Separation takes place at low pressure, approximately atmospheric pressure. Membranes with gas phases on both sides can also becalled dry membranes. The membraneeither works at high pressure>20 bar or at low pressures 8-10 bar. The separation is driven by thefact that different molecules of different sizehavedifferent permeability through themembrane. Other important factors for theseparation are pressuredifferencebetween thetwo sides of themembraneand temperatureof thegas. Carbon dioxideand hydrogen sulphidepass through themembraneto thepermeate sidewhereas methaneis retained on theinlet side. Also somemethanepasses through themembraneto thepermeatestream. There is a conflict between high methanelevels in thegas and at thesametimea high metha- nerecovery. High methanelevel in theupgraded gas can beachieved with larger size or several membranes in series. This on theother hand leads to high losses of metha- neinto thepermeatestream.If thepermeatestream can beused for instancein a com- bined heat and power plant together with raw gas or in a flox burner, it is possibleto utilisethemethanethat is lost in theprocess and at thesametimereducecost for investment and energy consumption for theupgrading. Thebiogas is compressed and dried beforebeing led to themembranewherecar- bon dioxideand somehydrogen sulphideareseparated. Further separation of hydro- gen sulphideis needed beforethebiogas can beused for vehicles or fed into thegas grid. Cryogenic separation Methanehas a boiling point of -160 C at atmospheric pressurewhereas carbon dioxidehas a boiling point of -78 C.This means that carbon dioxidecan beseparated from thebiogas as a liquid by cooling thegas mixtureat elevated pressure.Methanecan betaken out in gas or liquid phase,depending on how thesystem is constructed.When also methaneis condensed,nitrogen which has a even lower boiling point is separated and this is an advantagewhen dealing with landfill gas. Theseparated carbon dioxide is clean and can besold. Until today (2006) this method has only been tested in pilot plants in Europe. To avoid freezing and other problems in thecryogenic process water and hydrogen sulphideneed to bepre-separated.Theprincipleof cryogenic separation is that biogas is compressed and then cooled by heat exchangers followed by an expansions step for instancein an expansion turbine. Thecooling and theexpansion causes thecarbon dioxideto condensate. Compression as well as chilling can bedonein several steps. After carbon dioxidehas been removed as a liquid thegas can becooled further to con- densatethemethane. In-situmethaneenrichment Conventional techniques for separating carbon dioxidefrom biogas demand a lot of process equipment and themethods areusually suited for largeplants in order to reach a sufficient economy. In-situ methaneenrichment is a new technology under development in pilot-scalewhich promises a better economy also for smaller plants. Sludgefrom thedigestion chamber is led to a column whereit meets a counter flow of air.Carbon dioxidethat is dissolved in thesludgeis desorbed.Thesludgeis led back to thedigestion chamber.Morecarbon dioxidecan now dissolveinto thesludgeresul- ting in methaneenriched gas in thechamber. Theresults from lab-scaletests in Sweden indicatethat it is technically possibleto construct a system that increases themethanecontent of thegas to 95% and still keep themethanelosses below 2%. Removal of hydrogensulphide Hydrogen sulphideis formed from digestion of proteins and other material that contains sulphur. Sincehydrogen sulphideis highly corrosiveit is recommended to 21 22 Biogas Upgrading Gas upgradingtechnologies Gas upgradingtechnologies Biogas Upgrading separateit early in thebiogas upgrading process. It can beremoved in thedigestion chamber, in thegas stream or in theupgrading process. Someof themost common methods for removing hydrogen sulphidearein fact internal, iron chloridedosing to thedigester slurry or air/oxygen dosing to thedigester. Biological desulphurisation Micro-organisms can beused to reducethelevel of sulphidein biogas, by conver- ting it to mainly elementary sulphur and somesulphate.Thesulphur-oxidising micro- organisms mainly belong to thefamily of Thiobacillus.They arecommonly present in thedigestion material and thus dont haveto beinoculated.Furthermore,most of them areautotrophic,which means that they usecarbon dioxidefrom thebiogas as a carbon source. Oxygen needs to beadded to thebiogas for biological desulphurisation. Oxygen should beadded in stoichiometric amounts and thelevel needed depends on thecon- centration of hydrogen sulphide.Usual levels are26 % air in biogas. Thesimplest method for desulphurisation is to add oxygen or air directly into the digester chamber.With this method thehydrogen sulphidelevel can bereduced by up to 95 % to levels lower than 50 ppm. Thereareof courseseveral factors that affect the reduction rateliketemperature, placeand amount of air added and reaction time. When adding air into thebiogas safety measures need to betaken into consideration to avoid overdosing of air in caseof a pump failure. Methaneis explosivein therange of 515 % in air. Biological desulphurisation can also takeplacein a separatebio-filter filled with plastic bodies on which desulphurising micro-organisms areattached. In theunit up- flowing biogas meets a counter flow of liquid consisting of gas condensateand liquid from effluent slurry separation or a solution of minerals. Beforethebiogas enters the unit 510 % air is added. In theprocess thehydrogen sulphidelevel can bereduced from 30005000 ppm to 50100 ppm.Ammonia is separated at thesametime. Ironchloridedosingtodigester slurry Thelevel of hydrogen sulphidein thebiogas can bereduced in thedigestion cham- ber by adding iron chloride(FeCl 2 ). Theiron (Fe 2+ ) reacts with sulphideions (S 2- ) and forms iron sulphide(FeS). At themost, thelevel of hydrogen sulphideis reduced to around 100 to 150 ppm depending on theamount of iron chlorideadded. Impregnatedactivatedcarbon Activated carbon can beused to catalytically convert hydrogen sulphideto ele- mentary sulphur and water.As with biological desulphurisation oxygen can beadded to theprocess. Thecarbon is impregnated with potassium iodide(KI) or sulphuric acid to increasethereaction rate.Thesulphur containing carbon can either beregene- rated or replaced with fresh carbon when it is saturated.Impregnated activated carbon is a common method for separation of hydrogen sulphideprior an upgrading system with PSA. Ironhydroxideor oxide Hydrogen sulphidereacts with iron hydroxideor oxideto form iron sulphide(FeS). When thematerial is saturated it can either beregenerated or changed. In theregene- ration, iron sulphideis oxidised with air and iron oxideor hydroxideis recovered together with elemental sulphur. Theiron oxidecontaining material can beoxidised steel wool (rust coated), wood chips covered with iron oxideor pellets madeof red mud, a wasteproduct from alu- minium production.Wood chips areparticularly popular in theUS sincethey arelow cost and havea largesurfaceto volumeratio. Thehighest surfaceto volumeratio is found in pellets. Pellets arecommon at German and Swiss sewagetreatment plants that dont havedosing of iron chloride. Sodiumhydroxidescrubbing A water solution of sodium hydroxide(NaOH) can beused to sepa- ratehydrogen sulphide. Sodium hydroxidereacts with hydrogen sul- phideto form sodium sulphideor sodium hydrogen sulphide. These areboth insolublesalts which means that regeneration is not possible. Removal of tracegases Therearea number of tracegases in thebiogas that can harm the gas distributing system or thegas utilities: Damagecan becaused e.g. through corrosion, deposits or mechanical wear. Contaminants can also causeunwanted exhaust products likeSOx, HCl, HF, dioxins or furans. Water,particles and if present siloxanes and halogenated hydrocar- bons arecomponents which should beremoved for most of theappli- cations either for technical reasons or to reducemaintenancecost. It is not common that thegas has to betreated to reach emissions standards. Halogenatedhydrocarbonremoval Halogenated hydrocarbons, particularly chloro- and flouro-com- pounds arepredominately found in landfill gas. Thecompounds cause corrosion in CHP engines and can beremoved with thesamemethods used to removecarbon dioxide. Siloxaneremoval Organic silicon compounds areoccasionally present in biogas from landfills and biogas from sewagesludge. Activated carbon can beused to separateorganic silicon compounds from biogas. This method is very effectivebut it can beexpensivesince spent carbon cant beregenerated and needs to bereplaced.This means cost for dispo- sal as well as cost for new carbon. Another method for removing thecompounds is absorption in a liquid mixtureof hydrocarbons. Vessel s cont ai ni ng i ron oxi de t hat removes H2S f rom t he bi ogas 23 24 Biogas Upgrading Gas upgradingtechnologies Cost of upgrading Biogas Upgrading Thelevel of siloxanes in biogas can also bereduced through cooling thegas and separating thecondensed liquid. Thereareexamples of systems cooling thegas to 25 C which result in a clean up efficiency of 26 %. Thegas can becooled even furt- her to 70 C causing siloxanes to freeze, resulting in a clean up efficiency of 99 %. Cooling thegas can also becombined with an activated carbon system,giving thecar- bon a longer lifetime. Removal of oxygenandnitrogen If oxygen or nitrogen is present in thebiogas this is a sign that air has been sucked into thesystem.This is common in landfill gas which is collected from thelandfill with permeabletubes by applying a slight under pressure. Low levels of oxygen in thegas arenot a problem but high levels can posean explo- sion risk.In someupgrading processes likePSA and membranes theoxygen and nitro- gen content is also reduced to someextent. Removal of water Biogas is saturated with water vapour when it leaves thedigestion chamber.Before biogas is used as vehiclefuel or fed into thegas grid it needs to bedried. Drying can also benecessary when using thegas for CHP,especially in gas turbines.Refrigeration is a common method for drying biogas. Thegas is chilled with a heat exchanger and thecondensed water is separated. In order to reach higher dew points thegas can be compressed beforeit is cooled. Adsorption of water on thesurfaceof a drying agent is a common method used to reach thevery low dew points needed in vehiclefuel applications (i.e. 40 C or lower at 4 bar).Thedrying agent can besilica gel or aluminium oxide.In order to ensurecon- tinuous operation thesystem usually consist of two vessels onein operation and onein regeneration mode.Thevessels arepacked with drying agent and themoist gas is pas- sed through thevessel. Drying can bedoneat elevated or atmos- pheric pressure.This affects themethod of regeneration.When dry- ing at elevated pressurea small stream of thedry compressed gas is depressurized and used for regeneration. If drying is carried out at atmospheric pressure,air and a vacuum pump is used for regenera- tion. Thedisadvantagewith thelatter method is that it results in adding someair to thebiogas. Another drying method that can beused is absorption of water in glycol or hygroscopic salts.New salt needs to beadded in order to replacethesaturated or even dissolved salt.Thedrying medium can berecovered by drying at elevated temperatures. Cost of upgrading Thetotal cost for cleaning and upgrading biogas derives from cost of investment as well as of operation of theplant and maintenanceof theequipment.When producing biogas of vehiclefuel or pipelinequality themost expensivepart of thetreatment is the removal of carbon dioxide. Investment in a plant for full treatment to vehiclefuel quality depends on several factors. Onemajor factor is of coursethesizeof theplant. Theinvestment increases with increased capacity but at thesametimeinvestment per unit of installed capacity decreases for larger plants.Typical investment for a plant treating 300 nm 3 per hour of raw gas is in theorder of 1 million Euro as shown by thegraph below whereinvestment cost for 16 upgrading plants in Sweden is listed (Swedish Gas Center, 2006). It should bepointed out that theinvestments in theseplants havebeen madebetween 1998 and 2006.For themajority of theplants thebuilding,wheretheequipment is situated,is not included in theinvestment cost. Themajor operation costs for a plant with full treatment to vehiclefuel quality is electricity, personnel, and depending on technique, cost for consumption of i.e. water or chemicals. Theplant also has cost for maintenance. Investment as well as operation and maintenancecosts should bedivided per kWh produced in theplant. A typical cost for an upgrading plant treating 200 mn 3 raw gas per hour is in the order of 1.5 cents per kWh as shown by a Swedish study (seegraph below). Cost for land at which theupgrading plant is situated is not included in thepresented costs. Bi ogas used as vehi cl e f uel needs t o be dry. Wat er vapour can be removed by adsorpt i on on a dryi ng agent . 25 Case studies Injectionof upgradedbiogas intothegas gridof Hardenberg- TheNetherlands On thelandfill siteCollendoornin Hardenberg,located in theeast of theNether- lands, landfill gas is being upgraded to natural gas quality and introduced into thegas grid. Up to now this gas has no special use(it is not earmarked and used as green gas elsewhere). Thelandfill and theupgrading installations aretheproperty of Cogas, a small Dutch energy company. In 2006 around 200.000 nm 3 of upgraded gas werepro- duced.It used to beover 700.000 nm 3 /year in theearly years of theupgrading plant,but volumeof gas from thelandfill has decreased. Gas upgrading is performed by membranetechnology.In thefirst plant which was started in 1993, membranes operated with a gas pressureof 35 bar. Since2003 a new membraneseparation technology has been used enabling thegas pressureto belowe- red to 9 bar.This has reduced costs and improved theeconomic feasibility of theplant. Theupgraded gas has a methanecontent of 88%, a CO2 content of almost 5% and an N2 content of 7%. This results in a heating valueand a Wobbeindex of 35 and 44 MJ/nm 3 , respectively, which areboth similar to thevalues of therather low calorific Groningen natural gas in TheNetherlands. By preventing landfill gas escapeto the atmospherea CO2 emission reduction of approx. 3800 tons a year is obtained (in case of 200.000 nm 3 upgraded gas). Manureandwastefromfoodindustrybecomes vehiclefuel in Kristianstad- Sweden In thetown Kristianstad in thesouth east of Sweden biogas is produced at a co-digestion plant with a continuously stirred tank reactor. About 70,000 ton- nes of wasteis treated annually. About 50 % of theorganic material comes from liquid manure, 45 % arewasteproducts from the food industry and 5 % comes from household waste. Theraw biogas is transported in a 4 km long pipelineto theupgrading plant. Carbon dioxide is removed in a water scrubber without regeneration. Upgra- ded biogas leaving the system has a methane content of approx. 97 %. as demanded by theSwedish standard. In the same upgrading plant biogas from the sewage treatment plant, located nearby, is also treated. In 2006 a second upgrading plant was put into operation. Also this plant is based on absorption of carbon dioxidein water, but this system has regeneration of thewater. Two biogas plants and two upgrading facilities gives good redundancy in thesystem which is very important sincetheSwedish natural gas grid does not serveKristianstad. Thevehiclefuel is used in cars,lorries and buses.All town buses in Kristianstad,as well as someschool buses run on biogas.During 2005 1.2 million nm 3 of upgraded bio- gas was used in vehicles in thetown,thus replacing an equivalent of 1.3 million litreof petrol. 26 Biogas Upgrading Casestudies Casestudies Biogas Upgrading 27 M anure and wast e f rom t he f ood i ndust ry i s di gest ed i n Kri - st i anst ad, Sweden. The bi ogas i s used f or vehi cl es. Usingbiogas fromsewagesludgeinvehicles andapartments in Stockholm- Sweden Biogas has been produced in Stockholm,thecapital of Sweden,sincethebeginning of 1932 mainly as a by-product from thestabilisation of municipal sewagesludge.The gas has been used for heating as well as for power production; it has also been neces- sary to flarebiogas.About 10 years ago biogas was first used for vehiclefuel and since then production of biogas as vehiclefuel has been steadily increasing. The municipality considers that the highest environmental benefits are gained when using biogas as vehiclefuel compared to other options. This is valid both for emissions causing environmental and health impacts (regulated and unregulated) as well as emissions with impact on theclimate(primarily CO2-emissions). Biogas produced at thetwo main sewagetreatment plants, Henriksdal and Brom- ma, has a methanecontent of around 65 %. TheStockholm Water Company operates theplants. Thefinal upgraded product shall contain at least 97 % methaneand not morethan 23 mg/nm 3 H2S (Swedish standard,vehiclequality,SS 155438). Thegoal in Stockholm is to useall biogas from thesewagetreatment for vehiclefuel and to run all (120) inner city buses on biogas.Thebuses arere-fuelled at a bus depot a coupleof kilometres away from Henriksdal.Other vehicles can bere-fuelled at seven public biogas filling stations in the city. Five more stations are under con- struction/planned for thenear future. Today (2006), thereis a higher capacity in the upgrading plants than thereis supply of raw biogas. This has initiated projects for the search of other newpossiblefeedstock materials for biogas production in Stockholm. Henriksdals sewagetreatment plant, StockholmWater TheHenriksdal sewagetreatment plant processes sewagewater from theinner city and of southern parts of Stockholm,resulting in an annual production of about 9 mil- lion nm 3 of raw biogas. In 2001 an upgrading plant was built.Theupgraded gas is used as a vehiclefuel and for cooking and heating at an apartment complex, Hammarby Sjstad, closeto the sewageplant. The upgrading plant is adapted for treatment of about 1400 nm 3 raw gas per hour,which gives a possibility to producearound 6 million nm 3 of upgraded biogas per year.Thegas cle- aning is carried out by water scrub- bing with regeneration,wherecarbon dioxide and H2S are absorbed in water.After cleaning thewater is coo- led and used again whilethecarbon dioxide and the H2S are routed through theventilation system and to thechimney of theplant.Finally,an odour addi- tiveis added to thegas to makeit possibleto detect leaks. Thefinal product, theupgraded and cleaned gas, is stored at a pressureof about 350 bar. Thetotal storagecapacity is 7000 nm 3 . Henriksdal also has an LNG storage (liqufied natural gas) with a capacity of 66 000 nm 3 as a backup during maintenanceor shut down in production or upgrading. Brommasewagetreatment plant, StockholmWater TheBromma sewagetreatment plant produces biogas from theanaerobic digestion of municipal sewagesludge.From 1996 therehas been a continuous project at theplant with thepurposeof upgrading thebiogas to vehiclefuel quality and to increasethe upgrading capacity. Today, moreor less all biogas produced is upgraded and used for vehiclefuel. During theproject (erection, start-up and initial operation) therehave been obstacles,but today (2006),under normal daily operation,theupgrading process run smoothly and without any specific problems. At theBromma sewageplant thebiogas is upgraded in two parallel gas treatment lines with a total capacity of 3.0 (2*1.5) million nm 3 cleaned gas per year (600 nm 3 upgraded raw gas per hour).Thelines havefull redundancy and can beoperated sepa- rately or jointly to guaranteeat least half production capacity even during maintenan- ceand operational problems. In theupgrading process water is first removed from thebiogas by condensation to a specified dew point (<-35 oC at 260 bar).Thepressureof thegas is then increased to 5 bar pressureand H2S is separated in a pre-filter. Carbon dioxideis removed in the PSA (PressureSwing Adsorption) process; ThePSA plant has four separatesynchro- nised adsorption columns that work in a cyclic modechanging between adsorption and regeneration. Finally, thegas is compressed to a pressureof 260 bar and is trans- ferred to a storagewith a total capacity of 5000 nm 3 . MarquetteSewagetreatment plant, Lille- France TheMarquettesewagetreatment plant was built between 1969 and 1977.Today,the plant treats about 120 000 m 3 sewagewater per day and has two primary and two secondary digesters for sewagesludgetreatment. Theraw biogas from thedigesters contains at least 63 % methane. Between 1993 and 1995, a pilot biogas upgrading plant using water scrubbing was built. After start-up and optimisation of theequipment, about 80 nm 3 vehiclefuel could beproduced per hour having a methanecontent of around 97 %.This was suffi- cient to fuel four buses. During thefirst years of production therewereproblems reaching and keeping to thevehiclegas specification.This resulted in a need for recirculation of theproduct gas when it did not meet thespecification. In thebeginning thegas had to berecirculated several times to reach thedesired specification. Sincea lot of parts werenot madeof stainless steel, therewerealso problems with Upgradi ng pl ant i n Henri ksdal , St ockhol m, where t he equi val ent of 6 mi l l i on l i t re of pet rol can be produced annual l y. (Court esy M al mberg Wat er) 28 Biogas Upgrading Casestudies Casestudies Biogas Upgrading 29 wall and piping corrosion caused by thehigh H2S content in theraw gas (3000 ppm). Even whilethesekinds of problems wereexperienced, it was still possibleto run the upgrading plant for almost 9 years but, by 2004 corrosion had deteriorated theupgra- ding equipment to such an extent that it was not safeto operateit further and theope- ration of thefacility was eventually stopped. However, in 2006 thedecision was taken to construct a new upgrading facility at theMarquetteplant and at this time, not a pilot plant but a reliableindustrial installa- tion. Theoriginal principleof cogeneration will probably beretained and even if the biogas is primarily used for electricity and heating purposes,thecapacity of upgraded biogas for vehiclepurposes will beincreased to such an extent that at least ten buses can befuelled. Gridinjectionof upgradedbiogas fromOFMSW - Jona, Switzerland In spring 2005 a small scaledigestion plant for thetreatment of 5.000 tpy of sour- ceseparated organic waste(OFMSW) has started operation in Engelhlzli,Jona.It is a solid wastedigester operated at thermophilic temperatures (55 to 57C).Theretention timein thedigester is about 15 days. Thedigestateis mixed with garden wasteand post-composted in an enclosed hall. Thegas is upgraded with a new Genosorb washing system.Thehydrogen sulphide as well as thehumidity is preliminary removed by activated carbon. It is thefirst plant in Switzerland without an additional CHP. Theentiregas pro- duction is upgraded without intermediatestorageand is fed to thenatural gas grid. Process electricity is taken from thepower line, process heat is produced with a natu- ral gas boiler. Another novelty of theplant is theownership.In all previous plants in Switzerland theowner of thedigestion unit was also theowner of theupgrading plant. Hedelive- red theclean and odorised gas to thegrid.In Jona on theother hand hesells theraw gas to thegas company. They own and operatethe upgrading plant themselves. Thedesign capacity of theupgrading plant is 55m 3 of raw gas per hour. With an input to thedigester of about 20 tons of fresh wasteper working day, thegas production is often far higher then the treatment capacity. Hence, someof thegas has to beflared. Actually,theplant capacity is increased. Thesystem has been selected becauseit had thelowest produc- tion cost with 2.2 cents per kWh when compared to PSA and water washing on thebasis of offers. Further reading Guidance on gas treatment technologies for landfill gas engines, Environment Agency,United Kingdom 2004. Biogas-Netzinspeisung Rechtliche, wirtschaftlicheund technischeVoraussetzun- gen in sterreich, D. Hornbachner, G. Hutter, D. Moor, HEI Hornbachner Energie Innovation,2005. Adding gas from biomass to thegas grid,Report SGC 118,M.Hagen et al,Gastech NV,Danish Gas Technology Center,Swedish Gas Centre,2001. Evaluation of upgrading techniques for biogas, Report SGC 142, M. Persson, Swe- dish Gas Centre,2003. Studie Einspeisung von Biogas in das Erdgasnetz, Institut fr Energetik und Umwelt GmbH,Fachagentur NachwachsendeRohstoffee.V.,2006. 100% Biogas for urban transport in Linkping, Sweden. Biogas in thesociety IEA Bioenergy Task 37.www.iea-biogas.net/casestudies.htm Injection of biogas into the natural gas grid in Laholm, Sweden. Biogas in the society IEA Bioenergy Task 37.www.iea-biogas.net/casestudies.htm Upgradi ng pl ant i n Jona wi t h a washi ng and a regenerat i on t ower operat ed on Genosorb 30 Biogas Upgrading Casestudies Further reading Biogas Upgrading 31 Costcomparisonof upgradingprocesses for theJonaplant bases onoffers (55m 3 /h) The PSA i nst al l at i on i s set arbi t rari l y at 100% 32 Biogas Upgrading List of selectedreferenceplants as by2006 Listof selectedreferenceplants as by2006 Biogas Upgrading 33 An updated version of thelist of referenceplants can befound at www.iea-biogas.net. COUNTRY CITY PRODUCTION BIOGAS CH4 CO2 H2S PLANT IN GAS PRODUCTION REQUIRE- REMOVAL REMOVAL CAPACITYOPERATION UTILISATION (landfill MENTS TECHNIQUE TECHNIQUERAWGAS SINCE gas gridor gas/sew.sludge/ % FLOW vehicle fuel waste/manure) (m3/h) Aust ri a Pucki ng Gas gri d M anure 97 PSA Bi ol . f i l t er 10 2005 Act i vat ed carbon Canada Bert hi ervi l l e Gas gri d Landf i l l gas M embrane 2003 (Quebec) France Li l l e Vehi cl e f uel Sewage sl udge Wat er Wat er 100 1993 scrubber scrubber Li l l e Vehi cl e f uel Bi owast e, 97 Wat er Wat er 2 x 600 2007 manure scrubber scrubber Germany Jamel n Vehi cl e f uel M anure, energy 96 Sel exol Sel exol 100 2006 crops scrubbi ng scrubbi ng Kerpen Gas gri d Energy crops PSA Act i vat ed 500 2006 carbon Pl i eni ng Gas gri d Energy crops PSA Act i vat ed 2006 carbon St rael en Gas gri d Energy crops, manure PSA Act i vat ed 2006 carbon Rat henow Gas gri d Energy crops, manure PSA Act i vat ed 500 2006/ 2007 carbon Icel and Reykj avi k Vehi cl e f uel Landf i l l gas - Wat er Wat er 700 2005 scrubbi ng scrubbi ng Japan Kobe Vehi cl e f uel Sewage sl udge 97 Wat er Wat er 100 2004 Scrubbi ng scrub Kobe Vehi cl e f uel Sewage sl udge 97 Wat er Wat er 2 x 300 2007 scrubbi ng scrub Net herl ands Col l endoorn Gas gri d Landf i l l gas 88 M embrane Act i vat ed 375 1991 (Hardenberg) carbon Nuenen Gas gri d Landf i l l gas 88 PSA Act i vat ed 1500 1990 carbon Ti l burg Gas gri d Landf i l l gas 88 Wat er Iron oxi de 2100 1987 (Spi nder) scrubber pel l et s Wi j st er Gas gri d Landf i l l gas 88 PSA Act i vat ed 1150 1989 carbon Norway Fredri kst ad Vehi cl e f uel Sew.sl udge/ 95 2 PSA - 150 2001 wast e Spai n Vacari sses Vehi cl e f uel Landf i l l gas > 85 Chemi cal Act i vat ed 100 2005 (Barcel ona) absorpt i on carbon M adri d Vehi cl e f uel 96,5 Wat er Wat er 4000 2007 Scrubbi ng scrubbi ng Sweden Bors Vehi cl e f uel Bi owast e 97 Chemi cal Act i vat ed 300 2002 househol d and absorpt i on carbon i ndust ry Sewage sl udge Gt eborg Gas gri d Sewage sl udge 97 Chemi cal Act i vat ed 1600 2006 absorpt i on carbon Hel si ngborg Vehi cl e f uel Bi owast e 97 PSA Act i vat ed 350 2002 and gas gri d househol d and carbon i ndust ry manure St ockhol m Vehi cl e f uel Sewage sl udge 97 PSA Act i vat ed 600 2000 carbon St ockhol m Vehi cl e f uel Sewage sl udge 97 Wat er Wat er 600 2003 scrubber scrubber 800 2006 Skvde Vehi cl e f uel Sewage sl udge, 97 PSA 110 2003 sl aught er wast e Uppsal a Vehi cl e f uel Wast e f rom 97 Wat er Wat er 200 1997 f ood i ndust ry, scrubber scrubber 400 2002 manure, sewage sl udge Trol l ht t an Vehi cl e f uel Sewage sl udge, 97 Wat er Wat er 140 1996 organi c scrubber scrubber 400 2001 househol d wast e COUNTRY CITY PRODUCTION BIOGAS CH4 CO2 H2S PLANT IN GAS PRODUCTION REQUIRE- REMOVAL REMOVAL CAPACITYOPERATION UTILISATION (landfill MENTS TECHNIQUE TECHNIQUERAWGAS SINCE gas gridor gas/sew.sludge/ % FLOW vehicle fuel waste/manure) (m3/h) Norrkpi ng Vehi cl e f uel Sewage sl udge 97 Wat er Wat er 275 2004 scrubber scrubber Norrkpi ng Vehi cl e f uel Resi due f rom 97 Wat er Wat er 240 2006 et hanol scrubber scrubber product i on, energy crops Eski l st una Vehi cl e f uel Sewage sl udge 97 Wat er Wat er 330 2003 scrubber scrubber Jnkpi ng Vehi cl e f uel Sewage sl udge, 97 Wat er Wat er 150 2000 bi owast e i ndust ry scrubber scrubber Vst ers Vehi cl e f uel Bi owast e 97 Wat er Wat er 480 2004 househol d and scrubber scrubber past ure Sewage sl udge Kri st i anst ad Vehi cl e f uel Bi owast e 97 Wat er Wat er 300 1999 househol d and scrubber scrubber 600 2006 i ndust ry manure Sewage sl udge Li nkpi ng Vehi cl e f uel Bi owast e 97 Wat er Wat er 660 1997 househol d and scrubber scrubber 1400 2002 i ndust ry manure Sewage sl udge Swi t zerl and Bachen- Gas gri d Bi owast e 96 PSA Act i vat ed 200 1996 bl ach Vehi cl e f uel carbon Jona Gas gri d Bi owast e 96 Genosorb Act i vat ed 55 2005 Vehi cl e f uel washi ng carbon Lucerne Gas gri d Sewage sl udge 96 PSA Act i vat ed 75 2004 Vehi cl e f uel carbon Ot el f i ngen Vehi cl e f uel Bi owast e 96 PSA Act i vat ed 50 1998 carbon Prat t el n Gas gri d Bi owast e 96 Genosorb Act i vat ed 300 2006 Vehi cl e f uel washi ng carbon Rml ang Vehi cl e f uel Bi owast e 96 PSA Act i vat ed 30 1995 carbon Samst agern Gas gri d Bi owast e 96 PSA Act i vat ed 50 1998 Vehi cl e f uel carbon USA Los Angel es, Vehi cl e f uel Landf i l l gas 96 M embrane Act i vat ed 2600 1993 (CA) carbon Houst on (TX) Gas gri d Landf i l l gas Sel exol Sel exol 9 400 1986 scrubbi ng scrubbi ng St at en Isl and, Gas gri d Landf i l l gas Sel exol Iron oxi de 13 000 1981 (NY) scrubbi ng wood chi ps Ci nci nnat t i Gas gri d Landf i l l gas PSA 10 000 1986 (OH) Dal l as (TX) Gas gri d Landf i l l gas PSA 10 000 2000 Pi t t sburg - Gas gri d Landf i l l gas M embrane 5 600 2004 Val l ey (PA) Pi t t sburg - Gas gri d Landf i l l gas M embrane 5 600 2004 M onroevi l l e (PA) Shawnee (KS) Gas gri d Landf i l l gas Physi cal 5 500 2001 absorpt i on Dayt on (OH) Gas gri d Landf i l l gas Krysol 6 000 2003 (met hanol ) Rent on (WA) Gas gri d Sewage sl udge 98 Wat er Wat er 4000 1984 + scrubber scrubber 1998 34 Biogas Upgrading Someabbreviations anddefinitions SOME ABBREVIATIONS ANDDEFINITIONS AD, anaerobi c di gest i on M i crobi ol ogi cal degradat i on of organi c mat eri al i n t he absence of oxygen. CHP Combi ned heat and power. CNG Compressed nat ural gas. Gas rel at i ve humi di t y Rat i o of t he amount of wat er vapour i n t he gas t o t he maxi mum amount of wat er vapour t hat coul d be i n t he gas i f t he vapour were at i t s sat urat i on condi t i ons. H gas Nat ural gas wi t h hi gh heat i ng val ue. Heat i ng val ue Amount of energy rel eased when a f uel i s burned compl et el y. Hi gher heat i ng val ue i ncl udes recovered heat f rom condensi ng wat er vapour t hat i s produced i n t he combust i on. Al so cal l ed cal ori f i c val ue. L gas Nat ural gas wi t h l ow heat i ng val ue. nm 3 normal cubi c met er Vol ume at at mospheri c pressure (1.01325 bar) and 0C, al so cal l ed STP (st andard pressure and t emperat ure). M SW M uni ci pal sol i d wast e PSA Pressure Swi ng Adsorpt i on. Techni que f or separat i on of carbon di oxi de. Wobbe i ndex Heat i ng val ue di vi ded by t he square root of t he gas rel at i ve densi t y t o ai r.