MethanolProduction

1.1Productionmethods

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Thebyfardominatingproductionmethodofmethanolsynthesisisthroughthesynthesisgasprocessfirstdeveloped
duringthe1920s.Agasmixtureofhydrogenandcarbonmonoxide(usuallyalsocarbondioxide),knownassynthesis
gas(syngas)isthebasisforalmostallmethanolproductiontoday[1].

1.1.1Methanolsynthesiseswithsynthesisgas
Theproductionofmethanolusuallyconsistsofthreebasicstepsindependentoffeedstockmaterial:synthesisgas
preparation,methanolsynthesisandmethanolpurification.
Inordertoproperlyunderstandthechallengesofdifferentprocessestoproducethesynthesisgas,wefirstneedto
understandtheprocessfromsynthesisgastomethanol,themethanolsynthesis.Inessencetheprocessconsistsof
thethreefollowingequations:

CO+2H2CH3OHH298K=21.7kcal/mol(1)

CO2+3H2CH3OH+H2OH298K=11.9kcal/mol(2)
ReverseWGSCO2+H2CO+H2OH298K=9.8kcal/mol(3)

Allthreeequationsarereversibleandthustheprocessconditionsregardingtemperature,pressureandsynthesisgas
mixtureareimportanttocontrol.Itcanalsobenotedthatequation(1)and(2)areexothermic,i.e.theprocesses
produceheatandrequirecooling.Someheatisnormallyrecoveredandusedforotherpartsofthesynthesis.
Whileitwasoriginallybelievedthatthemainprocessthatproducemethanolwasthereactionbetweencarbondioxide
andhydrogen(equation1)itisnowunderstoodthatcarbondioxideisjustasimportantinthesynthesisprocess.CO2
evenusedtobescrubbedfromthereactantmixturebutascrubberfailureatImperialChemicalIndustries(ICI)witha
resultingincreaseofmethanolproductionshowedthatCO2wasactiveandimportantinthereaction.Subsequent
studieshasshownthatitismainlytheCO2thatisconvertedtomethanolwhileCOactasanreducingagentfor
oxygenatthesurfaceofthecatalyst[4].
Equation(3)describesthereversewatergasshiftreactionthatproducescarbonmonoxidefromcarbondioxideand
hydrogen.Thecarbonmonoxidethenreactswithhydrogentoproducemethanol(equation2).Equation2isactually
merelythesumof(1)and(3)[2].
Tosynthesisemethanol,notonlyisaspecificH2/COratioof2inthesynthesisedgasneededbutalsoa(H2
CO2)/(CO+CO2)ratio,calledstoichiometricnumber,equaltoorslightlyabove2[3].

1.1.2Synthesisgasproductionfromnaturalgas
Beforenaturalgasisprocessedtosynthesisgasimpuritiesneedstoberemoved.Themostimportantaresulphur
compounds(suchasH2S)becauseofthepoisonouseffectsthesehaveoncatalystsdownstream[5].Otherimpurities
suchascarbondioxide,nitrogena

1.1.2.1Steamreforming
Thetraditionallydominatingmethodisthroughsteamreformingwheremethanegasandsteamismixedathigh
temperatureandpressureandwiththehelpofcatalystsformcarbonmonoxideandhydrogen(Equation4).Thegas
mixtureistypicallyledthroughpipescoatedwithcatalystsinatubeinshellheatexchangerinordertoprovidethe
necessaryheat(850C)forthereactiontotakeplace.


Steamreforming2CH4+2H2O2CO+6H2H298K=49.1kcal/mol(4)
WatergasshiftCO+H2OCO2+H2H298K=9.8kcal/mol(5)

Carbondioxideistypicallyaddedtothegasmixturebeforethemethanolsynthesisbutcanalsobepresentinthe
naturalgasusedasfeedstock.
RememberingthattheH2/COratioshouldbe2formethanolsynthesisweobservethatsteamreformingproducesan
excessofhydrogenwhichneedstobesubtractedandisusuallyburnttoprovideheatforthereformationtotakeplace
butcanalsobeusedforotherpurposes.
Thesynthesisgasproductionisstronglyendothermicandrequiresalotofthermalenergy.Themethanolsynthesis
producesomeheatthatcanberecoveredbutheatisnormallyalsoprovidedbyburningaportionofthenaturalgas.
Thesynthesisgasproductionandsubsequentcompressionstandsforalargeamountoftheinvestmentcostina
methanolproductionplantandmostoftheenergyneedtopowertheprocessandrepresentsasmuchas60%ofthe
capitalcost[1][6].
Onestepreformingthroughsteamreformingusedtobethedominatingprocessbutistodaymainlyconsideredfor
smallerplantsupto2500MTPDwhereCO2isavailableatlowcostorcontainedinthenaturalgas[1].

1.1.2.2Partialoxidation
Anotherbasicroutforsynthesisgasproductionispartialoxidation.OriginallydevelopedbyShellinthe1950s[3].

CH4+0.5O2CO+2H2H_298K=8.6kcal/mol(6)
CO+0.5O2CO2H_298K=67.6kcal/mol(7)
H2+0.5O2H2OH_298K=57.7kcal/mol(8)

Thepartialoxidationprocessformethaneisslightlyexothermic.Theprocessoccursinthegasphaseviaradical
reactionwithintheflameoftheburner.Asmallexcessofoxygenisneededtofavoursomeoxidationtocarbondioxide
andwaterinordertobringupthetemperaturetothedesired10001200C[3],unfortunatelythatproducescarbon
dioxideandwaterthatlowersthestoichiometricnumbertoabout1.6whichisbelowthepreferred2butanimprovement
oversteamreforming.
Alargecostforapartialoxidationplantistheairseparatorneededtoproduceoxygen.Whileitispossibletouseair
mostmodernplantsusepureoxygentoavoidtheneedofseparatingmainlynitrogenfromthesynthesisgasafterthe
oxidationstep.

1.1.2.3Twostepreforming
Acombinationofsteamreformingandpartialoxidationoffersameantoimprovetheoverallprocessandtobetter
controlthecompositionoftheproducedsynthesisgas.Therightsystemconfigurationdependsonthecompositionof
thenaturalgasusedasfeedstock.Twostepreformingalsorequiresthatthesteamreformingoperateswithhigh
methaneslip,usually3545%,[1]toprovideahighenoughmethanecontentforthepartialoxidationstep.
Thetechniqueisfairlynewandwasfirstusedina2400MTPDcommercialplantinNorway2007anda5000MTPD
plantwithsimilartechnologyinSaudiArabia2008[1]

1.1.2.4Dryreforming
Byreactingmethaneandcarbondioxidesynthesisgasisproducedinaprocesscalleddryreformingasnosteamis
used.

DryreformingCH4+CO22CO+2H2H298K=59.1kcal/mol(9)

Thereactionismoreendothermicthansteamreformingandproducesagaswithsignificanthydrogendeficitfor
methanolsynthesis.Whilethisisadisadvantageformethanolsynthesisthegasmixturehastherightcompositionfor
otherapplications.

1.1.3Synthesisgasfromcoal
Theprocesstoconvertcoaltosynthesisgasisacombinationofpartialoxidationandsteamtreatmentcalled
gasification.[2].

C+0.5*O2COH298K=29.4kcal/mol(10)
C+H2OCO+H2H298K=31.3kcal/mol(11)
CO+H2OCO2+H2H298K=9.8kcal/mol(12)
CO2+C2COH298K=40.8kcal/mol(13)

Thedesignandprocessingconditionsvarygreatlydependingonthecompositionofthecoalusedasfeedstock.The
synthesisgasproducedhaveadeficitofhydrogenandmustbesubjectedtothewatergasshiftreaction(equation12)
inimprovetheH2/COratio.Thesynthesisgasproducedfromcoalisusuallyinhigherneedofpurificationthanthat
producedfromnaturalgas,especiallysulphurcompoundsmustberemovedbeforethemethanolsynthesistoprotect
thesensitivecatalystsfrompoisoning.

1.1.4Biomass
Incontrasttoethanol,methanolcanrathereasilybeproducedfromvirtuallyallbiomasssuchaswood,algae,
agriculturalwasteandmunicipalwastethroughgasification.Productionfrombiomassdoeshoweverofferchallenges
thatneedtobeaddressedespeciallyregardingthecostofproduction.Duetothecompositionofbiomassthe
productionplantsinquirehighcapitalinvestmentcostsandhaslowerenergyconversionefficiencycomparedtonatural
gasandcoal[7].
Theconventionalmethodtoproducemethanolfrombiomassisthroughgasificationofthefeedstockmaterial.An
attractivealternativeisenzymaticconversion,althoughmostresearchinthisareaiscurrentlyfocusedonethanol
production.Anotheralternativemainlyforseagrowingplantslikemacroandmicroalgaeaswellaswaterhyacinthand
cattailetc.isanaerobicdigestionthatproducesmethanethatcouldbeusedinthesamewayasnaturalgas.Aswith
enzymaticconversionthemethodsisstillinneedoffurtherresearchanddevelopmentbeforelargescalecommercial
implementationispossible[2].
Thegasificationprocessofbiomassissimilartothesynthesisgasprocessfromcoal.Forgasificationofbiomassthe
feedstockisfirstdriedandpulverized.Themoistcontentshouldgenerallybenohigherthan1520wt%.Thefirststep
inatwostepgasificationprocessiscalledpyrolysis,ordestructivedistillation.Thedriedbiomassisheatedto400600
Cinanoxygendeficientenvironmenttopreventcompletecombustion.Carbonmonoxide,carbondioxide,hydrogen,
methaneaswellaswaterandvolatiletarsarereleased.Theremainingbiomass(1025wt%),calledcharcoal.is
furtherreactedwithoxygenathightemperature(13001500C)toproducemainlycarbonmonoxide.
Thesynthesisgasproducedfromthepyrolysisandcharcoalconversionispurifiedbeforethemethanolsynthesis.
Comparedtocoalbiomassconsistsofmuchlesssulphurbutthetarcontentoffersoperationalchallengesasit
condenseeasilyinpipes,filtersandboilers.Thiscantoanextentbecontrolledbychoosingtherightoperational
patternandtechniqueaccordingtothecompositionoftheavailablebiomass.Aonesteppartialoxidationprocessisan
attractivealternativebutthetechnicalchallengeshavesofarpreventedlargescaleoperation.
Productionfrombiomassispossibleatsmallscalebutaswithnaturalgasandcoallargescaleproductionispreferred
duetothehighsystemcosts.Thelogisticalchallengesforabiomassplantarehowevergreatduetothelowerenergy
contentinbiomasscomparedtonaturalgasandcoalimplyingalargedemandoffeedstockmaterial.Thequantities
neededtofeeda2500MTPDplantisestimatedto1.5milliontonbiomassperyear[2]withputlargestrainson
collection,transportationandstorageofbiomassandmightbeoneofthelargesthurdlestowardstheconstructionon
megasizedplants[7].

Analternativethathasbeenproposedtosolveoreasethetransportationdemandsistofirstconvertthebiomassto
biocrudethroughfastpyrolysis.Driedandatomizedbiomassisquicklyheatedtoabout400600Cinatmospheric
pressureandthenquenchedtoavoidcracking[2].Theresultisablackliquidcalledbiocrudethatcanbetransported
moreeasily.

1.1.4.1Blackliquorfrompulp
Blackliquorfromthepulpindustryhasbeenidentifiedasaninterestingfeedstockforrenewableenergy.Blackliquoris
formedaspulpwoodismixedwithchemicals(whiteliquor)toproducepulpasaprestagetopaperproduction.Black
liquorcanbegasifiedandusedformethanolsynthesis.Thechemicalsarerecoveredandreused.
Blackliquorisavailableinlargequantitiesworldwideandoffersafeasiblewaytoproducemethanol.Anindustrialscale
demonstrationplantattheSmurfitKappapapermillinPite,Swedenhasbeenoperationalsince2010producingDME.

1.2Otherproductionmethods
Theproductionmethodofmethanolstandsbeforetwochallenges.Thefirstoneistomakethecurrentmethodsof
productionfromfossilfuelsmoreenergyandmoreenvironmentallyefficient.Whilethetwoisinterconnected,theyare
notnecessarilythesame.Energyefficientiseasilygraspedwhenrememberingthatthecurrentproductionmethods
requireasubstantialamountofheatwhichisusuallysuppliedbyburningaportionofthefeedstock.Withenvironmental
efficiencythatstandsmainlyforgreenhousegasemissions.Withnaturalgasresourcesstillvastachallengeisto
utilisethesebutatthesametimemitigatetheenvironmentalconsequences.

1.2.1Carnolprocess
TheBrookhavenNationalLaboratoryhavedevelopedamethanetomethanolprocessthatideallydoesnotcontributeto
CO2emissionsbyusingcarboncapturetechniquesforthecarbondioxideneededforthemethanolsynthesis.The
processreliesonthermaldecompositionofmethanethatproducethehydrogenneededforthemethanolsynthesis.
Theotherproductissolidcoalwhichiseasytotakecareof.
Methanetherm.decomp.
Methanolsynthesis
OverallCarnol
Themainchallengefortheprocessistocapturecarbondioxideinaneconomicalwayandtopurify,concentrateand
transportittothemethanolplantinaneconomicalway.Fortheshorttermindustrieswithlargeconcentratedemissions
ismostlikelythepreferredroutebutcapturefromtheatmosphereisapossiblefutureroute.
Itshouldbenotedthatthermaldecompositionfrommethaneisanendothermicprocessthatrequireexternalheating.
Theneedisnotasgreatasforsteamanddryreformingandispreferablysuppliedfromrenewablesources.
Thecarnolprocessisstillonthedevelopmentstagebutcouldofferapossiblewaytostillusethenaturalgassources
thatisavailablewithminimalenvironmentaleffects.

1.2.2Bireforming
BycombiningsteamreforminganddryreformingOlahet.al.[6]proposeamoreefficientwaytoproducesynthesisgas
fromnaturalgas.TheprocessproducessynthesisgaswiththerightH2/COratio,calledmetgas,inasingleortwostep
process.
Steamreforming(4)[2]
Dryreforming(9)
Bireforming

ThebigadvantagewithbireformingisthatthesynthesisgashastherightH2/COratioandthusallhydrogencanbe
usedformethanolproduction.Theprocessisthoughstillhighlyendothermicandrequiresasubstantialadditionof
heat.Thisheatispreferablysuppliedbyrenewableorevennuclearsources.

1.2.3Directoxidationofmethanetomethanol
Anattractivealternativeforsynthesisofnaturalgastomethanolwouldbeiftheenergyconsumingstepofsynthesis
gascouldbeavoidablebydirectlyinsertinganoxygenatominthemethanemoleculebydirectoxidation.Thedifficulty
isthatthehighreactivityoftheproductsthemselveseasilyresultsincompletecombustionofthemethanetocarbon
dioxideandwater.

Despitethedesireofsuccessnomethodhasbeenfoundtoachieveahighenoughselectivity,productivityand
catalyststabilityforindustrialapplications[2].

1.2.4CO2+H2
Withtheadvancesofrenewableenergyaswellasgreaterutilizationofexistingenergysourcessuchasthesunand
geothermalheatmethanolevolvesnotasanenergysourcebutasanenergycarrierwithgreatpotential.Whilebiomass
andotherwastematerialsisapossibleandprobableroutetograduallydecreaseourdependenceonfossilenergy
sourcestherearetechnologiesavailablethatallowsustoproducemethanolandatthesametimereducethecarbon
dioxideemissionsinouratmosphere.Theprocessconsistsofcombininghydrogenandcarbondioxidetoproduce
methanolwiththeonlybyproductbeingoxygenfromtheelect.
Electrolycisofwater

Theideaistoproducemethanolfromcarboncapturedfromtheatmosphere,mainlyfromlocalemitterssuchaspower
plantsandindustrialfacilitiesbutwithimprovingtechnologiesalsofromtheatmosphereitself.Toaccommodatethe
needforhydrogeninthesynthesisprocesselectrolysisofwaterisperformedwithelectricity.Electrolysisofwaterisan
oldtechnologythathasbeenusedformorethanacenturybutastheenergyconsumptionisveryhighonlyasmall
partwithhighpuritydemandsoftheworldproductionofhydrogenisthroughelectrolysis.Thebestenergyefficiencyis
todayaround73%withtheexpectancytoreachtoward85%withcurrentresearchanddevelopmentprograms[8].
Thesuccessofthistechnologyreliesofanabundanceofenergythatcancomefrommainlysolar,windandthermal
sourcesthatlackanyefficientmeanofstorageinotherways.CarbonRecyclingInternational(CRI)iscurrently
operatingoneplantonIcelandthatuseavailablegeothermalenergytoproduce5000m3methanolperyear[9]and
MitsuiChemicalshasannouncedconstructionofademonstrationplantcapableofproducing100tonnemethanolper
yearfromCO2.

1.3Methanolpurification
Regardlessofthesynthesismethodthecrudemethanolproducedcontainsimpuritiestoasmallerorlargerdegree.The
largestimpurityisusuallywaterwhichcanbeasmuchas18%[10].Thefirststageinacommontwosteppurification
processistoremovethelowboilingpurifications,typicallycalledlightends.Thisisdoneinatoppingcolumnwhere
thelowboilingcompoundsareboiledofftoproduceamixtureofmethanolandwater.

Arefiningcolumnisusedtoseparatewaterandmethanolunderheavyboiling.Therefiningcolumnneedstobehighas
methanolandwaterisreluctanttoseparateeasily.Goodqualitymethanoleventuallyaccumulatesinthetopofthe
columnandistransferredtoastoragetank.Wateraccumulatesinthebottomandtakentoatreatmentfacilitybefore
disposal.

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