Shenyan

ngUniversityofChemicalTechnology

DEPART
TMENT OF CHEMIC
CAL ENGIINEERING
G
Projject On Prep
paration an
nd Applicatiion of Catallyst for One
e Step Oxida
ation Synthesis of
Acrylic A
Acid from PPropylene

S
Submitted B
By:

MD. MAHFU
UZUR RAHM
MAN SIDDIK
KY

IID: 12990214

SYUCT
T, Shenyang
g, China

014
JJanuary, 20

S
SUBMITTED TO TH
HE DEPARTMENT
T OF CHEM
MICAL EN
NGNEERIN
NG

Under tthe Superrvision of

Lecturerr,

MR. S
SHUANGM
MING LI

Dep
partment o
of Chemiccal Engine
eering

SYUCT
T, Liaoning, China

ShenyangUniversityofChemicalTechnology

APPROVAL SHEET

This dissertation has been submitted to all the respected members of the
Board of Examiners in the Faculty of Chemical Engineering in partial
fulfillment of the requirements for the degree of Bachelor Engineering in
Chemical Engineering on January 2014 by MD. MAHFUZUR RAHMAN SIDDIKY
and has been accepted as satisfactory.

....

LECTURER,

MR. SHUANGMING LI

Department of Chemical Engineering, SYUCT

ShenyangUniversityofChemicalTechnology

Abstract

Thisprojectdealswiththemanufactureofacrylicfrompropylenebytheoxidationofpropylene.Acrylic
acid is an important chemical raw material. Its derivatives acrylate has been widely used in paint,
chemicalfiber,textileandpetroleumproductsandotherindustries.Acrylicacidproductionmethodshas
experiencedwithethanolmethod,rip(REPPE)method,ketenemethod,propylenesunnyandpropylene
oxidation, hydrolysis method. The front four process has gradually be eliminated due to technical an
economicreasons.In1980s,aftertheconstructionandexpansionoftheacrylicdeviceusingpropylene
oxidationmethodusedintheindustrialproductionprocessisdividedintotwosteps:(1)propaneand
propylene oxide formation; (2) generate acrylic acid oxidation of propylene. Twostep preparation
processrequireslargeinvestmentinequipmentandenergywasteisseriousbutrelativetotheonestep
highyieldofacrylicacid.So,ifwecanimprovetheyieldofacrylicacidthatacryliclegalsystemappliedin
industrialproduction.Itcansimplifytheproductionprocessreduceequipmentinvestmentandenergy
wasteandbringhugeeconomicbenefits.Thispaperstudiesonacrylicprocessstepreactionsystem.By
changingvariablescatalyst,temperature,spacevelocity,water,oxygenwithpropyleneratio,waterwith
propylene ratio on the reaction summed up the propylene step reactions of acrylate and acrylic
maximum yield the best condition is obtained. Through the experimental study, when using
Mo1V0.17Te0.11Nb1.3B0.11Oxcatalyst, acrylic acidyield wasbiggest andthe bestprocess conditions under
thecatalystforthetemperatureabout420 ,propylenevelocityis3.8mL/(g.min),oxygenpropylene
ratiowas1.9:1,waterpropyleneratiois0.8~6:1orso.Inthiscondition,thepropyleneconversionis
58.51%andselectivityis67.14%ofacrylicacid.Acrylicacidyieldwas39.48%,theselectivityandyieldof
aceticacidwere7.44%and4.37%respectively.

A details process for producing acrylic acid, preparation of catalyst, reagent, equipment and craft
researchofpropylenetoacrylicacidhavebeendiscussed.

Keywords:Acrylicacid;Propylene;Conversion;Selectivity;Yield.

ShenyangUniversityofChemicalTechnology

Contents

Abstract.........................................................................................................................................................1
Introduction..................................................................................................................................................6
ChapterI........................................................................................................................................................8
LiteratureReview......................................................................................................................................8
1.1IntroductionofAcrylicAcid.................................................................................................................9
1.2PropertiesofAcrylicAcid....................................................................................................................9
1.2.1PhysicalPropertiesofAcrylicAcid...............................................................................................9
1.2.2ChemicalPropertiesofAcrylicAcid.............................................................................................9
1.3MethodforProducingAcrylicAcid.......................................................................................................10
1.3.1CyanideEthanolMethod...........................................................................................................10
1.3.2PropyleneMethod.....................................................................................................................10
1.3.3AcrylonitrileMethod...................................................................................................................10
1.3.4HighReppeMethod...................................................................................................................11
1.3.5ImprovedReppeMethod...........................................................................................................11
1.3.6Stoichiometry.............................................................................................................................11
1.4MethodforPurifyingAcrylicAcid.....................................................................................................11
1.5UsesofAcrylicAcid...........................................................................................................................13
1.6PropyleneOxide................................................................................................................................14
1.7PropyleneOxidationReactionMechanismofAcrylicAcid...............................................................15
1.8ProcessTechnology...........................................................................................................................15
1.8.1Japans(NSKK)Technology........................................................................................................16
1.8.2MitsubishiChemical(MCC)Technology....................................................................................16
1.8.3BASFTechnology........................................................................................................................16
1.9TechnicalProgress............................................................................................................................16
ChapterII.....................................................................................................................................................18
ExperimentalMethod.................................................................................................................................18
2.1ReagentandEquipment....................................................................................................................18
2.1.1Reagent......................................................................................................................................18
2.1.2Equipment..................................................................................................................................18
2.2PreparationOfCatalyst.....................................................................................................................18

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2.3.CatalystEvaluation...........................................................................................................................19
2.4.CatalyticOxidationMethod.............................................................................................................20
2.5CalculationMethod...........................................................................................................................20
ChapterIII....................................................................................................................................................21
ResultandDiscussion..................................................................................................................................21
3.1TheOptimumCatalystSelection.......................................................................................................21
3.2TheOptimumChoiceofReactionCondition....................................................................................24
3.2.1EffectofTemperature................................................................................................................24
3.2.2TheImpactofSpacevelocityofPropylene................................................................................26
3.2.3RatioofOxygen/Propylene........................................................................................................27
3.2.4RatioofWaterPropylene..........................................................................................................29
Conclusions.................................................................................................................................................32
Acknowledgement......................................................................................................................................33
Reference....................................................................................................................................................34

ShenyangUniversityofChemicalTechnology

Introduction

Acrylic acid is an important intermediates for the preparation of fibers, synthetic rubbers, synthetic
resins and so forth. It is actually produced by gas phase oxidation of propylene with ever greater
demand on propylene for processes other than the above (e.g. polypropylene) and ever high cost of
crude, the cost of propylene feed material is escalating quickly. Some twenty years ago, scientist at
Mitsubishi chemical company discovered MoVNb(Te,Sb)O based catalyst are very effective for the
conversion of propylene to acrylic acid. MoVTeNb oxide catalyst is most promising one. An
appropriate MoVTeNb metal ratio is critical to the formation of active phase according to the two
patents of Ushikubo and Lin. The catalyst with metal ratio of Mo1V0.17Te0.11Nb1.3B0.11 has excellent
catalytic performance for selective oxidation of propylene to acrylic acid. In this paper
Mo1V0.17Te0.11Nb1.3B0.11 was used as catalyst for propylene to acrylic acid. Each of the constituent
elements Mo, V, Te and Nb was shown to be necessary both high conversion of propylene and high
activity to acrylic acid. In addition the grain size of catalyst and their oxidation state of metals also
greatly affect their catalytic performance. Besides the intrinsic characteristics of catalyst the reaction
conditions are important factors influencing the catalytic performance and propylene oxidation. The
most promising catalyst is MoVTeNbO mixed metal oxide which is belonged to system that we
presented. It was developed by Mitsubishi Chemicals and can achieve around 50% of acrylic acid. An
alternative rout could be partial oxidation propylene as feed. The economic importance of possibility
and successful manufacture of acrylic acid by selective oxidation of propylene has stimulated various
researches. However for long period all efforts remind a futile and yield reported in the literature,
exceptinapatentfromMitsubishiweredesperatelylow.Inthelastyearsuseofmulticomponentoxide
catalystbasedonMolybdenum,Vanadium,Niobiumandtelluriumseemstoleadtomajorbreakthrough
and promising development. So far open literature is mainly restricted to the study of catalyst
preparation, its structure and comparison with catalytically active systems. The catalytic behavior of
these materials has been related to presence of two or more moieties which should correspond to
presenceofdifferentcrystallinephases.However,thepreparationmethodandcompositionofcatalyst
influence strongly both the nature of crystalline phase and catalytic performance. Although slurry
method is mainly used, hydrothermal synthesis has been recently proposed. Ueda and Oshihara
reported the catalytic behavior of propylene oxidation of MoVTeNbO catalyst prepared by
hydrothermalsynthesisusingTeO2asstartingcompound.Inthiscase,yieldofacrylicacid12.4%were
reported.Thedirectoxidationofpropylenetoacrylicacidusingmolecularoxygenareasanoxidantas
recentlyattractedgreatattentioninbothacademiaandindustry.ThemostpromisingcatalystisMoV
TeNbO mixed metal oxide, which belong to the system that we presented. It was developed by
Mitsubishichemicalandcanachievearound50%ofAcrylicAcidyield.Asignificantamountofworkhas
been recently reported about these oxide catalysts in both publications and patent applications,
showing how the preparation methods, the calcinations conditions or the presence of each element
seemedtobecrucialtoachievehighcatalyticperformance.MoVNbTeOhasbeenproposedasoneof
thebestcatalystsinbothammoxidationandselectiveoxidationofpropylenewiththeyieldtodesired
productnear50%.Mostcatalystsusedforeitheroneofmolybdateasamaincomponentortellurium
compounds as cocatalyst.Japanese touch media companies began to study some method process in
1960.In1970tobuildthefirstproductionplantandarevolutionarychangedtotwostep.Itisreported

ShenyangUniversityofChemicalTechnology

in 6070% of the intermediatestep acrolein to acrylic acid which is further reacted to CO, CO2, acetic
acid and formaldehyde.Because of different kinetic parameters are the respective processes at the
sametimetotakeonestepofoptimaloperatingconditionsinallprocesses.Furthermore,thecatalyst
containing tellurium oxide compound as a cocatalyst which during operation is gradually reduced to
metal and the metal under the reaction conditions showed a steam pressure.Lead to the loss of
tellurium due to the continuous change of the selective effect of diminishing or catalyst. Therefore,
thereisaonestepthatweaknessesbuttheworldisstillongoingscientificresearch.Thekeyliesisinthe
development of oxidation catalysts. So, this work should be sufficient attentionhow to research and
study of the rapid selection of the catalyst, I hope from the reactor analysis and testing the
instrumentation,automation,miniaturizationtomentionforhighresearchproductivity.Forcatalystlife
study,thefirsttofindoutthemainreasonforthecatalystdeactivation(suchascatalystsmorphological
changes,poisoningofactivesites,halfmelting,coke,etc.).Inordertoimprovetheefficiencyofthelife
test, hope response automation and computer software and hardware devices and further
development.Some reports from abroad to come and life accelerated test method has been widely
usedandhasmadesomeprogress.Chinaalsocarriedoutwork.Theselectivityofthereactionandthe
catalystshouldbebasedonthemechanismbyadjustingitscompositiontoinhibitsidereactionsthereby
improvedselectivity.Catalystisasuccessfullysmallpilotstudyintotheplantisstillnotsufficientthatwe
should design the reactor angle and largescale production of catalysts angle continue to study.
Therefore,researchanddesignpersonnelshouldcooperatecloselytoimprovethecatalystefficiencyis
veryimportant(i.e.)thatimproveprocesseconomicsandneedtoreducethepressurenearthereactor
andreducingcatalystlayerwithadjustofcocatalystreactorsize,shapeandtemperatureotherwisethe
resultcannotshowfullycatalystperformance.Researchsystemshouldpayattentiontotheuseofmild
temperature, pressure and other operating conditions areto save the cost of construction andpublic
workseffectively.

Shenyan
ngUniversityofChemicalTechnology

Chapter I
Lite
erature Re
eview
This chapter aims to o present a brief review w of the vario
ous routes tthat have beeen used to synthesize
acrylic acid. In doingg so it takes a historical perspective of the industrially impoortant processses as the
methodsswhichneveersawtheligghtofthedayindustriallyy.Theprimeobjectiveis tohowever surveythe
workthaathasbeen donepertineenttothepresentfield ofinvestigattionthatistthecatalyzed dMoVTe
NbOaqueousphaseeoxidationoffpropylenettoacrylicacid d.

1.1 Inttroduction
n of Acrylic Acid
Acrylic aacid is an o
organic comp pound with the formulaa CH2CHCO2H. It is the simplest unsaturated
carboxylicacidconsistingofavin nylgroupcon nnecteddirectlytoacarb boxylicacidtterminus.Thiscolorless
liquidhaas acharacteeristic acrido ortart smell.Acrylic acid dis ausefulcompound becausepollymersand
copolymmersthereof areusedforrhighwaterabsorbingm materials,paints,adhesives,fibers,an ndthelike.
When aacrylic acid is producced though polymerizaation
inhibitorr is usedsincceacrylicaciid has a high h polymerizaation
propertyy that acrylicc acid polymmer is still forrmed. When the
polymerexistsinacrrylicacid,itsseemsthataacrylicacidteends
to polymerize morre easily. Further,
F when acrylic acid
polymer accumulatees, the interrruptionof th he process m
might
becauseedbyblockin ngtheprodu ucinglinewitththepolym mers.
Moreoveer, the polym mer influencces the puritty of acrylic acid
after puurification an nd it will b
be necessaryy to repeat the
purifyingg operation many times. Accordinggly, in order to
carry ou
ut the efficieent purification and con nsequently thhe productioon of acrylicc acid. It is needed to
excludeacrylicacidp polymersinccrudeacrylicacidasmuchaspossiblee.Itismisciblewithwater,alcohols,
ethersandchloroforrm.Morethaanonebillion nkilogramsaareproduced dannually.Itispolymerizzedtoform
polyacryylicacid.

Themoleecularstructtureofacryliccacidandesstersareasfo
ollow:

Acrylic aacid is produ

uced in very large amounts (1.1 billion pounds iin 1991) by four compannies in the
UnitedSStates.USdeemandforaccrylicacidis increasingatarateof4 4to5percen ntperyear.TThelargest
users of acrylic acid arecompan nies thatmakke acrylic estersandressins, chemicaals addedto protective
surface coatings and d adhesives. The fastest growing use of acrylic acid is in th
he production of super
absorben ntpolyacrylicacidpolymmers.Compaaniesalsouseeacrylicacid dtomakeoiiltreatment chemicals,
detergen ntintermediaatesandwattertreatmen ntchemicals.

ShenyangUniversityofChemicalTechnology

1.2 Properties of Acrylic Acid

1.2.1 Physical Properties of Acrylic Acid

Acrylicacidiscolorlessliquidwithanirritatingacrideodoratroomtemperatureandpressure.Itsodor
threshold is low (0.203.14 mg/m3). It is miscible in water and most organic solvents. Acrylic acid is
commerciallyavailableintwogrades:technicalgrade(94%)foresterificationandglacicalgrade(9899.5%
byweightandamaximumof0.3%waterbyweight)fortheproductionofwatersolubleresins.Acrylic
acidpolymerizeseasilywhenexposedtoheat,lightormetalsandsoapolymerizationinhibitorisadded
to commercial acrylic acid to prevent the exothermic polymerization. The inhibitor that are used in
acrylicacidpreparationsareasfollowing

Monomethyletherofhydroquinone(methoxyphenol)at200=20ppm
Phenolthiazineat0.1%
Hydroquinoneat0.1%
Methyleneblueat0.51.0%
N,Ndiphenylpphenylenediaminat0.05%canalsobeused

Acrylic acid reacts readily with free radicals and electrophilic or nucleophilic agents. It may
polymerize in the presence of acids (sulfuric acid, chlorosulfonic acid), alkalis (ammonium
hydroxide), amines (ethylenediamine, ethyleneimine,2aminoethanol), iron salts, elevated
temperature, light, peroxides, and other compounds that form peroxides or free radicals. In the
absenceofinhibitor,peroxidesareformedwhenoxygenisspargedintoacrylicacid..Thepresence
ofoxygenisrequiredforthestabilizerto functioneffectively.Acrylicacidmustneverbehandled
under an inert atmosphere. Freezing of acrylic acid occurs at 13C. Rethawing under inappropriate
temperature conditions is another frequent reason for acrylic acid polymerization. Acrylic acid is a
strong corrosive agent to many metals, such as unalloyed steel, copper and brass.

Table1.1NatureofAcrylicAcid

Molecular Freezing Boiling Flashpoint Relative Refractive Specificheat

Project
weight point point (opencup) density index capacity

Acrylic
72.06 13.5 141.5 54.5 1.052 1.4185 1.9J/(g )
acid(AA)

1.2.2 Chemical Properties of Acrylic Acid

Acrylic acid undergo reaction characteristics of both unsaturated acids and aliphatic carbolic acids or
esters.Thehighreactivityofthesecompoundsstemsfromthetwounsaturatedcenterssituatedinthe
conjugatedposition. Thecarbonatom,polarizedbycarbonylgroup,behavesasanelectrophile;
thisfovourtheadditionoflargevarietyofnucleophilesandactivehydrogencompoundstothevinyl
group. Moreover, the carboncarbon double bond undergoes radicalinitiated addition reactions,
DielsAlderreactionswithdienes,andpolymerizationreactions.Thecarboxylfunctionissubjectto

ShenyangUniversityofChemicalTechnology

the displacement reactions typical of aliphatic acids and esters, such as esterification and
transesterification.Joint reactions of the vinyl and carboxyl functions, especially with bifunctional
reagents,oftenconstituteconvenientroutetopolycyclicandheterocyclicsubstances.Acrylicacids
polymeriseveryeasily.Thepolymerizationiscatalysedbyheat,light,andperoxidesandinhibitedby
stabilizers, such as monomethyle ether of hydroquinone or hydroquinone itself. These phenolic
inhibiters are effective only in the presence of oxygen. The highly exothermic, spontaneous
polymerizationofacrylicacidisextremelyviolent.

1.3 Method for Producing Acrylic Acid

Acrylicacidhascurrentlybeenproducedbycatalyticvaporphaseoxidationofpropyleneand/oracrolein
in the industrial scale. Since catalytic oxidation is conducted with a solid catalyst in the presence of
molecular state oxygen and water vapor, the oxidation product is usually obtained in the form of an
acrylicacidcontainingaqueoussolution.Theacrylicacidcontainingaqueoussolutioncontainsmanyby
products other than acrylic acid such as acetic acid, formic acid, formaldehyde, furfural, acrolein,
acetaldehyde, propionic acid, maleic acid, Benz aldehyde, protoanemonin and the like.As the method
forremovingwaterfromtheacrylicacidcontainingaqueoussolution,thefollowingmethodshavebeen
known.

1.3.1 Cyanide Ethanol Method

Cyanide ethanol is the industrial production of dry acrylic acid and esters. Germany and the U.S,
respectivelyin1927and1931builtusingthistechnologyinindustriallevel.Sincethereactionprocess
willgenerateavarietyof polymers, acrylicsoclosetolowrate ofonly60%70%andthehighlytoxic
cyanidecausesseriouspollutionoftheenvironmentsotheuseofthismethodofproduction.

1.3.2 Propylene Method

Thisrecentlydevelopedprocessinvolvestheoxidationofpropylenetohydroxypropionicacid.Oxidesof
nitrogenornitricacidactascatalystforthereaction.Subsequently,dehydrationyieldsacrylicacid.The
stepwiserepresentationcanbeshownasfollows:

CH3CH=CH2 + 3/2 O2CH3CHOHCOOHCH2=CHCOOH + H2O

An alternative route is the catalytic oxidation to acrolein, CH2CHCHO and then to acrylic acid with
oxygenandcertainmetalliccatalystsuchasMo, Co or Ce.

1.3.3Acrylonitrile Method
Caremustbeexercisedinthisacidhydrolysissinceboththestartingacrylonitrileandtheproductacrylic
acidarepolymerizable.Theacrylonitrileshouldremaininthereactionzoneandmustbewellinhibited.
Amajoradvantageofthismethodistheincreaseinmolecularweightonhydrolysisfrom53to72which
providesadefiniteyieldimprovement.

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Shenyan
ngUniversityofChemicalTechnology

2CH2= CHC
CN + H2SO4 +
+ 4H2O2CH
H2=CHCOOH
H + (NH4)2SO
O4

1.3.4 H
High Rep
ppe Metho
od
In the eearly 1930s, Germany W Wafer Reppe Bo ten foun nd using hiss invention R Reppe reactiion can be
directly acetylene production frrom acrylic aacid and acrylic esters. In the meth hod acetylen ne, carbon
monoxid de and wateer as raw material
m when the reactiion temperaature was 15 50 and thhe reaction
pressureewas1.523..04Mpa.Nickkelactasaccatalystwith alightliquid dphasereacctionofacrylicacidand
its esters. Due to temperaturre, pressuree, the reacttion is slow w and nickeel carbonyl (BP 43C)
decompo osition and volatilizationn loss seriouusly. Acetylene and acryylic acid (esteer) polymer can easily
cause daanger. To this end the G German company BASF aand Badischee make this improvemen nt of using
tetrahyd mide, copper bromide promoter at 200 and
drofuran as aa solvent usee as catalystt nickel brom
pressureeof14MPa.A Acrylicacidinnayieldofaacetylene90rr/cforayield dof85%carb bonmonoxid deproduce
methyl o or ethyl acryylate with an
n ion exchannge are resin n as the cataalyst for prod
ducing acryliic acid and
butylestterwiththe abovecarbo onofcontinu uousesterificcation.Althoughthenew wdeviceshavveadopted
BASFpro opyleneoxidationmethodbutthismeethodofindustrialequip pmenthomeisstillrunnin ng.

1.3.5 IImproved
d Reppe M
Method
In1948, Rohm&HaasandToaC Coseichemicaalcompany usedthismeethodandhaasbeenimprovedwith
onlyasmmallamountofcarbonyl.Nickelandccarbonmono oxiderequireedforthereactiondoesnotrelyon
humanp parttoprovideacarbonyylgroup.Thiismethodis commonlykknownasmo odifiedRepp pemethod.
By the 1
1960s, with the Reppe method or improved
i prroduction off acrylic acid
d and its estters Reppe
process was domin nant with petrochemic
p cal technolo
ogy development and the strengtthening of
environm mentalproteectionrequireementsimprrovedReppe method.

1.3.6 S
Stoichiom
metry
Thereacctionofacetyyleneasarawmaterial,aacidandnickkelcarbonylinthepresen nceofnormaalpressure
at40 ccarryouttheereaction:4C2H2+4ROH +2HCl+Ni(C CO)44CH2= CHCOOR+N NiCl2+H2Wh hereinRis
hydrogen,alkylorarrylgroup.Sinncereleaseooffreehydroogenwithaccrylicacidorrestersmay befurther
reacted byproducts up to 20% and separating trapped difficult low
w yield requirred for the rreaction of
carbonm monoxidepro ovidebynickkelcarbonyl.Nickelcarboonylishighccost,toxicsothatthepro ocessroute
isfarfromideal.

1.4 Me
ethod for Purifying
g Acrylic A
Acid
Acrylicacidhasapro opertyofeassilypolymeriizingbythe actionofheaat,light,peroxides,impu
uritiessuch
asaldehydesandso on,alargeaamountofpo olymersisprroduced
when the acrylic acidcontain ning aqueou us solution which
containssmanybyprroductsissubjectedtod dehydrationtthrough
azeotrop pic distillatio
on by feeding directly to an azeeotropic
dehydrattioncolumn.Itisknown thatthesep polymerscau usesnot
only deccrease in heaattransfer performance
p by adheringg ontoa
heat surface of a reboiler for distillationn column but
b also
blockadee of a disttillation colu umn leadingg to the situation

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Shenyan
ngUniversityofChemicalTechnology

includinggunwilledstopofoperattion.Therefo ore,preventio onofthepollymerizationisveryimpo ortantfrom

theindu ustrialviewpo ointasameeansforprevventingpolym merizationo ofacrylicacidd,ithasconvventionally
beenpro oposedand conductedttoaddpolym merizationinhibitorstotheacrylic accidcontainin ngsolution.
As repreesentative po olymerization inhibitors are known phenols succh as hydroq quinone, hyd droquinone
monomeethyletheraandthelike,aaminessuchasphenothiiazine,dipheenylaminean ndthelike,co oppersalts
such as copper dibutyldithiocarb bamate and the like, maanganese saltts such as mmanganese acetate and
the like, nitro compounds, nitro ous compoun nds and so o
on. These poolymerization n inhibitors have been
usedindependentlyo orincombin nationwithth hemselvesorrincombinationwitham molecularstaateoxygen
containin ng gas. In addition,
a since the presence of imp purities suchh as aldehyddes has receently been
deemed tobeaprob blemintheccaseofprodu ucingawateerabsorptiveresinandapolymericco oagulantin
which thhe polymerizzation of acrrylic acid is affected greeatly by impu
urities, theree have beenn proposed
methodssforpurifyingacrylicacid dasfollows.

Figgure1.1Metthodforpuriifyingacrylicacid

(1)Ameethodforpurrifyingacryliccacidinwhicchanaromatticamine,an
naliphaticam
mine,oranottheramine
suchasaanamide,an nimine,aniimide,apolyyamineorthhelikeisadddedtoacruddealdehydecontaining
acrylicaccidandthem
mixtureisdisstilledtorem
movealdehyd
desfromacryylicacid.

(2)Ameethodforpreeventingpolyymerizationo ofacrylicacidand/oram
methodford
decomposinggaldehydes
containeedinacrylicaacidinwhich
hatleastoneecompoundselectedfrom mthegroupconsistingofammonia,
methylamine, ethylaamine, dim eethylamine, diethylamide and salts thereof are added to aacrylic acid
obtaineddbycatalyticcvaporphaseeoxidationo ofpropylene and/oracrolein.

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ShenyangUniversityofChemicalTechnology

(3)Amethodforpurifyingacrylicacidinwhichacrylicacidobtainedbycatalyticvaporphaseoxidation
ofpropyleneand/oracroleinistreatedwithamolecularsievehavinganadsorbedhydrazinecompound
oranaminecompoundtodecomposeandremovealdehydescontainedinacrylicacid.

(4)Amethodforpurifyingacrylicacidinwhichaprimaryamineand/orasaltthereofand,inaddition,at
leastoneorganicsulfonicacidand/orasaltthereofareaddedtoacrylicacidcontainingaldehydes,and
acrylicacidisseparatedfromthemixturebydistillation.

(5) A method for producing acrylic acid in which, in the evaporative purification of acrylic acid with
additionofadealdehydeagentafterazeotropicdehydrationofanoxidationproductcontainingacrylic
acid obtained by catalytic vapor phase oxidation of propylene and/or acrolein, at least one amine
selected from aliphatic amines, heterocyclic amines and aromatic monoamines and a aldehyde agent
areaddedtothesolutionafterazeotropicdehydration.

1.5 Uses of Acrylic Acid

Acrylic acid has traditionally been used as the raw material for acrylic esters, methyl acrylate, ethyl
acrylate,butylacrylateand2ethylhexylacrylate.Thesebulkacrylateswereoriginallyusedtoproduce
solventbased acrylic resins but environmental concerns over solvent use led to the development of
waterbased acrylics. Applications for waterbased acrylics are primarily in decorative, masonry and
industrialcoatingsbutotherusesincludeadhesives,paperandleathercoatings,polishes,carpetbacking
compounds and tablet coatings. Acrylic acid is used for the manufacture of polyacrylates which are
usedasthickeners,dispersantsandtheologycontrollers.Acrylicacidisalsoemployedasacomonomer
with acrylamide in anionic polyacrylamide and to produce hydroxyl acrylates for using in industrial
coatingformulations.Fromthemid1980s,twonewapplicationssuperabsorbentpolymers(SAPs)and
detergentpolymershaveemerged.SAPsarecrosslinkedpolyacrylateswiththeabilitytoabsorband
retain more than 100 times their own weight in liquid. They have experienced very strong growth,
primarily in baby diapers (nappies), although the US and West European markets have now matured.
SAPsaccountforover30%ofworldacrylicacidconsumption.

(1)Paint and Varnish

Acrylicpaintproductsareconsumedthelargestuseroftheproduct.About30%oftheworldiswitha
seriesofacrylicmonomers.Inthepaint,acrylicresinasaseriesoffilmformingcoatingmaterialcanbe
preparedbyanemulsionpolymerlatexandthepolymersolutioncanbeusedasindustrialpaint.

(2)Chemical Fiber and Textile Processing

Thetextileindustryisthesecondconsumelargeacrylicproductsforabout25%ofacrylicfabric.InChina,
the textile industry is the largest user of acrylic products.Acrylic acid copolymer is having excellent
properties that synthesizes the number of fibers and used as a comonomer and copolymers.Methyl
acrylatemonomeristhesecondpolymerizationofacrylicfibers.Acrylicacidsyntheticestersmayalsobe
usedasaprocessingaid.

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ShenyangUniversityofChemicalTechnology

(3) Leather Processing

Inlightleathertanningwatersolubleacrylicresinseriesisagoodassistanttanningagent.Acrylicresin
emulsionlightisusedtofillandfinishleatheracrylateafterprocessing,excellenttextureandsoftness,
morebeautifulcolorutilizationcanbegreatlyimproved.

(4)Paper Processing
Inthepaperprocessingindustry,anemulsiontypeacrylicbasedresinusedasbinderthesurfaceofthe
coated paper greaseproof paper coating that impregnating the paper can also be used to increase
strength.

(5) Adhesives
Emulsion,solutiontype,powdertypeandsolventtypeacrylicbasedresincoatingliquidinavarietyof
plasticfilm,paper,nonwovenfabric,metalfoil,canbemadeofpressuresensitiveadhesiveproducts.It
isimportantpackagingmaterials.

(6)Synthetic Rubber
Ethylacrylateorbutylacrylateacrylicrubberasthemainrawmaterialisspecialsyntheticrubberwith
excellent performance. Adhesive with excellent heat resistance and oil resistance are with the
temperatureupto170~180 .

(7) Plastic
Acrylateusedasplasticizersintheplasticsindustrycangreatlyimprovetheperformanceofplastics.

1.6 Propylene Oxide

Thelate1960s,withtherapiddevelopmentoftheworldpetrochemical,propylenepricesarebecoming
cheaperduetothehighlyreactive,highlyselectiveandlonglifecatalystdevelopmentmakingthedirect
oxidationofpropylene to acrylic acidindustrializedmethodsforindustrial level.Afterthe1980s,new
andexpandedacrylicdevicesareusingatwostepoxidationofpropylene.Twostepoxidationmethod
comprisingafirststepfortheoxidationofpropylenetoacroleinandthesecondsteptoacrylicacidis
furtheroxidizedtoacrole.

Themainreactionstep:CH2CHCH3 + O2 CH2CHCHO + H2O

Thesubstepreaction:CH2CHCHO +0.5 O2 CH2CHCOOH

2CH2CHCH3 +7.5 O2 3CO2 +3CO +6 H2O

CH2CHCH3 +2.5 O2 CH3COOH +3CO2 + H2O

Thesecondstepofthemainreactionis:CH2CHCHO +0.5 O2 CH2CHCOOH

Thesecondstepofthesideeffectsis:2CH2CHCHO +5.5 O2 3CO2 +3CO +4 H2O

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Shenyan
ngUniversityofChemicalTechnology

4CH2C CHCHO +2 H H2O + O2 44CH2O + CH3CHO

Oxidationof propyleeneto acrylicc acidisthemainbyprooductwhich istheformaationof acetic acid,CO
andCO2.Industrialu
useoftwosttepreaction helpcatalystcompositio onandtheoptimizationo ofreaction
conditionstoimprovveselectivityyoftheoxidaationreactionofpropylene.Thefirst setofpropyyleneoxide
raw producing devicce consists o
of UCC Com mpany was fo
ounded in the United SStates, Japan
n since the
catalystMitsubishiChemical,BASSFandothercompaniesh havebuiltind
dustrialequipmentposition.

1.7 Pro
opylene O
Oxidation Reaction Mechanissm of Acry
ylic Acid
Mamoru
uAiproposed
dthefollowingreactionm
mechanism:

Oxidationpathways ofpropyleneeoxidationo overaMoVTeNbOcattalystwasreecentlypropo osed.With
the exceeption of 2ppropanol, thee existence o of all other partial oxidaation produccts is supporrted by the
experimeentalfindinggs.Inthisview w,propaneispartiallyoxxidizedtoacrrylicacidwithmolecularoxygenvia
propylen neandacroleeinasinterm mediates.Oxidativedehyd drogenationofpropanettopropyleneeandallylic
oxidation nofpropylenearethetw wokeystepsswhichdeterminetheseelectivitytoaacrylicacid.O Otherthan
carbon ooxides, acetiic acid is the major byproduct, wh hich is formeed mostly th hrough an u undesirable
pathwayywithaceton neasinterm mediate.Furtheroxidation nofacrylicaacidandund desirableimp pactingthe
selectivitty to acrylic acid. In add
dition, the d
direct CC brreakage of acrolein
a or p
propylene to C1 and C2
moleculeeswithoutggoingthrough hacrylicaciddmayalsoco ompetewith htheselectivvitytoacrylicacid.The
majorpaathwayfrompropaneto acrylicacid overthisMo oVTeNbO catalystissiimilartothattproposed
over thee Te/VPO syystem. Howeever, this type of similarity may no ot always hoold. Recentlyy, different
propanee oxidation p pathways, as shown in Fiig. 9, were p proposed forr Mo1:51Ni1Tee0:01P0:02Ox m mixed oxide
catalyst. Over this catalyst, direct oxidation of propylen ne to CH3CHO O or COx waas proposed. Aldehyde
intermed diateswere observedexperimentallyyintheprod ductstreamw whileacetic acidwasnottdetected.
ThesediifferencesbeetweentheTTeP/NiMoO OandMoV VTeNbOcatalystscould dbeattributedtoboth
chemical and structu ural differences of the ccatalyst systeems involved d, despite the fact that m
major path
from proopane to accrylic acid co ontains the ccommon intermediates propylene and acrolein. Here, the
competittion among the desirab ble and undeesirable path hways could d dictate thee product distribution,
while the catalytic aactivity, whicch is indepen ndent of thee product disstribution, could greatly affect the
performance..
overallp

1.8 Pro
ocess Technology
Oxidation of propylene to acryylic acid pro ocess technoology makes high performance cataalyst. Early
oxidationn of propyleene to acrolein remindeers agent is copper oxid de catalysts and MoBi was soon
replacedd by the catalyst. In 195
57 U.S. Sohio Corporatio
on, the first successful d developmentt of MoBi
basedcaatalystsafterralongreseearchdevelop pmenthasb beenformedtoMo,Bi,FFe,Co,Ni,M Mn,Mgand
other multimetal oxxide catalystt system. Mo oBi based catalyst is ccharacterizedd by acrylic aacid which
completedconversio onwithtimeeandselectivvityisgood morethan9 90%theyield dofacrolein nsincethis
catalyst propyleneco onversionraatewithoutp propylenegaascirculation nsothattheeproductionprocessis
widelyusediintheindustry.
shorterw

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ShenyangUniversityofChemicalTechnology

1.8.1 Japans (NSKK) Technology

JapanCatalysis(NSKK)Technologyisusedinoxidationofpropylenetoacroleinprocessischaracterized
by the MoBi catalyst added elements Co thereby increasing the selectivity and onepass yield of
acrolein. Process superposed mainly by the fixed bed reactor column separation system Composition
andacrylicacidyieldrangefrom83%to86%(mol).

1.8.2 Mitsubishi Chemical (MCC) Technology

The process characterized by high concentrations of propylene as raw material that onepass yield
above87%acrylicacidofunreactedcatalyst.Alkenyloracroleinisnotrecycled.Twofixedbedreactors
inserieswereusedasMoBibasedandMoVbasedoxide.Materialsactascatalystlifewas6yearsand
acrylicacidseparationprocessusethreetowerprocesses.

1.8.3 BASF Technology

BASF'sacrylicacidproductionplantistheworld'ssinglelargestseriesofdevices.Itstechnologyadopted
with a fixedbed twostep oxidation. Propylene oxide with MoBi based or MoCo catalyst single pass
yieldofacroleinwas80%orso.FurthercatalyticoxidationofacroleinwithMo,W,V,Fecatalystpasses
the yield greater with a highboiling organic solvent as the suction than 90% (Molar Absorbent;
oxidationreactionofpropyleneintherecyclegaswithoutwatervapor).Itstechnicalcharacteristicsare
propyleneoxidationreactiongasdoesnotabsorbwaterbutnitrogenreducesthegenerationofwaste
acid.Thepurificationofthefivemaintowercompletedthatacrylicacidesterificationreactioniscarried
out without a mixer device. Enoic acid methyl ester and ethyl does esterification catalyst without ion
exchangeresinbutsulfuricacid.Propyleneoxidationtoacrylicacidunitfixedconsumptioncomparedin
Table1.2.

Table1.2PropyleneoxidationtoAcrylicacidunitconsumptionquotacomparison

Name JapanCatalysis(NSSK) JapansMitsubishiChemical(MCC) BASF

Propylene(100%),t/t 0.680 0.676 0.72

Coolingwater,t/t 350 438 105
Electricity,KWh/t 330 130 <700
Steam,t/t 0.4 0.4 4.6

1.9 Technical Progress

Acrylic acid and esters technology after 30 years of development, the design of the reactor, catalyst
performance,equipmentcorrosion,aspectsofheatsensitive,antiaggregationtechnologyofmaterials,
suchasacrylicacidrefininghavebeengreatlyimprovedandenhanced.Acryliccraftsteptwooxidation
technologyisquitemature.

(1)Reactordesignsandpatentsprovidersaredevelopingasinglereactororsuperimposedreactor.Our
developmentofasinglefixedbedshellandtubeisheatexchangerreactorandthehousingisdivided

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ShenyangUniversityofChemicalTechnology

into two separate cooling medium circulation alone space. A reaction tube filled with acrolein and
acrylicacidfromthebottomtothetopofthecatalystandthecatalystloadingbetweenthetwofillinert
material.Thetemperatureofthelowerportionofthetubeat325 andthetemperatureofthegas
enteringtheupperportionofthetubeismaintainedat265 .Earlyreactionsstepresultconversionof
propylene was 89.5%. BASF is studying the twostep divided into two successive reaction zones. The
reaction zone control reaction temperature higher than the temperature of a reaction zone prior to
adapttohighloadsofpropyleneandacroleinreactionrequirements.Adjustingthefeedofoxygenanda
propylenefeedratioofacroleininspacevelocityoptimizethereactiondepthdevelopedbyDuePont
movingbedprocessinasmallamountofoxygenormolecularoxygenfreeunder(latticeoxygen)the
conditions and the amount of oxygen increased by less acid selectivity and reduce the amount of
byproducts.

Propyleneoxidecatalystsinthedevelopmentofefficienthavealonglifebecausethecatalystcosts
account for a considerable proportion of production improve the selectivity and conversion extended
catalystlifestudybecomesslow.ItisreportedthattheJapanesecompanyisdevelopingapropylene
step catalytic oxidation. The study of the esterification catalyst, the solid catalyst and an organic acid
insteadofaninorganicacidreducewasteemissionsinthepropyleneoxidationcatalystresearchhavea
long life in the development of efficient catalysts since the catalyst costs account for a considerable
proportion of the cost of production. To improve selectivity and conversion rate prolong catalyst life
becometheresearchrelatedKey.

In acrylic refining technology, in order to produce highpurity acrylic acid and the patent study
differentproviderseparationtechnologyinSwisscompanySulzerdevelopedafallingfilmcrystallization
methodofhighpurityacrylicacid.FallingFilmcrystallizationmethodhavelowstateoperationandthe
polymer production can be reduced. Chemical Company such as Nippon Shokubai and Japan's
Mitsubishi Chemical Company uses azeotropic distillation and distillation towers in BASF added using
thinfilmevaporatorflowprocesstoproducehighpurityacrylicacidwithoutentraine.

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ShenyangUniversityofChemicalTechnology

Chapter II

Experimental Method

2.1Reagent and Equipment

2.1.1 Reagent
Ammonium meta vanadate, Ammonium paramolybdate, Hydrogen peroxide, deionized water, telluric
acid,Niobiumhydroxide,Oxalicacid,Nitricacid(1:1).

2.1.2 Equipment
(i)Rotaryevaporator,(ii)Boxtyperesistancefurnace,(iii)Tubularresistancefurnace.

2.2 Preparation Of Catalyst

1.Weighed amount of Amonium Paramolybdate (NH4)6Mo7O24.4H2O) and Ammonium meta
vanadate (NH4VO3) were dissolved in 80mL of deionized water at 80 and then cooled at room
temperaturetoproducethefirstsolution(solutioncolortoyellow).

2.Quantitativetelluriumacid(TeO2)mixedinhydrogenperoxide(H2O2)anddissolvedtoobtaina
secondsolution.

3.Weighedamountofniobiumhydroxide(Nb(OH)O7)dissolvedintheappropriateamountofasolution
ofoxalicacid(C2H2O4.2H2O)toprepareathirdsolution.

4.Thefirstsolutionandsecondsolutionaremixedtogenerateabrightyellowturbidsolutionandstiron
amagneticstirrermixingatagiventemperatureandthedurationperiodoftimewhereabrightyellow
solutiongraduallybecameturbiddarkred.

5. Added niobium oxalate solution, dark red color of the solution becomes deeper (With boron and
ceriumadditivescontinuetoaddthecatalystBoricacidorceria)with1:1nitricacidsolutiontoadjust
the solution pH. Magnetic stirrer stirring the mixture in specific temperature heating continued for a
certaintimethatfollowed by rotary evaporationtodrynessby rotary evaporation temperature range
from80~85 .

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Shenyan
ngUniversityofChemicalTechnology

6. Finallyy, roasting ccalcining in two steps in the air atmosphere usin

ng a muffle furnace. Thee first step
firingtem mperatureaat260 in aair,duration n2h.Theseccond step caalcinationtemmperatureaat500 in
nitrogen n,calcination ntime2h.

Schematicrepresentationofcatalysttpreparationareshown:

2.3. Ca
atalyst Eva
aluation
The catalytic performance of Mo1V0.16Te0.19Nb0.65Ox was w evaluateed for the selective oxxidation of
propylen ne to acrylic acid in a co
ontinuousflo
ow fixedbedd micro reacctor at atmo
ospheric preessure. The
reactorwwasmadeoffquartztubee,40cmlongand0.8cm mdiameterm mountedverticallyandheatedwith
anelectricfurnace.A Amixtureoffpropylene airsteamwaasfedfrom thetopofth hereactor.TTheoffgas
wascond densedandttheliquidph haseseparateedfromtheggasphaseinacoldtrap.Boththegassandliquid
phaseso oftheproducctstreamsw wereanalyzed dwithGCtodeterminetthevaluesoffpropylenecconversion,
acrylicaccidyieldandthedistributionofotherrproducts.

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Shenyan
ngUniversityofChemicalTechnology

2.4. Ca
atalytic Ox
xidation M
Method
Reactionn at atmosphheric pressure in a continuous flow fixed bed sstainless steeel tubular reeactor ( =
8mm)caarriedout.Th heamounto of2gcatalysttpackedinthhemiddleoffthe
reactortthermocouplleplacedintthecenteroffthecatalysttbed.Propyllene,
air,wateervaporinproportiontoothefeedgasintothereeactiontube,the
reaction occurredattasuitablettemperature.Reactionfrromtheexhaaust
omatograph online testing the liquiid product o
gas chro obtained by the
reaction is conden nsed by thee injector into the q quantitative gas
chromattography.

2.5 Callculation Method

1.Propyyleneyieldcaalculation:

AcrylicacidyieldY%=mRT/MPV*100%,

m=fmsA/as,m=massofacrylicacidiinthereactio
wherem onproduct

R:Molarrgasconstan
nt

T:Reactiiontemperatture

P:Propylenepressurre

meofpropylene
V:Thereeactionproceessintotherreactorvolum

f:Correcctionfactorp
proportionalcoefficient(m
measuredbyyexperimentt)

Ms:Themassoftheinternalstan
ndard

A:Acryliccpeakarea

As:Peakkareaofinternalstandard
d

2.SelecttivitytoacrylicacidS%=YY%/X%

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ShenyangUniversityofChemicalTechnology

Chapter III

Result and Discussion

3.1 The Optimum Catalyst Selection

In the present study, the process variable is the catalyst, temperature, space velocity, the ratio of
oxygenandpropylene,theratioofthewaterandpropylene.Wegetavarietyofcatalyststhatfindthe
mostsuitablecatalystundertheconditionsobtainedbycomparingdata.Thecatalystunderthereaction
conditionsoftheoptimumtemperature,optimumspacevelocity,theoptimumratiooftheoxygenand
propylene, the optimum ratio of water and propylene are shown in figures. Large number of
experimentsintheearlybasis,wehavechosenthesameairspeedpropyleneof3.5ml/(gmin)andthe
ratio of oxygen and propylene (2.02.3):1, the ratio of water and propylene 4.5:1, converted reaction
temperatures tests, choose four different catalysts. From the experimental data and experimental
results,thebestcatalystscanbefound.

80

70
the conversion of propylene(%)

60
MoV0.16Te0.19Nb0.65
MoV0.16Te0.19Nb0.65Ce0.08
50 MoV0.16Te0.19Nb1.3B0.11
MoV0.16Te0.19Nb1.3

40

30

20

10
400 420 440 460
temeperature()

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ShenyangUniversityofChemicalTechnology

Figure3.1Conversionofpropylenewithcatalystsatfourdifferenttemperatures.

Itcanbeobtainedfromtheanalysisofthefigurethattheconversionofthecatalystsincreasedwiththe
temperature.Mo1V0.16Te0.19Nb0.65andMo1V0.16Te0.19Nb0.65Ce0.08bothatthesametemperaturerangeand
the conversion rate was less than Mo1V0.17Te0.11Nb1.3B0.11 and Mo1V0.17Te0.11Nb1.3. And at the same
temperatureconversionofMo1V0.17Te0.11Nb1.3B0.11ismaximum.

MoV0.16Te0.19Nb0.65
90
the selectivity of acrylic acid(%)

MoV0.16Te0.19Nb0.65Ce0.08
MoV0.16Te0.19Nb1.3B0.11
80 MoV0.16Te0.19Nb1.3

70

60

50

40

30

400 420 440 460

temperature()

Figure3.2SelectivityofAcrylicacidinfourdifferentcatalystswithtemperature

Fromtheabovechartwecanseethechangeofdifferenttemperature,acrylicacidcatalystunderthe
fourtemperaturehaveeffectedthedegreeofselectivity.Mo1V0.16Te0.19Nb0.65catalystcomparedwiththe
other three catalysts has less affected by the temperature and the Mo1V0.16Te0.19Nb0.65Ce0.08,
Mo1V0.17Te0.11Nb1.3B0.11 with the temperature rising and the selectively reducing, Mo1V0.17Te0.11Nb1.3
catalyst with the increasing of the temperature it first raises and then decreases, at 420 has the
maximum selectivity. Compared to the overall representing, Mo1V0.16Te0.19Nb0.65Ce0.08 and
Mo1V0.17Te0.11Nb0.13B0.11 have better selectivity and Mo1V0.16Te0.19Nb0.65Ce0.08 is the best catalyst.
Mo1V0.17Te0.11Nb1.3B0.11 catalyst at 400420 temperature regions with a small decrease, when the
temperaturerisesto420 ,theselectivityofthiscatalysthasgreatlydecreased.

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ShenyangUniversityofChemicalTechnology

40

the yield of acrylic acid(%)

35

30

25

20

MoV0.16Te0.19Nb0.65
15
MoV0.16Te0.19Nb0.65Ce0.08
MoV0.16Te0.19Nb1.3B0.11
10
MoV0.16Te0.19Nb1.3

400 420 440 460

temeperature()

Figure3.3Acrylicacidyieldfourdifferentcatalystsinthetemperaturedependence

Fromtheabovechartanalysisshowsthat,Mo1V0.16Te0.19Nb0.65catalystsinstudytemperatureregionshas
the minimum yield, and yield little change with temperature changes. The yield of
Mo1V0.16Te0.19Nb0.65Ce0.08 catalyst with temperature rise high yield rate is on the rise, but the yield of
Mo1V0.17Te0.11Nb1.3 catalyst is lower than Mo1V0.17Te0.11Nb1.3B0.11. The producing of Mo1V0.17Te0.11Nb1.3
took the lead with the temperature rises,itreachesamaximumtemperatureabout420 and withthe
rise of temperature the producing decrease. The temperature continues to rise with decrease in the
yield. The yield of Mo1V0.17Te0.11Nb1.3B0.11 is also firstly increasing with the temperature higher and
reaches the maximum at about 440 . To compared with two catalysts, the productivity of
Mo1V0.17Te0.11Nb1.3B0.11catalysthasahigherrateandinthetemperaturerangehasagoodtrend.

Catalystselectiontakingthesethreecasesexist,firstly,accordingtothecatalystperformanceanalysis
theMo1V0.17Te0.11Nb1.3B0.11catalystintemperaturezonestheconversionrateandyieldarethebest.And
inthetemperaturerangetheselectiveofcatalystbehindMo1V0.16Te0.19Nb0.65Ce0.08andthetrendisalso
good.Comprehensiveanalysisofthethreeknowncatalyst,Mo1V0.17Te0.11Nb1.3B0.11istheoptimalcatalyst.

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ShenyangUniversityofChemicalTechnology

3.2 The Optimum Choice of Reaction Condition

Fromtheaboveanalysisofthecatalyticperformanceofthebestcatalyst,hereweusethefollowingfour
aspects.Mo1V0.17Te0.11Nb1.3B0.11oxidationcatalystpropyleneacrylicstepreactionprocesswerestudied.

3.2.1 Effect of Temperature

Maintainingthespacevelocityofpropyleneisabout3.5mL/(gmin),alkyleneoxygenratiois(2.02.3):
1 and the water conditions of alkenyl ratio is of 4.5:1. The conversion of six different reaction
temperaturestestimpactofthecatalystMo1V0.17Te0.11Nb1.3B0.11,thetestdataisplottedasshown:

80
conversion/selectivity/yield(%)

70

60

50

40

30

the conversion of propylene

20 the selectivity of acrylic acid
the yield of acryliv acid
360 380 400 420 440 460

temperature/

Figure3.4Temperatureonpropyleneconversion,selectivityandyieldofacrylicacid

Itcanbeobtainedfromthediagramanalysis,thepropyleneconversionratehasbeenincreasedwiththe
increasing of temperature from 30.97% in 360 to 74.23% in 460 . Selectivity of acrylic acid with
increasing temperature itfirstlyincreaseandthen decreased, at380 reachingthemaximum,butin
thetemperaturerangeof380420 itdeclinemoreslowlythan420 ,theselectivityof68.42%in380
haslittledifferwiththebiggestselectivityof73.23%in420 ,thetemperaturecontinuestorisewhile
above420 the selectivesharpdeclinedownto440 of39.71%.Yieldofacrylicacidwithtemperature
increases firstly and then decreases, at 360400 temperature range it closing rate increased
considerably,at400440 temperaturerangetheyieldcontinuestoincrease,buttheincreaseisvery
slowly and only from 400 of 38.23% increase to 440 of 40.07%. The difference is small and the
temperaturecontinuestoriseandselectivesharplydecline.

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ShenyangUniversityofChemicalTechnology

the selectivity/yield of acetic acid(%)

the seclectivity of acetic acid

the yield of acetic acid
10

360 380 400 420 440 460

temperature/

Figure3.5Temperaturesonselectivityandyieldofaceticacid

Figureanalysiswecanknowthattheselectivityandyieldofaceticacidinthetemperaturerangeboth
withthetemperatureriseitfirstlyincreasesandthendecreases,reachesthemaximumat380 .The
temperaturecontinuestorise,theselectivityandyieldofaceticacidhasbeenreduced.

Therefore,abovetheanalysissummaryshowsinthetwographsweknow,becauseofconversionrate
ofpropylenehasbeenincreasedwithtemperatureincreasingandtheacrylicselectivemaximumpoint
at380 , butat420 ithaslittledifferencewiththeselectivityofacrylicacid.Themaximumyieldpoint
at 440 and at 420 the differences is very small contrast. The comprehensive conversion of
propylene,acidselectivityandtheyieldofacrylicacidandproductionsituationofbyproductaceticacid,
wechoose420 asthebestselectedconditionspoint.Inthisoptimumtemperature,theconversionof
propylene and acrylic acid selectivity and yield are all at a larger value, and at the same time the
selectivityandyieldofaceticacidatalowerlevel.

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ShenyangUniversityofChemicalTechnology

3.2.2 The Impact of Space Velocity of Propylene

Maintainingtheoptimumreactiontemperature420 ,alkyleneoxygenratio(2.02.3):1andthewater
conditionsalkenylthan4.5:1, variableconversionofpropylenedifferentspacevelocitytestpropylene
Mo1V0.17Te0.11Nb1.3B0.11differentspacevelocitiesofthecatalystmeasuredtestdataplottedasshown:

80
conversion/selectivity/yield(%)

70
the conversion of propylene
the selectivity of acrylic acid
60 the yield of acrylic acid

50

40

30

2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

space velocity/ml/(gmin)

Figure3.6Airspeedofpropyleneconversion/selectivityofacrylicacid

Analysis the figure, propylene conversion with the versus space velocity increases firstly and then
decreased,whenairspeedis5.0mL/(gmin)thepropyleneconversionreachesaminimumfor37.75%
and when airspeed continues to increase the propylene conversion increased but the increase is not
largely. Acrylic acid selectivity increases withspacevelocity increase firstly and thendecreased, when
the airspeed was 5.0mL / (gmin), the acrylic acid selectivity reaches at the maximum 80.25%, space
velocity continues to increase, the selectivity of acid has slightly decrease. Acrylic acid yield with the
space velocity increases it firstly increases and then decreases and finally stabilized. When the space
velocity was 3.8mL / (gmin), the acrylic yield reaching the maximum rate of 39.68%. With the space
velocitycontinuestoriseandtheyieldofacrylicacidreducing,whenthespacevelocitycontinuestorise
over5.0mL/(gmin)andtheacrylicacidyieldremainedstable.

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ShenyangUniversityofChemicalTechnology

6
seclectivity/yield (%)

4 the seclectivity of the acetic acid

the yield of the acetic acid

2
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

space velocity/ml/(gmin)

Figure3.7Spacevelocityontheselectivityandyieldofaceticacid

In the figure, before the space velocity reaches 3.1mL /(gmin)the selectivity and yield of acetic acid
weretestedincreasingtrendpotentialandthegrowthofaceticacidselectivitygreater.Spacevelocity
continued to increase, and after the airspeed reach from 3.1mL / (gmin) to 6.3mL / (gmin), The
selectivity and yield of acetic acid have a minimum value and acetic acid selectivity has minimum in
spacevelocity3.8mL/(gmin).Theaceticacidyieldminimumappearedinspacevelocity5.0mL/(gmin)
andwhenthespacevelocityover5.0mL/(gmin),theselectivityandyieldofaceticacidweretested
growthtrendpotential.

Summinguptheaboveanalysistwographsresultitobtainedthat,whenthespacevelocityis3.8mL/
(gmin) and the acrylic acid yield has the largest value. And in this space velocity, the propylene
conversionandselectivityofacrylicacidarestillrelativelyhigh.Ingeneralbothselectivityandyieldof
acetic acid maintain a lower level. So, space velocity of 3.8mL / (gmin) is the catalyst of optimal
conditions.

3.2.3 Ratio of Oxygen/Propylene

Maintaining the temperature at 420 , propylene space velocity is about 3.5ml / (gmin) and water
alkenylconditionsisobtainedthan4.5:1.Theratioofoxygenandpropylenetestingdifferentalkylene
oxygenratioofthecatalystMo1V0.17Te0.11Nb1.3B0.11test.

Thedataisplottedasshown:

27

ShenyangUniversityofChemicalTechnology

80

conversion/seclectivity/yield(%)
70

60

50

40

30
the conversion of the propylene
the selectivity of the acrylic acid
the yield of the acrylic acid
20
1.0 1.5 2.0 2.5 3.0 3.5 4.0

O2/CH3CH=CH2

Figure3.8onoxygenpropyleneconversionratio,selectivityandyieldofacrylicacid

Itcanbeseenfromthisfigure,acrylicacidselectivityandyieldwhenoxygenpropyleneratiois1.9:1and
ituptothemaximum,althoughtheconversionofpropylenehasnotobtainthemaximumratioin1.9:1,
whentheratiooftheoxygenpropylenewas1.9:1andtheconversionofpropyleneat53.07%.Whenthe
oxygenpropylene ratio is 2.5:1, then the propylene conversion is 54.75%. So obviously, when the
oxygenratiois1.9:1,itcanmeetthepropyleneconversionandselectiveandyieldsofacrylicacidare
maintainedinwellcondition.

28

ShenyangUniversityofChemicalTechnology

10
the seclectivity of acetic acid
the yield of acetic acid

seclectivity/yield(%) 8

1.0 1.5 2.0 2.5 3.0 3.5 4.0

O2/CH3CH=CH2

Figure3.9Oxygenpropyleneimpacttheselectivityandyieldofaceticacid

Itcanbeseenfromthefigure,theyieldofaceticacidreachedthemaximumratiowhichtheoxygen
propylene ratiois1.9:1. With theoxygenpropyleneratioisgreater over 1.9, with theincreaseofthe
ratioofoxygenpropyleneandtheyieldofaceticacidwasreduced.Theselectivityofaceticacidhaslittle
changeswhentheoxygenpropyleneratiois1.31.9.Whentheratioexceedingthan1.9,theselectivity
ofaceticacidisreducing,whentheoxygenpropyleneratiois3.8,theyieldandselectivityofaceticacid
arebothminimum.Therefore,fromtheaboveanalysisitshowsthatwhentheoxygenpropyleneratiois
1.9:1, although the yield and selectivity of byproduct acetic acid is both higher, the integrated
conversion of propylene and acrylic acid selectivity and yield of acrylic acid we choose the oxygen
propylene ratio is 1.9:1. Under this condition, the yields and selectivity of acrylic acid are the largest,
relativelytheconversionrateishigher.

3.2.4 Ratio of WaterPropylene

Whilemaintainingthereactiontemperatureat420 ,propylenespacevelocityisabout3.5mL/(gmin).
Alkyleneoxygenratiois(2.02.3):1thatregulatedifferentratioofwaterandpropylenetotestdifferent
wateralkenylthantheimpactofthecatalystMo1V0.17Te0.11Nb1.3B0.11.Thetestdataisplottedasshown:

29

ShenyangUniversityofChemicalTechnology

80

conversion/selectivity/yield(%) 70

the conversion of acrylic acid

60 the selectivity of acrylic acid
the yield of acrylic acid

50

40

30

0 5 10 15 20 25 30

H2O/CH3CH=CH2

Figure3.10Waterpropylenecomparedtopropyleneconversion,selectivityandyieldofacrylicacid

Fromtheabovediagramanalysis,whenthewaterpropyleneratiorangesbetween01.5thepropylene
conversion,theselectivityandyieldofacrylicacidwereallincreasingwiththeincreaseofwater.When
the waterpropylene ratio range 1.53, the change of propylene conversion rate is small, and the
selectivity of acrylic acid is decreased so that the yield of acrylic acid also has a small magnitude of
decline. In the waterpropylene ratio range 327, the propylene conversion rate overall tested
downwardtrendandtheoverallselectivityofacrylicacidwasstabletrendwhiletheyieldofacrylicacid
inthisrangehasasmallfluctuations.Whenwedidnotaddwatertothereaction,ithaslittleinfluence
aboutthe conversion of propylene, but has great effects on selectivity so that it results as the acrylic
acidyieldwasminimal.Therefore,thegenerationofwateronacrylicacidplaysanimportantrole.

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ShenyangUniversityofChemicalTechnology

10

selectivity/yield(%)
8

2
the seclectivity of acetic acid
the yield of acetic acid
0 5 10 15 20 25 30

H2O/CH3CH=CH2

Figure3.11Waterpropyleneimpacttheselectivityandyieldofacrylacetate

From the figure it can be obtained that with the waterpropylene ratio increasing, the yield and
selectivity of acetic acid has some fluctuations but overall are presented increasing trend. When the
waterpropyleneratiorangeis0.86,theselectivityandyieldofaceticacidisrelativelysmall.Reaction
without water also has impact on the formation of acetic acid. Based on the above two figure, when
waterpropylenerangeis00.8andthepropyleneconversionandyieldofacrylicacidarebothingrowth
phase, but also at a low level. When the waterpropylene ratio of 0.86:1, the yield of acrylic acid is
stable at 35%. The conversion of propylene and acrylic acid selectivity are still relatively good. By
productofaceticacidislower.Inthiscatalyst,theoptimumwaterpropyleneconditionis0.8to6:1.

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ShenyangUniversityofChemicalTechnology

Conclusions
First,theexperimentalresultshavebeenobservedthat

1.Theprocessforthecatalystsinthisstudy,theoptimalcatalystisMo1V0.17Te0.11Nb1.3B0.11.

2.Usedtheoptimumtemperatureofthecatalystisabout420 .

3.Ifbestwhenusingthecatalystspacevelocityofpropyleneis3.8mL/(gmin)orso.

4.Ifbestwhenusingthecatalystpropylenewithoxygenratioisabout1.9:1.

5.Ifbestwhenusingthecatalystofwaterpropyleneratioisabout0.8~6:1.

In summary, the using of the catalyst is obtained when the optimum conditions for the temperature
about 420 , propylene airspeed is 3.8mL/(gmin), alkylene oxygen ratio is about 1.9:1 and water
propyleneratioisabout0.8~6:1.Inthiscondition,conversionofpropylenewas58.51%,selectivityof
acrylicacidisabout67.14%thatacrylicacidinayieldof39.48%.Selectivityandyieldofaceticacidwere
7.44% and 4.37% respectively. Second, the experimental problems and prospects an improved way
catalystloadingusingaproportionof610meshquartzsandmixedwiththecatalystintothefixedbed
reactorthereactiontoincreasestrongthermalperformanceofthecatalystbedreducingthereaction
and produce hot spots for promoting the stability. The carbon balance solve problems not only can
enhancethereliabilityoftheexperimentalresults.Theprocessofthereactioncanbecarriedoutmore
accurate understanding and analysis of the mechanism for the more indepth study provides more
experimentalbasis.

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Acknowledgement

Firstofall,IwouldliketoexpressmydeepestgratitudetoAllahforhisdivineblessingswithoutwhomit
wouldhavebeenimpossibleformetocompletethisprojectsuccessfully.Iameternallygratefultomy
parentsandfamiliesfortheirconstantloveandsupportthroughoutmyacademicstudies.Ithasbeenan
immensepleasureandagreathonourformetoshowmygreatrespecttomysupervisor,LecturerMr.
ShuangmingLi,fromtheDepartmentofChemicalEngineering,SYUCT,whohasrenderedmewithhis
continuousguidanceandencouragementthroughoutmyfinalyearofmyacademicofmystudieswith
hisvaluableadvices.Hisgenerosityandinterestisanexemplaryforthisreport.Iwouldliketothankall
the respectable members of the faculty especially all the teachers from the Department of Chemical
EngineeringofSYUCTfortheirfeedbackandinspirationthatwasreallyhelpfulwhilewritingthisthesis
Atlastbutnottheleast,Iwouldliketooffermyheartful thankstoallofmyfriendsfor helpingmeby
offeringtheirrigorousreviewsofthisworkandinspiringsuggestions.

Ithink,thisiscarriedoutwherethepurposeandsignificanceofthethesis.Duetothelimitedleveland
therelationshipoftime,thisdesignwillinevitablybemanyomissionsanddeficiencies,pleaseteacher
award,assessmentandcorrection.

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ShenyangUniversityofChemicalTechnology

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[15] zhenfcheng En, 2008. Acrylic Industry overview, see: Chinese Chemical Society of Professional
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Graduation Thesis Grading Evaluation

The thesis submitted by MD. MAHFUZUR RAHMAN SIDDIKY, majored in chemical engineering
and technology, has been inspected by the graduation thesis evaluating committee of chemical
engineering, Shenyang University of Chemical technology on 7th January, 2014.

Title: Preparation and Application of Catalyst for One Step Oxidation Synthesis of Acrylic
Acid from Propylene

Advisor:

Reviewer:

Committees evaluation:

The candidate has searched and read plenty of related references, and determined the
research direction with some innovative points in the thesis. The thesis was written logically,
fluently and formally .During the oral defense, the candidate clearly stated the main results of
the thesis and answered the questions correctly.

Based on the research work of the thesis and the candidates oral defense, five members of the
Defense Committee recommends that the grade is

The chair of the Defense Committee (signature)

Date:

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