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MethanolEnergyAnalysis

SteveAtkins,PE ArizonaSyntheticFuelsProject SustainableEnergySolutionsGroup NorthernArizonaUniversity ThefollowingisareportontheenergyrequiredtosynthesizeMethanolfrom atmosphericcarbondioxideandhydrogen. Unlikesimilaranalysesassociatedwiththe energybalanceofEthanol,thisanalysisdoesnotquantifyfossilfuelinputsintothe synthesisofMethanolbecause,forourprocess,therearenofossilfuelinputs. AswithanEthanolenergybalanceanalysis,thisMethanolenergybalanceanalysis doesnottakeintoaccounttheenergyrequiredtomanufacturetheapparatusnecessary forthesynthesisofMethanol.Wetrackandquantifytheinputstothesynthesisof Methanolaswellastheoutputs,andcomparethemtotheintrinsicenergycontentof Methanol. OurprocessisbasedonICIslowpressureMethanolprocedureintroduced commerciallyin1966andonworkdoneby Mr.MichaelSpechtandMr.AndreasBandi fromtheCenterofSolarEnergyandHydrogenResearch(ZSW),locatedinStuttgart Germany,intheearly1990s. ThisprocessofMethanolsynthesishasonlythreeinputs:water,electricityand atmosphericcarbondioxide,andfouroutputs:Methanol,water,Oxygenandheat. No allowanceismadefortheproductionofoxygen. Itisarequirementthattheelectricityinputbefromanonfossilfuel(andcarbonneutral) sourcesuchaswind,hydro,solar,biomass,geothermal,etc.Evennuclearisan acceptableelectricitysourceasfarasthisanalysisisconcerned. TheactualMethanolsynthesisprocessiscontinuousandunderautomaticcontrol. And, unlikefarming,wemaintainthatnodirectlaborinputsarerequiredforMethanol synthesis(thoughitcouldbearguedthatnosystemiscompletelyautomaticandthat somehumansupervisionandmaintenancepersonnelarerequired). ThegoverningchemicalequationforthesynthesisofMethanolis: CO2 +3H2 CH3OH+H2O
H=49.7kJ/mole

(1)

Thisreactionisexothermicandtakesplaceat260Cand1200psi.

CO2 isprovidedincompressedform(approx850psi)bytheownerofthefermentation processor(i.e.MogollonBrewingCo.).Hydrogenisobtainedbythesplittingofwaterin acommercialelectrolyzersuchastheH2 IGENfromHydrogenSystems. Thehydrogenandcarbondioxidearemixedina3:1molarratio,compressedto1200 psiandintroducedintoareactorvesselcontainingaCu/ZnObasedcatalyst.Atbest, 25%ofthefeedgasesareconvertedtowetMethanol(amixtureofmethanoland water). Theproducts,gaseousMethanol,waterandunreactedCO2 andH2 areexpansively cooledtoabout40Cintheknockoutdrumwherethewetmethanolsettles.Theun reactedCO2 andHydrogenareredirectedtothereactorbyarecyclecompressor makeupgasesofH2 andCO2 areaddedtothereactorsothatthereactoroperatesina continuousmannerataconstantflowrateaspacevelocityof8000litersperhourper literofcatalyst. Thewetmethanolisdistilled,separatingtheMethanolandwaterthewaterisfedback totheelectrolyzertoproduceHydrogen. ENERGYGAINANALYSIS Thefollowingenergybalanceanalysiswillbebasedontheproductionof1Kgof Methanol. 1KgofMethanolisequivalentto31.25molesofMethanol(31.25moles* 32.04g/mole=1000g)soequation1canberewrittenas: 31.25CO2 +93.75H2 31.25CH3OH+31.25H2O Inmassterms: 1.375KgofCO2 +0.1875KgofH2 1.0KgCH3OH+0.5625KgH2O Heatisevolvedat(H=49.7kJ/mole)49.7KJ/mole*31.25moles=1.5MJ Reactionheat=1.5MJ CO2 isprovidedbuttheHydrogenmustcomefromthesplittingofwater: H2OH2 +Oorrebalancing: 93.75H2O93.75H2 +93.75O Inmassterms: 1.6875KgH2O0.1875KgofH2 +1.5KgO Sincethe0.5625KgofH2Oproducedinequation2isrecycled,thenetwaterrequired toproduce1KgofMethanolis1.68750.5625kg=1.125Kg.1KgofMethanolis equivalentto1Kg/0.791Kg/liter=1.264litersand1.125Kgofwaterisequivalentto 1.125liters.Fromthiswecanconclude: (2)

Ittakes0.89litersofwatertoproduce1literofMethanol. Nootheramountsofwaterisconsumedintheprocess.Assumingthiswaterispumped fromadepthof100meterswith75%efficiency(perPatzek),theenergyrequiredto inputthiswatertotheelectrolyzeris: 1.125kg*100m*9.81m/s/0.75=1,472J. Waterpumping=0.0015MJ AssuminganalkalineelectrolyzersuchastheH2IGENisused,thefeedwateris electrolyticallypressurizedandfilteredbeforebeingsplit.Theenergyrequiredtosplit waterislistedas3.9KWh/Nm^3ofHydrogen,equivalentto14MJ/m^3or156MJ/Kg H2. Fromequation2,weneed0.1875KgH2 perKgofMethanolsotheenergycostofthe electrolyzeris: (156MJ/KgH2)*(0.1875KgH2)=29.3MJ ElectrolyzerEnergy=29.3MJ TheCO2 andH2mustbecompressedpriortoenteringthereactorandtheunreacted gasesrecompressedinacyclicloop.Thepowerrequiredtocompressagasis dependentontheinletpressure,outletpressureandflowrate.TheH2IGEN electrolyzerdeliversHydrogenat375psi,theCO2 isassumedtobedeliveredat850psi andthepressureintheknockoutdrumisafunctionofdrum volume.Therequired outletpressureisthatofthereactor,1200psi. Tosimplifycalculationsandtoallowtheuseofpublishedcompressorstatisticsfrom HydroPac,Inc.wewillconservativelyassumethatallinletpressuresareat300psiand theoutletpressuresare1500psi. Inthiscase,theHydroPacModelC1.503140/300LXhydrogencompressorwilldeliver 10.1scfm (17.2Nm^3/Hr)usinga3hp(2.25KW)electricmotor,whichwewillassume is75%efficient. Equation2isconvertedfromamassequation(atStandardTemperatureandPressure, STP)toavolumeequationatSTPbyusingtheknowndensitiesofCO2 (1.98Kg/m^3), H2 (0.08988Kg/m^3),Methanol(791Kg/m^3)andwater(1000Kg/m^3),gives: 0.69Nm^3ofCO2 +2.09Nm^3ofH2 1.26litersofCH3OH+0.56litersofH2O (3)

Thus,thecompressorsmustcompress2.78Nm^3ofreactantgasesintothereactor. In reality,thereareatotalofthreecompressorsoneforCO2,oneforhydrogenandonefor therecirculationofCO2 andH2.Butsincetheinletandoutletpressuresarethesame andthecompressorsareassumedidentical,wecan,forthepurposesofcalculation, combinethemallintoone.

Now,2.78Nm^3ofgasesmustbepushedthroughthereactorandconvertedinto1Kg (1.26liters)ofMethanoland0.56Kg(0.56liters)ofwater. Butthereactionisonly25% efficient,soaftertheinitial2.78Nm^3ofgashasgoneoncethroughthereactor,75%or 2.09Nm^3ofthegasremainsandmustbepushedthroughthereactoragain.This process,intheoryneverends(muchlikeacapacitorcharging)however,inpracticewe stoptheprocessafter95%to99%ofthegaseshavereacted.Notethatthisisjustan artifactofproducingjust1KgofMethanolinrealitytheoperationiscontinuous. Pass 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Total InitialVolume 2.78 2.08 1.56 1.17 0.88 0.66 0.50 0.37 0.28 0.21 0.16 0.12 0.09 0.07 0.05 0.04 0.03 0.02 0.02 0.01 11.09 FinalVolume 2.08 1.56 1.17 0.88 0.66 0.50 0.37 0.28 0.21 0.16 0.12 0.09 0.07 0.05 0.04 0.03 0.02 0.02 0.01 0.01

Thus,atotalof11.09Nm^3ofgasrunsthroughourhypotheticalcompressor,whichcan pumpthisgasatarateof17.2Nm^3/Hrusinga3hp(2.25KW)electricmotor,which wewillassumeis75%efficient.Thismeansourcompressorrunsfor11.09/17.2=0.64 hoursandconsumes(2.25KW)*(0.64hours)/.75=1.93KWhsorabout7.0MJ. Compressorenergy=7.0MJ ThewetMethanolhasbeenliquefiedbytheexpansivecoolingthattakesplacewhen thehot,highpressurevaporisdepressurizedintheknockoutdrum noexternal energyisneeded.ButthewetMethanol,consistingofamixtureof1.26litersof Methanoland0.56litersofwaterneedstobedistilledtoextractpureMethanol. TodistillthewetMethanol,themixture,initiallyat40Cmustberaisedtoaminimumof 65C.Thisrequireslifting1KgofMethanol25C:

(1Kg)*(2510J/KgC)*(25C)=.06MJ plusraising0.56Kgofwater25C:(0.56Kg)*(4184J/KgC)*(25C)=0.06MJ. Thentoboiloff1KgofMethanolrequiresvaporizationenergy: (1Kg)*(1.23MJ/Kg)=1.23MJ Finally,thegaseousMethanolmustbecooled/condensedtoaliquidstateeitherby convectivecooling,forcedaircooling,evaporativecooling,oraclosedloopsystem consistingofafan,radiator,pumpandcoolant. Wenotethat,whilewastefulofwater, evaporatingKgofwaterwouldbesufficienttocondense1KgofMethanolandwould addaminiscule650Jtothepumpingenergy. Butwewillassumeanothermethod consuming0.35MJisusedforcondensingouttheMethanol. Totalfordistillation:1.7MJ Summingalltheenergycosts,wehave: Waterpumping: HydrogenProduction(Electrolyzerenergy) Compressorenergy Distillation Reactionheat TotalEnergyCostsfor1KgofMethanol: EnergyContentof1KgofMethanol EnergyBalance(22.7/36.5) 0.0015MJ 29.3MJ 7.0MJ 1.7MJ 1.5MJ 36.5MJ 22.7MJ 62%

Toputthesenumbersinperspective,itisusefultocompareMethanoltoliquid Hydrogen.Toobtainthesameenergycontentof1Kg(1.26liters)ofMethanolone needs0.167Kg(1.86m^3)ofHydrogen.IfthisHydrogenisproducedbythesame electrolyzer,werequire(3.9KWh/m^3)*(1.86m^3)=7.25KWhor26MJofenergy. This1.86m^3ofHydrogencanbecondensedinto2.35litersofliquidHydrogen (density70.8g/l)buttheliquefactionprocessimposesaminimum30%energycostof8 MJ.ThusthetotalcostofliquidHydrogenwiththesameenergycontentof1Kgof Methanolis34MJandtheenergybalanceis22.7/34=67%. IncomparisontoMethanol,liquidHydrogenrequirestwicethevolumeperenergy contentandacryogenicstoragesystem,whichwillexperienceboilofflossesof between1and5%perday(dependingonthesizeofthetank).

Appendix Methanol,alsocalledmethylalcoholorwoodalcohol,isacolorless,watersolubleliquid withamildalcoholicodor.Itfreezesat97.6C,boilsat64.6Candhasadensityof 0.791at20C. Propertiesof Chemicalformula Molecularweightg/mole Meltingpoint C Boilingpoint C Density@20CKg/m^3 EnergycontentMJ/Kg EnergyofvaporizationMJ/Kg SpecificheatJ/KgC Methanol CH3OH 32.04 97.6 64.6 791 22.68 1.23 2510 Hydrogen H2 2.0 259.1 252.9 0.08988 135.8 Water H2O 18.0 0 100 1000 2.26 4184

Someusefulconversionfactors: 1KWh=3.6MJ 1calorie=4.184J 1hp=746Watts 1Watt=1J/sec 1BTU=252calories