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AcrylicAcidProduction

AcrylicAcidProduction
viatheCatalyticPartialOxidationofPropylene
CENG403Project1:ReactorDesign

GroupFour:
ChristineLaskowski,ProjectLeader
MatthewHayenga
MiguelCastillo
October12,1998

Abstract|Introduction|ProposedDesign|CostAnalysis|Conclusions|References

Abstract
Acrylicacidisacommonlyused,yetextremelyvaluable,chemicalintermediateusedtoproduce
polymers,textiles,andnumerousotherindustrialandconsumerproducts.Becauseofthe
lucrativemarketforthisproduct,thisdesignprojectfocusesontheoptimizationofanacrylic
acidplant.Duetothesimplicityoftheinitialdesignoftheplant,thisoptimizationinvolved
moreinvestigationofnativereactionkineticcharacteristicsratherthanextrapiecesof
equipment.Byloweringthereactiontemperaturefrom310Cto190Cthethreereactionsin
competitionallowthedesiredproducttohaveitshighestconversion(94%versustheoriginal
69%),therebygeneratingmuchhigherprocessrevenue.Toaidinthisaggressivecoolingeffort,
amoltensaltstreamsimilartotheoriginalspecificationsshouldbesatisfactoryinforming
nearlyisothermalconditionsinsidethereactor.Beyondthis,ithasbeendeterminedthatthelast
5metersofthereactordonotproduceenoughacrylicacidtoovercometheoperatingandcapital
costsinvolved.Therefore,bydecreasingthereactorlengthby50%andloweringthe
temperature,thisoptimizedprocesshasthecapabilityofincreasingitsrevenueby37%overthe
olderdesignatrulycompetitivealternativetothecurrentdesign.

Introduction
Acrylicacidisacommonlyusedchemicalintermediate,whichbecauseofitswidespreaduses,is
avaluablechemicalcommodity.Becauseofthisfact,thisdesignprojectinveststheoptimization
ofanacrylicacidplant,toseeifsuchaplantcouldbeaprofitableundertaking.
Themostwidelyacceptedprocessformakingacrylicacidisthevaporphaseoxidationof
propylene.Thisisnormallydoneasastandardprocessinvolvingtworeactorsinseries,utilizing
twoseparatecatalysts.Inthisarrangement,thefirstreactorconvertsthepropylenetoacrolein
whilethesecondreactorcompletestheconversionfromacroleintoacrylicacid.Insteadof
utilizingthiscommonmethodforproduction,thisdesignprojectspecifiesaonereactorsystem
usingamoltensaltheattransfermediuminordertorelievethesystemoftheheatofreaction
produced.Whenimplementedproperly,theparabolictemperaturedistributionshouldresultin
approximately90%conversionofpropylene.
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Underasimplifiedarrangement,thereactiontooptimizeistheconversionofpropyleneto
acrylicacidthroughtheuseofacatalyzedreaction,givenby:
C3H6+1.5O2C3H4O2+H2O(1)
Thereare,however,acoupleofcompetingreactionsinvolved:
C3H6+2.5O2C2H4O2+CO2+H2O(2)
C3H6+4.5O23CO2+3H2O(3)
Thefirstcompetingreactionproducesasellablecommodity,aceticacid,whilethesecondonly
producespurgegases.Fortunately,kineticsarefavorableforthedesiredproduct,acrylicacid,
andthesecondaryproduct,aceticacid.
Eventhoughtheindustrystandardprocessinvolvestwoseriesreactorswithseparatecatalysts,
thesystemcanbemodeledasasinglereactorwithonecatalystasstatedearlier.Thisallowsfor
aneasiersolution,butcouldproduceartificiallylowcostnumbers.Also,becauseoftime
constraints,onlythereactorportionoftheplantwasstudiedindepth,leavingthequenchingand
separationsforalaterinvestigation.Here,again,therewillbesomeminorcostingassumptions
becausethefulldutyonequipmentdownstreamcannotbedetermined.
Followingaresomemoreintroductorytopicstoacquaintonewithotherconsiderationsbuiltinto
thisstudy.
Catalyst:
Aspreviouslymentionedthereactionsweareconsideringtakeplaceoverasingle
stagecatalyst.Whilenotinuseonanindustrialscale,suchacatalystforthisprocess
doesexist.Whilespecificsarenotwidelypublished,thecatalystconsistsof
polyvalentmetaloxides.Inparticular,molybdenumasacomponentandtelluriumas
anaidtoproductselectivitycanbeutilized.However,duetoactivitylossatahigher
rateintellurium,thisinnotfeasibleinlargescaleproduction.
Morecommonistheuseoftwoseparatecatalysts,onetopropeleachofthe
oxidationsteps:frompropylenetoacroleinandfromacroleintoacrylicacid.Based
ononearticle,thesecatalystscanlastinupwardsof3years,makingthemhighly
effectiveforplantuse.Inparticular,theoxidationofpropyleneactivatesovera
mixtureofmetallicoxides.TheseincludeMn2O3,V2O5,andMoO3ground
togetherandthencalcinatedathightemperatures.
Reactors:
Inthetrueprocess,therearetworeactorsinseries,eachwiththeirowntypeof
catalyst.Designofthereactorsthemselvesisheavilydictatedbytherequirementfor
theremovaloftheheatofreaction.Duetothis,thereactorsconsistofmanysmall
diametertubescarryingaheattransfermedium(usuallymoltensalt)surroundedby
thereactinggasphase.
Themoltensaltstreammostcommonlyusedconsistsof50%KNO3,43%NaNO2,
and7%NaNO3.Heattransferfluidswillbefurtherdiscussedlater.
Safety:
Sinceacrylicacidisextremelyreactive,specialattentionhastobepaidtoits
handlinganduse.Thespecifiedstoragetemperaturerangeisbetween59and77F
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atatmosphericpressure.Also,becauseofitsflammability,onlysparkresistanttools
shouldbeoperatedinitspresence.
Corrosionisalsoaconcernwhileusingacrylicacid,andanyprocessusingacrylic
acidshouldusetherecommendedmaterialsforvesselsandpiping(seeAppendix).
If,bychance,theseguidelinesarenotfollowed,theacrylicacidcouldgothrough
polymerization,releasingalargeamountofheat.
EndUses:
Acrylicacidschemicalnaturemakesitahighlydesirablecomponentinapolymer
system.Besidespolymerapplications,themoleculealsofollowsthecharacteristics
ofbothacarboxylicacidandacrylateester,makingitsuitableforchemical
intermediatesaswell.Thelargestapplicationforacrylicacidisintheindustrial
coatingsarea.And,becauseitismisciblewithwater,alcohols,andethers,the
wettingabilitycanbeenhancedbasedonthespecificemployment.
Anareaofgrowthforacrylicacidiswithacrylicacidhomopolymersandacrylic
acid/starchgrafts.Thesecombinationsprovideahighrateofabsorption,perfectfor
useinhygieneproducts.Otherminorusesincludeviscositymodifiersforrubber
latticesandadhesives,detergents,fibersizing,andsoilconditioners.

ProposedDesign
UsingthesimulationpackageAspen,ananalysisoftheacrylicacidprocesswasperformed.
Beforemodelingthesaltstreamcoolantsystemofthereactor,thisprojectfocusedmainlyon
establishingrealisticboundsofoperation.Thisinvolvedmodelingbothisothermalandadiabatic
reactorcases.
Fortheisothermalcase,severaldifferenttemperatureswereusedinordertoestablishanytrends
inthereactionrates.Fromisothermalplugflowtemperaturerunsthefollowinggraphwas
obtained:
Figure1

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Thetemperaturerangewaschosenbasedontheinletstreambeingcloseto190Candthe
upperboundforthereactionbeinglistedinpapersat400C.Clearlyfromthisgraph,the
productionofaceticacidisbetteratlowertemperatures.
Next,fortheadiabaticcase,thefollowingtableprovidesanoverviewoftheinletandproduct
stream:
Table1

AdiabaticCase,NormalPlugFlowReactor
Stream

Temperature(C)

25.0

159.0 25.0

1327.0

Pressure(bar)

1.0

6.0

3.5

11.5

MolarFlow(kmol/hr) 1362.9 992.3 127.0 2491.6

O2

280.9 0.0

0.0

0.0

N2

1056.7 0.0

0.0

1056.7

H2O

25.3

992.3 0.0

1202.3

CO2

0.0

0.0

0.0

156.5

C3H6

0.0

0.0

127.0 44.0

C2H4O2

0.0

0.0

0.0

3.9

C3H4O2

0.0

0.0

0.0

28.2

Bycomparingtheresultsoftheadiabaticcaseandisothermalcasewherethereactorisat310
C,ourrunincludingthemoltensaltcoolantcanbeexpectedtohaveanoutletmolarflowof
acrylicacidbetween28and100kmol/hr.
Nextinthesimulationprocedurewastodesignandimplementthemoltensaltstreamintothe
acrylicacidprocess.ThiswasarelativelydifficulttaskwithAspenandrequiredminor
variationsofthesamestepsinorderforittoacceptthedatacorrectly.ThePFDforthisprocess
lookslikethefollowing:
Figure2

Thisusesacountercurrentcoolantstreamvaryingintemperaturefrom200Cattheexitofthe
reactorto250Cattheentranceofthereactor.Forthefirstrun,themoltensaltwasplacedinto
thetubesystem.Thefollowingdatatabledescribesthestreaminformation:
Table2
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MoltenSaltCoolantCase
Stream

Temperature(C)

25.0

159.0 25.0

310.3

Pressure(bar)

1.0

6.0

3.5

11.5

MolarFlow(kmol/hr) 1362.9 992.3 127.0 2492.3

O2

280.9 0.0

0.0

0.0

N2

1056.7 0.0

0.0

1056.7

H2O

25.3

992.3 0.0

1202.5

CO2

0.0

0..0

0.0

157.2

C3H6

0.0

0.0

127.0 44.4

C2H4O2

0.0

0.0

0.0

3.9

C3H4O2

0.0

0.0

0.0

27.7

Asonecansee,thisdoesnotfallwithintheboundsfoundintheearlieranalysis.Soeventhough
thesaltstreamtemperaturesaroundthepumpandheatexchangerarecorrect(seeAppendix)
basedontheauthor'sdata,thisdoesnotprovidetheproperconversions.Furtherinvestigation
findsthatthetemperatureprofileforthisreactorisfarfromnormalandreachestemperatures
thatareunacceptablefortheprocessspecifications:
Figure3

Thepeaktemperaturereachesalmost1200C,whichallowsfortheunfavorablereaction(3)to
dominatewhilethedesiredproductconversionsuffers.Thisversionofthemoltensaltstream
simulationandothersfailtofallwithintheboundsofreason,butfortunatelyfromdataalready
seen,onecanfindamoreelegantwaytooptimizethisprocess.
FollowingtheisothermalrunsinFigure1,itisobviousthatoperatingtemperaturesbetween180
and200Carethemostselectiveforthedesiredreaction.Thisisrelativelyconvenientsince
thefeedstreamtemperatureisusuallybetween180190Csonootherheatingorcooling
sourceisnecessarytobringthereactantstothereactortemperature.Then,thedifficultycomes
withhowtoprovideanisothermalreactorwithoutspendinganexorbitantamountonthecoolant
stream.Luckily,becauseofthedecreasedreactortemperature,thecalculatedreactordutyis
roughly79GJ/hour.Versustheprovidedmoltenstreamoutputof83.4GJ/hour,weseethatitis
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bothplausibleandcosteffectivetooperateclosetoisothermalconditionsinthistemperature
range.Thisincreaseinconversiontoacrylicacidlowerstheconversionwiththesidereactions,
whichreleasethemajorityoftheheat.So,notonlyisthemoredesiredproductcreated,butthe
safetyconcernsregardingrunawayreactionsandcoolingdutyarealsolessened.Stream
informationforthisisprovidedbelow:
Table3

IsothermalCaseat194C
Stream

Temperature(C)

25.0

Pressure(bar)

1.0

159.0 25.0

182.8

194.0

6.0

5.0

4.3

11.5

MolarFlow(kmol/hr) 1362.9 992.3 127.0 2482.2 2421.9

O2

280.9 0.0

0.0

280.9

78.2

N2

1056.7 0.0

0.0

1056.7 1056.7

H2O

25.3

992.3 0.0

1017.6 1150.7

CO2

0.0

0.0

0.0

0.0

C3H6

0.0

0.0

127.0 127.0

0.2

C2H4O2

0.0

0.0

0.0

0.0

3.2

C3H4O2

0.0

0.0

0.0

0.0

120.5

12.6

Oneofthemainconcernsinanexothermicreactionwiththepossibilityofanexplosiverun
awayscenarioisheattransferinsidethesystem.Fortheaboveanalysisandoptimizationthe
requirementofasclosetoisothermalaspossiblehasbeenplacedonthecoolantsystem.And,as
found,theheatdutyonsuchasystemis79GJ/hour,whichisfeasiblesincethebasecasehada
coolantrequirementof83.4GJ/hour.Insidethecoolantloop,thecoolantmediumitselfrequires
someconsideration.Thetablebelowlistssomecommonheattransfermediums:
Table4

Fluid
Steam
DowthermA
DowthermE
Oil
MoltenSalts
Air

ValidTemperatures(C)
90590
230400
150260
0320
140540
01100

ValidPressures(psig)
04500
0145
072
0
0
0100

FromthiswecanseethatDowthermA,DowthermE,andoilareallsomewhatlackingeither
theydonotextendlowenoughforthereactiontemperature,ortheyvaporizeattemperaturesthat
couldexistinsidethereactor(i.e.hotspots).Airhasbyfarthebesttemperaturerange,however
itsheattransfercoefficientislowascomparedwithsteamormoltensalt.Moltensalthasthe
bestheattransferrate,butitscorrosiveeffectsanddangerofleakageintothesystemarenot
attractivefeatures.Steam,whilenothavingashighaheattransferrate,doeshavetheadvantage
thatifitleaksintothesystem,therewouldbenocostlycleanup,sincesteamactsasathermal
bufferinthefeedstreamtobeginwith.Furtherstudyintotheseissuesmightbeofconsiderable
help,butatthecurrenttime,sincethemoltensaltstreamhasthebestheattransferparameters,it
istherecommendedoption.
Now,workingwiththelowerreactiontemperatureasthebasecase,someotherimprovementsto
theprocessdesignfollowed.Varyingthestreampressuresandcompositiondidnotsignificantly
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changetheacrylicacidoutput.Ofcourse,changingthepropylenefeedwillgreatlyincreasethe
reactionrates,butduetosafetyconsiderations,thiswasnotadjusted.Thelargestalterationwe
foundinrespecttothefeedstreamswasthatthecompressedaircouldbebroughtinat4bar
insteadof5barwithoutloweringthereactionrates.However,thisdoesnottrulyaffectthecost
enoughtomakeupforthelackofadaptationtolaterprocessimprovements.Inconclusion,since
anyimprovementsvariationsinfeedcompositionandpressurewouldprovidewouldbesmall,
andthedataavailableonthesourcestreamforthesteamandpropyleneislimited,thesechanges
cannotbejustified.But,inthefuturethesecanbetreatedashandlesontheprocess.
Figure4

Finally,withthelowertemperaturesinmind,thereactordimensionswereinvestigatedinorder
todetermineifanyadjustmentscouldbemade.First,inchangingthediameterofthereactor,
andconsideringdutychanges,itwasfoundthatthediametercouldbedecreasedfrom3.6mto3
mwithoutaffectingeithertheacrylicacidoutputorheatduty.Asseeninthefigureabove,this
curvereachesaverydistinctplateauat3mreactordiameter.However,becausethereisnota
largedifferenceinthediameters,andtheheattransfertubeswouldhavetoundergomore
significantchanges,leavingthediameteratthegivenlengthof3.6misacceptable.Also,
becausewearetryingtoachieveanisothermalreactor,moreofthereactormustconsistofthe
heattransfertubesthanintheprovidedsystem.Byallowingthediametertoremainat3.6
meters,the"unnecessary"20%canbeusedforheattransfertubing.
Incontrast,reactorlengthprovidedamoredrasticreductioninreactorsize.Althoughthecurve
comparingtheacrylicacidoutandreactorlengthdoesnothaveasstrictofalevelingoffeffect
asthediameter,onecanclearlyseethatafterabout5to6meters,theadditionallengthdoesnot
payforitselfinproduct.
Figure5

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Therefore,thenecessarydeductioninreactorvolumeismadeentirelyinthelengthdimensionin
ordertoavoidaffectthefluidizedbedandheattransfertubes.
Thus,byprovidingadequatecoolingtokeepthereactiontemperaturetoroughly190C,the
reactorlengthdecreasesby50%whilestillprovidinganincreaseintheconversiontoacrylic
acidfrom69%to94%.

CostAnalysis
Asmentionedabove,mostoftheoptimizationofthisprocessresultsfrominnatepropertiesof
thesystem,notradicaldesignalterations.Therefore,whencomparingcostsoftheprocess
operationsandcapitalcosts,thefinalnumbersarenotasstrikingaswhentheoverallprofitis
viewed:
Table5

Cost
Labor
PropyleneFeed*
CoolingWaterElectricity
AirCompressorElectricity
SaltPumpElectricity
SteamfromBoiler
Total

BookProcess($)
246,000
11,948,000
107,000
1,085,000
16,000
946,000
14,348,000

OptimizedProcess($)
246,000
11,948,000
101,000
1,085,000
14,000
946,000
14,340,000

*costdatafromTurton,1993

Moresavingsisrealizedinthecapitalexpendituressummarizedbelow:
Table6

Equipment
Reactor(R301)
AirCompressor(C301A/B)
SaltPump(P301A/B)
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BookCase($)
2,262,000
33,000
121,000

OptimizedCase($)
1,504,000
33,000
121,000
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SaltHeatExchanger(E301)
TotalCapitalCost

62,000
2,478,000

62,000
1,720,000

Theabovesavingsof31%areduesolelytothereductioninreactorsize.
Afterthefirstyearofproduction(assuming8000hrs/yearofproductiontime)therevenuewill
bebasedinthesaleofthetwoproducts,acrylicacidandaceticacid.Comparisonoftherevenue
isprovidedbelow:
Table7

Revenue
AceticAcid*
AcrylicAcid*
Total

BookCase($)
2,113,000
79,490,000
81,603,000

OptimizedCase($)
1,051,000
109,901,000
111,454,000

*costdatafromTurton,1993

Asseenabove,thisprovidesonewitha37%increaseinrevenueascomparedwiththebooks
case,resultingina45%increaseinfirstyearprofitsforthissectionoftheplant(includescapital
costsandfirstyearoperations).However,sincethisonlylooksatthereactorportionofthe
process,trueprofitcannotbecalculatedatthistime.Also,thereareassumederrorsinsucha
coststudyhereitisroughly+30%to20%.

ConclusionsandRecommendations
Theoriginalsystemhasonefeatureinparticularthatisextremelydesirable:simplicity.By
addingfunctionalitytothissimplicity,webelievethisoptimizationschemeisthebestforthe
overallprocess.Byapplyingtheinherentfeaturesoftheparallelreactionseries,namely
loweringthereactortemperaturetotheneighborhoodof190C,theselectivityisincreased
whiletheheatofreactionisdecreased.Insummation,thefollowingchangeswillbebeneficial
aswellasprofitable:
Lowerthereactortemperaturetoroughly190C.
Providenearlyisothermalconditionswiththeexistingmoltensaltstreamdesign.
Reactorlengthcanbedecreasedto5mversustheoriginal10m.
Thesemodificationsresultinlowercapitalcostsaswellasamuchhigheroutletstreamof
acrylicacid.Inaddition,thereareacoupleotheradvantagestotheloweringofreaction
temperaturethatarealittlesubtler.First,becausethereactoroutletstreamleavesatalower
temperature,thequenchingareaoftheplant(whichdirectlyfollowsthereactor),willexperience
muchlessload.Secondly,thecatalystwillmostlikelymaintainisproductivitylongerthanthe
normal23years.Finally,duetothevolatilenatureofsomeofthecomponents,thesafetylevel
isgreaterwhenthereactiontemperatureislowered.Thesepoints,tonamejustafew,will
contributeadditionalsavingstotheprocessoverthelifetimeoftheplant.

References
Armeniades,C.D.PersonalInterview.
CelaneseChemicalCompany.ProductDescriptionforAcrylicAcid.1998.
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CelaneseChemicalCompany.ProductHandlingGuideforAcrylicAcid.1998.
McKetta,J.J.andW.C.Cunningham.EncyclopediaofChemicalProcessingandDesign.Ed.Vol.
1,402428,1976.
Turton,Richardet.al.Analysis,Synthesis,andDesignofChemicalProcesses.NewJersey:
PrenticeHall,1998.
Turton,Richard.Emailcorrespondence.
Ziolkowski,JacekandJanuszJanas."CatalyticPropertiesofDefectiveBranneriteType
Vanadates."InstituteofCatalysisandSurfaceChemistry.AcademicPress,1983.

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