SYNTHESISOFMETHYLMETHACRYLATEFROMCOALDERIVED

SYNGAS
MakarandR.Gogate1,JamesJ.Spivey1,JosephR.Zoeller2,RichardD.Colberg2,GeraldN.Choi
3,andSamuelS.Tam4
1

ResearchTriangleInstitute,P.O.Box12194,ResearchTrianglePark,NC2770921942Eastman
ChemicalCompany,P.O.Box1972,Kingsport,TN3766251503Bechtel,P.O.Box193965,San
Francisco,CA9411939654Bechtel,P.O.Box2166,Houston,TX772522166INTRODUCTION
Themostwidelypracticedcommercialtechnologyforthesynthesisofmethacrylicacid(MAA)
andmethylmethacrylate(MMA)istheacetonecyanohydrin(ACH)process.About6billion
poundsofMMAareproducedannually,correspondingtoroughly$4.5billioninsales.TheACH
processrequireshandlingoflargequantitiesofextremelytoxicandhazardoushydrogencyanide
andgeneratescopiousamountsofammoniumsulfatewasteswhichareeitherdiscardedor
reclaimedatsubstantialcost.TheACHtechnologyiscurrentlyenvironmentallyand
economicallyuntenableforanynewexpansions.Thereisastrongdrivewithinthechemical
industryforaprocessthatisbasedondomesticallyproducedcoalderivedsyngas(Gogateetal.,
1996;Spiveyetusingal.,CO1995a,generated1996).fromTheprocesscoal(Spiveyproposed
etal.,here1995a,(Figure1995b;1)isMcKetta,basedon1989).C2
=

hydrocarbonylation
Note:Thisprocess
consistsofthreesteps:Step1ethylenecarbonylation,Step2formaldehydecondensationofthe
Cknown3
producedart.StepsinStep1and1to2producepresenttechnicalMAA,andchallengesStep3
esterificationforsuccessfulofcommercialMAAtoMMA.demonstrationStep3is
andarethefocusofthisproject.
TheresearchonStep1isfocusedontwotasks:(1)developmentofahomogeneouscatalystfor
propionatesynthesis,and(2)preliminarydesignandeconomicanalysis.
Figure 1. RTI-Eastman-Bechtel three-step HOPr/MeOH-based MMA process (with external
formaldehyde feed).

1
Theresearchonthesecondstepalsoconsistsoftwotasks:(1)developmentofanacidbase
catalystforcondensationreaction,and(2)developmentofcombinedmethanolpartialoxidation
condensationcatalystforonestepMMAsynthesis.
RESULTSANDDISCUSSION
Step1.Ethylenecarbonylation.Althoughhomogeneouscatalystsforthisreactionarewell
known(Sameletal.,1993),commercialapplicationhasbeenlimitedtoahighlytoxicand
volatileNi(CO)catalystoperatingathighpressures(>180atm)andhightemperatures(>270C)
4(Bertleff,1986;Sameletal.,1993)toproducepropionicacid.Processesoperatingat
lowerpressuresandtemperaturesgenerallyrequireexpensivecatalystssuchasRh,Ir,orPdand
nonehavebeenemployedcommercially(Bertleff,1986;Colquhounetal.,1991;Forsteretal.,
1981,Mullen,1980;Pinoetal.,1977).AlthoughCrgroupmetalshavebeenusedincombination
withknowncarbonylationcatalystssuchasCo,Ni,Rh,andIr,theyhavenotbeenshowntohave
significantcatalyticactivityinisolation.Inthestudyreportedhere,ahalidestabilizedMo(CO)
6
homogeneouscatalystisusedat130to170ECand350to750psig.
TheresultsofbatchexperimentscomparingtheobservedorderofreactivityfortheGroup6
metalsshowsthatMo>>W>CrandthatthehalideemployedmaybeeitherBrorI.Substitution
ofbromineforiodineonlyleadstoasmallchange(25percentdecrease)inreactionrate,
suggestinganelectrontransferprocess(Huberetal.,1995).Whentheprocessisoperatedwitha
catalystcomposedofBuPI,Mo(CO),andEtI,the
46Mocatalyzedcarbonylationofethylenetopropionicanhydrideatanearlylinearratewith
time,untila75to85percentconversionofthepropionicacidisachieved,atwhichpointthe
reactionbeginstoslowmarkedly.AtypicalreactionprofileforthisprocessappearsinFigure2.
EffectofTemperature,DeterminationofActivationParameters.Theeffectoftemperaturewas
measuredinbatchexperimentsbetween130and170ECusingidenticallevelsofgasand
catalystcomponentsthroughoutthefullrangeoftemperatures.Theapparentactivationenergy(E
)was39.3
actkcal/mol.The
rateexpressionis:
Initial composition: EtI, 0.7 mol; EtCOOH, 7.5 mol; Mo(CO) , 22 mmol; Bu PI, 40 mmol. Conditions: 160
EC,

6 4 55 atm. Gas compositions: 5% H , 50% C H , 45% CO.

224

Figure 2. Reaction profile for the carbonylation of ethylene to propionic anhydride.

2
Theenthalpyofactivation()H)andentropyofactivation()S)weredeterminedfromthe
Eyeringplot:[ln(k/Tvs.(l/T)])Hwasfoundtobe+38.4kcal/moland)Swasestimatedtobe
+40cal/mol/K.Theseactivationparameterssuggestaratedeterminingstepinvolvingthe
dissociationoftheMoCObondinMo(CO)6
(EhlersandFrenking,1993,1994).
Step2Condensation.Thecondensationofformaldehydewithpropionicacidiscatalyzedby
acidbasecatalysts,asshowninFigure3(Gogateetal.,1997).
Thecatalystdevelopmentefforthasfocusedondevelopingastable,selective,andactive
condensationcatalystforthisreaction.Fixedbedmicroreactorstudiesofmorethan80potential
catalyticmaterialshaveshownthatGroupVmetals(V,Nb,andTa)areactivecondensation
catalystsandthatniobiumcatalystsarethemostactive.
Theresultsdeactivates.Ta/SiOstrength2
areshowTheshownlongtermthatintheFigure20deactivationpercent4.Thedeactivation
Nb/SiOofa2
10ispercenttheofmosttheseNb/SiOactivecatalysts2
catalyst.,VSiPhasbeenHowever,1:10:2.8,correlatedandthe10catalyst
withpercent
theanddistributionoftheacidandbasesitesonthecatalyst.Thereappearstobeanoptimum
balancebetweenthesesitesthatisnecessarytopromotethecondensationreaction.Figure5
showsthatanoxidativetreatmentofthedeactivatedcatalystpartiallyrestorestheactivity.Work
isunderwaytominimizedeactivation.
EconomicsoftheOverallProcess.AneconomicanalysiswascarriedoutbyEastmanand
Bechtelbasedontheresultsonthe20percentNb/SiO2
catalystat300C,2atm,flowratesof
opropionicacid:
formaldehyde:nitrogen72:16:200mmol/h,5gcatalystcharge(0.7to1.1mmsizefraction),and
avolumehourlyspacevelocityof1,080cm3/gcat@h.Reactionkineticsareassumedtobefirst
orderinformaldehyde.ThisprocesswascomparedtofivecommercialtechnologiesforMMA
manufacture:
ConventionalACHbasedprocess(Rohm&Haas),
(New)MitsubishiGasChemical(MGC)ACHbasedprocess,
ibutyleneoxidationprocess(Lucky,JapanMethacrylic),
tbutanoloxidationprocess(Kyodo,MitsubishiRayon),and
Propynecarbonylation(Shell,ICI).
k'
]1.17Rate@[P
co[Mo(CO)
6
]0.62[EtI]0.52[I&]

3
Figure 3. Representative mechanism for propionic acid and formaldehyde.

.
Acomparisonofcapitalcost,productioncost(orproductvalue),andthesensitivityofcapital
costandproductvaluetocapacitywascarriedoutbasedona250Mlb/yearplant(exceptforthe
propynecarbonylationprocess,forwhicha100Mlb/yearcapacityisassumedduetothevery
limitedworldwidesupplyofpropyne).Toaccountforcatalystdeactivation,theprocessdesign
includesparallelfixedbedreactors.
TheproductvaluecomparisonfortheRTIEastmanBechtelHOPr/MeOHroutewithfive
commercialroutes(Figure5)showsthattheRTIEastmanBechtelthreestepprocessat52/lb
MMAiscompetitivewithallcommercialtechnologiesforMMAmanufacture,exceptpropyne
carbonylation(at44/lb).[ThecurrentsellingpriceforMMAisroughly75/lb.]However,the
propynecarbonylationtechnologysuffersfromlimitedrawmaterialsupplyandisnotlikelyto
beacommercialtechnologyintheUnitedStates.BoththeconventionalACHandMGCACH
basedprocesses(at73/lband70/lbMMA,respectively)aremorecostlythantheRTI
EastmanBechtelthreestep
Figure 4. Long-term activity check on V-Si-P 1:10:2.8, 10% Ta-Si, and 10% Nb-Si catalysts.

Figure 5. MMA processes, product value comparison (10% ROI).

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route,asistheibutyleneoxidationroute(at59/lb).IntheUnitedStates,theibutylenerouteis
notlikelytobecommercialbecauseoftherawmaterialdemandsformethyltertbutylether
(MTBE)plants.tButanoloxidationprocessat55/lbMMAappearsquitecompetitivewiththe
RTIEastmanBechtelthreestepprocess.
AsensitivitystudycarriedoutbyEastman(Figure6)showsthatthegreatestuncertaintyisinthe
capitalcost.Thereactionrate(gMAA/kgcat@h),rawmaterialprice(formaldehyde,methanol,
andethylene)andMAAselectivityalsohaveapronouncedeffectontheMMAproductvalue.
Forexample,atanominalreactionrateof200gMAA/kgcat@h(correspondingtothatofthe
catalyst20percentNb/SiOcatalyst),the
2MMAproductvalueis58/lb;however,atareactionrateof3,300g
MAA/kgcat@h(assumingfirstorderreactioninpropionicacid,firstorderinformaldehyde,no
nitrogendiluent,PA/HCHO=1.5),theMMAproductvaluedecreasestoabout50/lb.Thus,
evenwiththecurrentunoptimizedcatalyst,theRTIEastmanBechtelthreestepprocessiscost
competitivewithallothercommercialtechnologiesforMMAmanufacture.Eventhoughthe
currentcatalystdoesdeactivate,thesensitivityoftheproductvaluetothenumberof
condensationreactors(1or2)isminimal.Tomaketheseeconomicassertionsmoresound,
knowledgegapsincludingcatalystdeactivation,intrinsicreactionkinetics,andformaldehyde
generationandrecoveryneedtobeaddressed.
FUTUREWORK
Longtermcatalystactivityeffectofvariouspromotersoncatalystlifewillbeexaminedand
possiblebeneficialeffectsofoxygencofeedandreactionregenerationcyclestomaintainthe
catalystactivitywillalsobestudied.
CatalyststructureThestructureoftheniobiumcatalystwillbestudiedingreaterdetailto
elucidatethedifferenceinphysicalandchemicalpropertiesofthefreshanddeactivated
catalysts.
IntrinsickineticsEastmanseconomicanalysisassumedafirstorderkineticsin
formaldehyde.Activationenergy,temperature,andconcentrationdependenceoftheMAA
reactionratewillbedetermined.TheMAAreactionrateisthesinglemostimportantparameter
affectingtheMMAproductvalue,basedonEastmansanalysis.
Figure 6. RTI-Eastman-Bechtel three-step HOPr/MeOH- based MMA process-sensitivity study.

5
CONCLUSIONS
ApreliminaryeconomicevaluationoftheRTIEastmanBechtelthreestepmethanolprocess
consistingofexternalformaldehydegeneration,condensationofformaldehydewithpropionic
acid,andexternalesterificationofresultingmethacrylicacidwithmethanoltoformMMA.The
resultsshowthatfora250Mlb/yrproductand10percentrateofreturnoninvestment,the
productvalueofRTIEastmanBechtelthreesteprouteisat52/lbandiscostcompetitivewith
alltechnologiesforMMAmanufacture,exceptpropynecarbonylation,whichsuffersfrom
limitedrawmaterialsupply.Furtherresearchoncondensationcatalysis,particularlyin
enhancingcatalystlongevityisunderway.
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