Вы находитесь на странице: 1из 6

MethanolProduction

1.1 Productionmethods

Print

Thebyfardominatingproductionmethodofmethanolsynthesisisthroughthesynthesisgasprocessfirstdeveloped

duringthe1920s.Agasmixtureofhydrogenandcarbonmonoxide(usuallyalsocarbondioxide),knownassynthesis

gas(syngas)isthebasisforalmostallmethanolproductiontoday[1].

1.1.1 Methanolsynthesiseswithsynthesisgas

Theproductionofmethanolusuallyconsistsofthreebasicstepsindependentoffeedstockmaterial:synthesisgas

preparation,methanolsynthesisandmethanolpurification.

Inordertoproperlyunderstandthechallengesofdifferentprocessestoproducethesynthesisgas,wefirstneedto

understandtheprocessfromsynthesisgastomethanol,themethanolsynthesis.Inessencetheprocessconsistsof

thethreefollowingequations:

CO + 2H 2 CO + 3H 2 2 Reverse WGS CO + H ⇌
CO + 2H
2
CO
+ 3H
2
2
Reverse WGS
CO
+ H
⇌ CH OH
⇌ CH OH + H O
⇌ CO+H O
Δ
(1)
3
H298K
Δ
(2)
3
2
H298K
Δ
= ‐21.7 kcal/mol
=‐11.9 kcal/mol
= 9.8 kcal/mol
(3)
2
2
2
H298K

Allthreeequationsarereversibleandthustheprocessconditionsregardingtemperature,pressureandsynthesisgas

mixtureareimportanttocontrol.Itcanalsobenotedthatequation(1)and(2)areexothermic,i.e.theprocesses

produceheatandrequirecooling.Someheatisnormallyrecoveredandusedforotherpartsofthesynthesis.

Whileitwasoriginallybelievedthatthemainprocessthatproducemethanolwasthereactionbetweencarbondioxide

andhydrogen(equation1)itisnowunderstoodthatcarbondioxideisjustasimportantinthesynthesisprocess.CO

evenusedtobescrubbedfromthereactantmixturebutascrubberfailureatImperialChemicalIndustries(ICI)witha resultingincreaseofmethanolproductionshowedthatCO wasactiveandimportantinthereaction.Subsequent studieshasshownthatitismainlytheCO thatisconvertedtomethanolwhileCOactasanreducingagentfor

oxygenatthesurfaceofthecatalyst[4].

2

2

2

Equation(3)describesthereversewatergasshiftreactionthatproducescarbonmonoxidefromcarbondioxideand

hydrogen.Thecarbonmonoxidethenreactswithhydrogentoproducemethanol(equation2).Equation2isactually

merelythesumof(1)and(3)[2].

Tosynthesisemethanol,notonlyisaspecificH/COratioof2inthesynthesisedgasneededbutalsoa(H­

CO)/(CO+CO)ratio,calledstoichiometricnumber,equaltoorslightlyabove2[3].

2

2

2

2

1.1.2 Synthesisgasproductionfromnaturalgas

Beforenaturalgasisprocessedtosynthesisgasimpuritiesneedstoberemoved.Themostimportantaresulphur

compounds(suchasHS)becauseofthepoisonouseffectsthesehaveoncatalystsdownstream[5].Otherimpurities

suchascarbondioxide,nitrogena

2

1.1.2.1 Steamreforming

Thetraditionallydominatingmethodisthroughsteamreformingwheremethanegasandsteamismixedathigh

temperatureandpressureandwiththehelpofcatalystsformcarbonmonoxideandhydrogen(Equation4).Thegas

mixtureistypicallyledthroughpipescoatedwithcatalystsinatubeinshellheatexchangerinordertoprovidethe

necessaryheat(≈850°C)forthereactiontotakeplace.

Steam reforming

2CH

4

+ 2H O 2CO + 6H

2

2

ΔH

298K

Water gas shift

CO + H O CO

2

2

+ H

2

ΔH

298K

= 49.1 kcal/mol

(4)

= ‐9.8 kcal/mol

(5)

Carbondioxideistypicallyaddedtothegasmixturebeforethemethanolsynthesisbutcanalsobepresentinthe

naturalgasusedasfeedstock.

RememberingthattheH/COratioshouldbe2formethanolsynthesisweobservethatsteamreformingproducesan

excessofhydrogenwhichneedstobesubtractedandisusuallyburnttoprovideheatforthereformationtotakeplace

butcanalsobeusedforotherpurposes.

2

Thesynthesisgasproductionisstronglyendothermicandrequiresalotofthermalenergy.Themethanolsynthesis producesomeheatthatcanberecoveredbutheatisnormallyalsoprovidedbyburningaportionofthenaturalgas. Thesynthesisgasproductionandsubsequentcompressionstandsforalargeamountoftheinvestmentcostina

methanolproductionplantandmostoftheenergyneedtopowertheprocessandrepresentsasmuchas60%ofthe

capitalcost[1][6].

Onestepreformingthroughsteamreformingusedtobethedominatingprocessbutistodaymainlyconsideredfor smallerplantsupto2500MTPDwhereCO isavailableatlowcostorcontainedinthenaturalgas[1].

2

1.1.2.2 Partialoxidation

Anotherbasicroutforsynthesisgasproductionispartialoxidation.OriginallydevelopedbyShellinthe1950s[3].

CH + 0.5O ⇌ CO+2H Δ (6) 4 2 2 H_298K CO + 0.5O ⇌
CH
+ 0.5O
⇌ CO+2H
Δ
(6)
4
2
2
H_298K
CO + 0.5O
⇌ CO
Δ
= ‐8.6 kcal/mol
= ‐67.6 kcal/mol
= ‐57.7 kcal/mol
(7)
2
2
H_298K
H 2
+ 0.5O
⇌ H O
Δ
(8)
2
2
H_298K

Thepartialoxidationprocessformethaneisslightlyexothermic.Theprocessoccursinthegasphaseviaradical reactionwithintheflameoftheburner.Asmallexcessofoxygenisneededtofavoursomeoxidationtocarbondioxide

andwaterinordertobringupthetemperaturetothedesired1000­1200°C[3],unfortunatelythatproducescarbon

dioxideandwaterthatlowersthestoichiometricnumbertoabout1.6whichisbelowthepreferred2butanimprovement

oversteamreforming.

Alargecostforapartialoxidationplantistheairseparatorneededtoproduceoxygen.Whileitispossibletouseair

mostmodernplantsusepureoxygentoavoidtheneedofseparatingmainlynitrogenfromthesynthesisgasafterthe

oxidationstep.

1.1.2.3 Two­stepreforming

Acombinationofsteamreformingandpartialoxidationoffersameantoimprovetheoverallprocessandtobetter controlthecompositionoftheproducedsynthesisgas.Therightsystemconfigurationdependsonthecompositionof thenaturalgasusedasfeedstock.Twostepreformingalsorequiresthatthesteamreformingoperateswithhigh

methaneslip,usually35­45%,[1]toprovideahighenoughmethanecontentforthepartialoxidationstep.

Thetechniqueisfairlynewandwasfirstusedina2400MTPDcommercialplantinNorway2007anda5000MTPD

plantwithsimilartechnologyinSaudiArabia2008[1]

1.1.2.4 Dryreforming

Byreactingmethaneandcarbondioxidesynthesisgasisproducedinaprocesscalleddryreformingasnosteamis

used.

Dry reforming

CH

4

+ CO 2 2CO + 2H

2

ΔH

298K

= 59.1 kcal/mol

(9)

Thereactionismoreendothermicthansteamreformingandproducesagaswithsignificanthydrogendeficitfor

methanolsynthesis.Whilethisisadisadvantageformethanolsynthesisthegasmixturehastherightcompositionfor

otherapplications.

1.1.3 Synthesisgasfromcoal

Theprocesstoconvertcoaltosynthesisgasisacombinationofpartialoxidationandsteamtreatmentcalled

gasification.[2].

C + 0.5*O ⇌ CO ΔH (10) 2 298K C + H O ⇌ CO
C
+ 0.5*O
⇌ CO
ΔH
(10)
2
298K
C
+ H O ⇌ CO + H
ΔH
(11)
2
2
298K
CO + H O ⇌ CO
+ H
ΔH
298K
CO
ΔH
= ‐29.4 kcal/mol
=31.3 kcal/mol
= ‐9.8 kcal/mol
=40.8 kcal/mol
(12)
2
2
2
+ C ⇌ 2CO
(13)
2
298K

Thedesignandprocessingconditionsvarygreatlydependingonthecompositionofthecoalusedasfeedstock.The

synthesisgasproducedhaveadeficitofhydrogenandmustbesubjectedtothewatergasshiftreaction(equation12)

inimprovetheH/COratio.Thesynthesisgasproducedfromcoalisusuallyinhigherneedofpurificationthanthat

producedfromnaturalgas,especiallysulphurcompoundsmustberemovedbeforethemethanolsynthesistoprotect

thesensitivecatalystsfrompoisoning.

2

1.1.4 Biomass

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(≈10–25wt%),calledcharcoal.is

furtherreactedwithoxygenathightemperature(1300­1500°C)toproducemainlycarbonmonoxide.

Thesynthesisgasproducedfromthepyrolysisandcharcoalconversionispurifiedbeforethemethanolsynthesis.

Comparedtocoalbiomassconsistsofmuchlesssulphurbutthetarcontentoffersoperationalchallengesasit

condenseeasilyinpipes,filtersandboilers.Thiscantoanextentbecontrolledbychoosingtherightoperational

patternandtechniqueaccordingtothecompositionoftheavailablebiomass.Aonesteppartialoxidationprocessisan

attractivealternativebutthetechnicalchallengeshavesofarpreventedlargescaleoperation.

Productionfrombiomassispossibleatsmallscalebutaswithnaturalgasandcoallargescaleproductionispreferred duetothehighsystemcosts.Thelogisticalchallengesforabiomassplantarehowevergreatduetothelowerenergy contentinbiomasscomparedtonaturalgasandcoalimplyingalargedemandoffeedstockmaterial.Thequantities

neededtofeeda2500MTPDplantisestimatedto1.5milliontonbiomassperyear[2]withputlargestrainson

collection,transportationandstorageofbiomassandmightbeoneofthelargesthurdlestowardstheconstructionon

megasizedplants[7].

Analternativethathasbeenproposedtosolveoreasethetransportationdemandsistofirstconvertthebiomassto

bio­crudethroughfastpyrolysis.Driedandatomizedbiomassisquicklyheatedtoabout400­600°Cinatmospheric

pressureandthenquenchedtoavoidcracking[2].Theresultisablackliquidcalledbiocrudethatcanbetransported

moreeasily.

1.1.4.1 Blackliquorfrompulp

Blackliquorfromthepulpindustryhasbeenidentifiedasaninterestingfeedstockforrenewableenergy.Blackliquoris

formedaspulpwoodismixedwithchemicals(whiteliquor)toproducepulpasaprestagetopaperproduction.Black

liquorcanbegasifiedandusedformethanolsynthesis.Thechemicalsarerecoveredandreused.

Blackliquorisavailableinlargequantitiesworldwideandoffersafeasiblewaytoproducemethanol.Anindustrialscale

demonstrationplantattheSmurfitKappapapermillinPiteå,Swedenhasbeenoperationalsince2010producingDME.

1.2 Otherproductionmethods

Theproductionmethodofmethanolstandsbeforetwochallenges.Thefirstoneistomakethecurrentmethodsof

productionfromfossilfuelsmoreenergyandmoreenvironmentallyefficient.Whilethetwoisinterconnected,theyare

notnecessarilythesame.Energyefficientiseasilygraspedwhenrememberingthatthecurrentproductionmethods

requireasubstantialamountofheatwhichisusuallysuppliedbyburningaportionofthefeedstock.Withenvironmental

efficiencythatstandsmainlyforgreenhousegasemissions.Withnaturalgasresourcesstillvastachallengeisto

utilisethesebutatthesametimemitigatetheenvironmentalconsequences.

1.2.1 Carnolprocess

TheBrookhavenNationalLaboratoryhavedevelopedamethanetomethanolprocessthatideallydoesnotcontributeto CO emissionsbyusingcarboncapturetechniquesforthecarbondioxideneededforthemethanolsynthesis.The processreliesonthermaldecompositionofmethanethatproducethehydrogenneededforthemethanolsynthesis. Theotherproductissolidcoalwhichiseasytotakecareof.

2

Methanetherm.decomp.

Methanolsynthesis

OverallCarnol

Themainchallengefortheprocessistocapturecarbondioxideinaneconomicalwayandtopurify,concentrateand

transportittothemethanolplantinaneconomicalway.Fortheshorttermindustrieswithlargeconcentratedemissions

ismostlikelythepreferredroutebutcapturefromtheatmosphereisapossiblefutureroute.

Itshouldbenotedthatthermaldecompositionfrommethaneisanendothermicprocessthatrequireexternalheating.

Theneedisnotasgreatasforsteamanddryreformingandispreferablysuppliedfromrenewablesources.

Thecarnolprocessisstillonthedevelopmentstagebutcouldofferapossiblewaytostillusethenaturalgassources

thatisavailablewithminimalenvironmentaleffects.

1.2.2 Bi­reforming

BycombiningsteamreforminganddryreformingOlahet.al.[6]proposeamoreefficientwaytoproducesynthesisgas

fromnaturalgas.TheprocessproducessynthesisgaswiththerightH/COratio,calledmetgas,inasingleortwo­step

process.

2

Steamreforming

(4)[2]

Dryreforming

(9)

Bi­reforming

Thebigadvantagewithbi­reformingisthatthesynthesisgashastherightH2/COratioandthusallhydrogencanbe

usedformethanolproduction.Theprocessisthoughstillhighlyendothermicandrequiresasubstantialadditionof

heat.Thisheatispreferablysuppliedbyrenewableorevennuclearsources.

1.2.3 Directoxidationofmethanetomethanol

Anattractivealternativeforsynthesisofnaturalgastomethanolwouldbeiftheenergyconsumingstepofsynthesis

gascouldbeavoidablebydirectlyinsertinganoxygenatominthemethanemoleculebydirectoxidation.Thedifficulty

isthatthehighreactivityoftheproductsthemselveseasilyresultsincompletecombustionofthemethanetocarbon

dioxideandwater.

Despitethedesireofsuccessnomethodhasbeenfoundtoachieveahighenoughselectivity,productivityand

catalyststabilityforindustrialapplications[2].

1.2.4 CO +H

2

2

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 operatingoneplantonIcelandthatuseavailablegeothermalenergytoproduce5000m methanolperyear[9]and

MitsuiChemicalshasannouncedconstructionofademonstrationplantcapableofproducing100tonnemethanolper

yearfromCO.

3

2

1.3 Methanolpurification

Regardlessofthesynthesismethodthecrudemethanolproducedcontainsimpuritiestoasmallerorlargerdegree.The

largestimpurityisusuallywaterwhichcanbeasmuchas18%[10].Thefirststageinacommontwo­steppurification

processistoremovethelowboilingpurifications,typicallycalled“lightends”.Thisisdoneina“toppingcolumn”where

thelowboilingcompoundsareboiledofftoproduceamixtureofmethanolandwater.

Arefiningcolumnisusedtoseparatewaterandmethanolunderheavyboiling.Therefiningcolumnneedstobehighas

methanolandwaterisreluctanttoseparateeasily.Goodqualitymethanoleventuallyaccumulatesinthetopofthe

columnandistransferredtoastoragetank.Wateraccumulatesinthebottomandtakentoatreatmentfacilitybefore

disposal.

References

[1]

K.Aasberg‐Petersen,C.StubNielsen,I.Dybkjær,andJ.Perregaard,“LargeScaleMethanolProduc onfrom

NaturalGas,”2008.

[2]

G.A.Olah,A.Goeppert,andG.K.S.Prakash,BeyondOilandGas:TheMethanolEconomy,2nded.

Weinheim:Wiley‐VCHVerlagGmbH&Co.KGaA,2009.

[3]

J.‐P.Lange,“Methanolsynthesis:ashortreviewoftechnologyimprovements,”Catal.Today,vol.64,no.1–2,

pp.3–8,Jan.2001.

[4] K.C.Waugh,“MethanolSynthesis,”Catal.Le ers,vol.142,no.10,pp.1153–1166,Sep.2012.

[5]

K.Aasberg‐Petersen,I.Dybkjær,C.V.Ovesen,N.C.Schjødt,J.Sehested,andS.G.Thomsen,“Naturalgasto synthesisgas–Catalystsandcataly cprocesses,”J.Nat.GasSci.Eng.,vol.3,no.2,pp.423–459,May2011.

[6]

G.A.Olah,“TheRoleofCatalysisinReplacingOilbyRenewableMethanolUsingCarbondioxideCaptureand Recycling(CCR),”Catal.Le ers,vol.143,no.10,pp.983–987,Sep.2013.

[7]

L.BrombergandW.K.Cheng,“Methanolasanalterna vetransporta onfuelintheUS:Op onsfor sustainableand/orenergy‐securetransporta on,”Cambrige,2010.

[8]

G.A.Olah,G.K.S.Prakash,andA.Goeppert,“Anthropogenicchemicalcarboncycleforasustainable

future.,”J.Am.Chem.Soc.,vol.133,no.33,pp.12881–98,Aug.2011.

[9]

“CarbonRecyclingInterna onal.”[Online].Available:h p://www.carbonrecycling.is/.[Accessed:03‐Dec‐

2013].

[10] J.Jackson,“AMPCOMethanolProcessBasicDescrip on,”2006.

[11]

M.Funk,“MethanolFuelQualitySpecifica onStudyForProtonExchangeMembraneFuelCells,”Poway,

2002.

[12] T.Stenhede,“EffShipWP2:Presentandfuturemari mefuels,”Gothenburg,2013.

[13]

h p://gemfuel.com/newsblog/1370344337200/.[Accessed:05‐Dec‐2013].

[14] G.J.Suppes,“PastMistakesandFutureOpportuni esofEthanolInDiesel,”SAETech.Pap.840118,1984.

[15] B.Westman,“Ethanolfuelindieselenginesforenergyefficiency.”Scania,2005.

GEMFuel,“GEMFuellaunchedinFIAJuniorWRCinGreece,”2013.[Online].Available: