1
Bachelo Disse a ion
Bachelo o Science in Chemical Enginee ing
Aspen HYSYS Simula ion o Maleic Anhyd ide
P oduc ion om n-Bu ane ia Pa ial Oxida ion
Simulación con Aspen HYSYS de la p oducción de
Anhíd ido Maleico a pa i de la oxidación pa cial de
n-Bu ano
Au ho : Xaquelina K. Oli a Kowalsky
Disse a ion supe iso : D . Ángel Luis Villanue a Pe ales
Depa men o Chemical and En i onmen al Enginee ing
Highe Technical School o Enginee ing (ETSI)
Uni e si y o Se ille
Se ille, 2017
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
Bachelo Disse a ion
Bachelo o Science in Chemical Enginee ing
Aspen HYSYS Simula ion o Maleic Anhyd ide
P oduc ion om n-Bu ane ia Pa ial Oxida ion
Au ho :
Xaquelina K. Oli a Kowalsky
Disse a ion supe iso :
D . Ángel Luis Villanue a Pe ales
Associa e P o esso
Depa men o Chemical and En i onmen al Enginee ing
Highe Technical School o Enginee ing (ETSI)
Uni e si y o Se ille
Se ille, 2017
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
Bachelo Disse a ion: Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial
Oxida ion
Au ho :
Xaquelina K. Oli a Kowalsky
Disse a ion supe iso :
D . Ángel Luis Villanue a Pe ales
The O al De ense Commi ee in cha ge o judging he a o emen ioned Bachelo Disse a ion is composed by:
P esiden :
Membe s a la ge:
Sec e a y:
Ha e ag eed o g an a inal sco e o :
Se ille, 2017
The Sec e a y o he Commi ee
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
i
Acknowledgemen s
P o ound hanks o my disse a ion supe iso , D . Villanue a who has been a con inuing sou ce o in o ma ion
as well as a solid guide h oughou he de elopmen o his wo k.
I am deeply g a e ul o my amily whose pa ience and mo i a ion ha e always helped me b ing ou he bes o
me.
I would like o exp ess deep g a i ude o Luis Miguel C. who, since eshman yea , has been my main pee
emo ional suppo and has ne e le me down; o Ja ie N. who has augh me how o be a g ea eam playe and
an ou s anding iend; o Jose Da id J. o p o iding me wi h un ailing suppo , con inuous encou agemen and
an endless sou ce o inspi a ion.
To Debo a A. who has helped me in he pas yea s o ca e o e en he smalles de ails. I am g a e ul o he
pa ience, gene osi y and amazingly p ecise and conside a e edi ing.
I am also g a e ul o Da id G., A mando C., Césa P. and Ma ina V., among o he s, who o e he yea s ha e,
wi h g ea gene osi y, in di e en ways helped me o lea n, become a be e pe son and who ha e been
ema kable emo ional suppo .
Xaquelina K. Oli a Kowalsky
Se ille, 2017
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
ii
Abs ac
The documen a ion o he a ious echnologies bo h cu en and ou da ed o he p oduc ion o maleic anhyd ide
was pe o med he i s place. A e wa ds. he modeling and simula ion o a maleic anhyd ide p ocess plan was
ca ied ou in his disse a ion. Maleic anhyd ide is p oduced ia n-bu ane pa ial oxida ion. The so wa e used
o he simula ion is Aspen HYSYS. Technical da a we e collec ed om a ious sou ces such as pa en s and
manuals. The chosen echnology o he oxida ion sec ions and un eac ed n-bu ane ecycle is Dupon ’s
ci cula ing luidized bed (CFB) which is based on US Pa en 4,668,802 and uses VPO ca alys in he CFB
eac o . The chosen echnology o he eco e y sec ion de eloped by Monsan o has been ollowed h ough US
Pa en 4,188,403.
Th oughou he simula ion, he e ha e been empe a u e es ic ions conce ning liquid mix u es o wa e and
maleic anhyd ide in o de o p e en eac ions ha lead o maleic acid and uma ic acid. The gaseous mix u e
and o ganic sol en in e ac ion a e conside ed as ideal mix u es. The p oduc ion capaci y o he chosen plan is
oughly 36,800 me ic ons pe yea . Pe cen ages highe han 99 % conce ning p oduc pu i y and ecupe a ion
we e ob ained as well as eac i e losses o abou 20 %
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
iii
Table o Con en s
Acknowledgemen s i
Abs ac ii
Table o Con en s iii
Lis o Tables
Lis o Figu es i
Lis o symbols and abb e ia ions iii
1 In oduc ion, Backg ound in o ma ion, Objec i es, and Bounda ies 1
1.1 Backg ound in o ma ion ............................................................................................................................... 1
1.1.1 Desc ip ion 1
1.1.1.1 Physical p ope ies 1
1.1.1.2 Chemical p ope ies 1
1.1.2 Applica ions 2
1.2 Objec i es ....................................................................................................................................................... 3
1.3 Bounda ies ..................................................................................................................................................... 4
2 S a e O The A 5
2.1 Maleic Anhyd ide Global Ma ke ................................................................................................................. 5
2.2 P ocess ou es ................................................................................................................................................ 6
2.2.1 Benzene oxida ion 6
2.2.2 Linea C4 hyd oca bon eeds ock 7
2.2.3 By-p oduc o ph halic anhyd ide 7
2.3 Technologies .................................................................................................................................................. 7
2.3.1 Mul i- ubula ixed bed eac o s 7
2.3.1.1 Hun sman 8
2.3.1.2 Halcon-Scien i ic Design (HSD) 11
2.3.1.3 Ruh ol-Lu gi 13
2.3.1.4 Ruh ol-Baye 13
2.3.1.5 SAVA 13
2.3.1.6 BASF 13
2.3.2 Fluidized bed eac o s 18
2.3.2.1 Mi subishi 18
2.3.2.2 ALMA 20
2.3.2.3 Badge 20
2.3.2.4 BP-UCB 20
2.3.3 T anspo bed eac o s (CFB) 24
2.3.3.1 Du Pon ’s C-4 eeds ock 25
2.4 P oduc ion s ages ........................................................................................................................................ 27
3 Me hodology 29
3.1 P ocess desc ip ion ...................................................................................................................................... 29
3.2 Technical Speci ica ions............................................................................................................................... 31
3.2.1 Feed 31
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
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1 INTRODUCTION, BACKGROUND INFORMATION,
OBJECTIVES, AND BOUNDARIES
1.1 Backg ound in o ma ion
1.1.1 Desc ip ion
aleic anhyd ide (MAN) is an o ganic compound wi h he chemical o mula C4H2O3 which main
ea u es a e wo ca bonyl g oups and a double bond as seen in Figu e 1 (1). This chemical is a
s ong i i an o skin, eyes, and mucous memb anes o he uppe espi a o y sys em (2). I is
also known by o he names such as 2,5- u andione, dihyd o-2,5-dioxo u an, oxilic anhyd ide, and cis-
bu enedioic anhyd ide (3).
Figu e 1 – S uc u al o mula o maleic anhyd ide (3)
1.1.1.1 Physical p ope ies
A oom empe a u e, his o ganic compound i is a whi e c ys alline solid wi h a pungen odo which begins
mel ing a 52.8 °C and boils a 202 ºC. Howe e , o handling easons, du ing p oduc ion, i is a liquid o gas
(2).
Typical speci ica ions call o a HAZEN colo o 20 o less o mol en maleic anhyd ide (4).
This chemical compound is soluble, om g ea es o lowes , in ace one, benzene, oluene, o-xylene and ke osene
among o he o ganic componen s (5). Howe e , condi ions mus be ca e ully adjus ed o a oid isome iza ion o
maleic and uma ic acid (3).
1.1.1.2 Chemical p ope ies
Due o he ex emely eac i e double bond, maleic anhyd ide eac s eadily (hyd olyzes) wi h wa e o o m
maleic acid (MA) a abou 60 ºC and uma ic acid (FA) a 100 ºC. Fuma ic acid c ys allizes and is no eadily
soluble in wa e . The mal ea men and ca alys a e used o enhance o ma ion o uma ic acid by maleic acid
isome iza ion (3). This eac ion is shown in Figu e 2.
By limi ing he aqueous maleic anhyd ide acid concen a ion o 40 % and he empe a u e o less han 85 ºC,
uma ic acid will no o m in > 0.1 % weigh o he eac ion mix u e.
Maleic acid can be he mally dehyd a ed om an aqueous solu ion o h ough azeo opic dis illa ion o maleic
anhyd ide (3).
M
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
2
Figu e 2 – Reac ions om maleic anhyd ide o maleic acid and uma ic acid (6)
Maleic anhyd ide is also sui able o homopolyme iza ion and copolyme iza ion o ming polyme s such as
s y ene-maleic anhyd ide (SMA) o Ac ylic Acid Maleic Anhyd ide (MA/AA) (5).
1.1.2 Applica ions
Unlike maleic acid, he anhyd ide is a mul i unc ional chemical in e media e which has g ea impo ance in he
chemical indus y. The global uses o his compound o he yea 2009 (Figu e 3) a e in o de o impo ance:
unsa u a ed polyes e esins, bu anediol ela ed chemicals and o he s which include lube oils and addi i es,
maleic copolyme s, uma ic and malic acid and ag icul u al chemicals among o he applica ions.
Figu e 3 – Maleic Anhyd ide uses in he Uni ed S a es du ing he yea 2009 (7)
Unsa u a ed Polyes e Resins (UPR) hold almos wo- hi ds o he cha . These esins happen o be he
majo end use o maleic anhyd ide as eeds ock in i s p oduc ion. These lamina ing esins, which ha e
high s uc u al s eng h and good dielec ic p ope ies a e used bo h in glass- ein o ced and in
un ein o ced applica ions. The da a in he ollowing pie cha (Figu e 4) co e s he wide ange o uses
o UPR du ing he yea 2000 including: A hi d o he cha in cons uc ion such as building panels,
almos a qua e in o he which co e s di e se uses; o example, luggage o ba h ubs. In hi d place,
ma ine and anspo a ion indus y hold almos he same weigh co e ing aspec s such as molded boa s
and au omobile bodies. Co osion applica ions co e en and a hal pe cen and include uses like
cons uc ion o chemical s o age anks. Las ly, smalle amoun s o UPR a e used in elec ical
applica ions such as ada domes holding no e en wo pe cen (1)(2).
60%
8%
32%
Uses o Maleic Anhyd ide
Unsa u a ed polyes e esins
Bu anediol ela ed chemicals
O he s
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
3
Figu e 4 – Uses o Unsa u a ed Polyes e Resins in he Uni ed S a es, 2000 (3)
Maleic anhyd ide is a key eeds ock in he manu ac u ing o copolyme s since i is a low-cos monome
ha adds unc ionali y o adi ional pe ochemical polyme ma e ials such as binding wood in o ibe
plas ic, inhibi ing co osion, c ea ing p o ec i e coa ings o wi es o e en epelling wa e in sunsc eens
(8)(7). The a o emen ioned copolyme , SMA, is used o enginee ing plas ics while MA/AA is used in
he de e gen indus y (1).
Smalle amoun s o MAN a e used in ag icul u e, mo e speci ically in he p oduc ion o pes icides
(cap an, mala hion) and g ow h inhibi o s (maleic acid hyd azide) (5).
Maleic anhyd ide h ough con e sion o uma ic and malic acids, is a i al componen o gelling agen s,
la o enhance s, and ood p ese a i es. I is also essen ial o he p oduc ion o elas ane (Spandex)
ibe s, a i icial swee ene s, pape -sizing, wa e ea men s, ha dene s o epoxy cu ing, hai sp ays,
pha maceu icals, ag icul u al chemicals and mo o oil addi i es (8).
O he end p oduc s include lube oils addi i es, plas ics, succinic acid and su ace ac i e agen s (2).
A e he yea 2000, maleic anhyd ide began o be used as aw ma e ial in he p oduc ion o 1,4-
bu anediol (BDO), gamma-bu y olac one and e ahyd o u an (THF). I is impo an o highligh ha
nowadays, BDO is one o he wo ld’s as es g owing chemicals which is used as aw ma e ial in he
manu ac u ing o plas ics, elas ic ibe s and polyu e hanes explaining husly he eason o which his
chemical compound does no appea in he pie cha (1).
1.2 Objec i es
The pu pose o his p ojec is he modeling and simula ion o he p oduc ion p ocess o maleic anhyd ide ia n-
bu ane pa ial oxida ion wi h Aspen Plus.
The p oduc ion capaci y o he plan is chosen 36,800 cubic me e s pe yea , in o he wo ds, abou 48,500 me ic
ons pe yea o maleic anhyd ide a a pu i y o 98% n/n. This capaci y is simila o ha o a nea ela i ely small
scale maleic anhyd ide p oduc ion plan (9).
The chosen echnology o he oxida ion sec ion and un eac ed n-bu ane ecycle is Dupon ’s ci cula ing luidized
bed (CFB) which is based on US Pa en 4,668,802 and uses VPO ca alys in he CFB eac o due o he
achie emen o high selec i i ies and low isks o explosions.
The chosen echnology o he eco e y sec ion de eloped by Monsan o has been ollowed h ough US Pa en
4,188,403 due o high p oduc eco e y and use o he mally s able sol en s ha do no equi e mul iple s ipping
16,2
34,2
10,4
15
1,9
22,3
Uses o Unsa u a ed Polyes e Resins
Ma ine Cons uc ion Co osion
T anspo a ion Elec ical O he
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
4
s ages in o de o be sepa a ed om maleic anhyd ide.
1.3 Bounda ies
In his wo k, i has been a oided, a all imes, liquid phase wa e and maleic anhyd ide mix u es a empe a u es
abo e 60 ºC in o de o p e en eac ion be ween hese wo componen s ha leads o maleic acid (60 ºC) and
uma ic acid (130 ºC). I has also been conside ed he ac ha he gaseous mix u e in e ac ion wi h he o ganic
sol en we e ideal mix u es.
Wha occu s inside he CFB eac o has no been aken in o accoun in his wo k. I has been conside ed a black
box. The e o e, he quan i y o ca alys has no been calcula ed. Aspec s such as e luen ea men , aw ma e ial
p e ea men , economic s udies, p ocess con ol and auxilia y sys ems a e beyond he scope o his wo k.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
5
2 STATE OF THE ART
his chap e will begin by co e ing maleic anhyd ide global economic aspec s h oughou he ea ly
2000s. Secondly, he main p ocess ou es used since 1930 shall be c i ically discussed. Including
ou da ed p ocesses such as benzene eeds ock and newe ones like C4 hyd oca bons. The exis ence o
a ious echnologies depending on he chosen eac o is s udied in he hi d subsec ion o his chap e .
A e analyzing all h ee di e en eac o s used o maleic anhyd ide p oduc ion – ixed bed eac o ,
luidized bed eac o and anspo bed eac o – he compa ison o he main pa en ed echnologies has been
included. Las ly, his chap e co e s he gene al p oduc ion p ocess o maleic anhyd ide indica ing i s key s ages.
2.1 Maleic Anhyd ide Global Ma ke
As seen in Figu e 5, he ba cha illus a es a o al MA demand o app oxima ely 1.3 m. . wi h a ma ke alue
o 900MUS $ o he yea 2000. The bigges p oduce s o maleic anhyd ide in ha same yea 2000 we e Sisas
(225,000 /yea ), Hun sman (110,000 /yea ) and Ashland (63,000 /yea ) (10). As o he ollowing yea s, he
global maleic anhyd ide ma ke in 2005 d opped o abou 1.25 m. . which la e inc eased by 0.45 m. . in he yea
2009.
Figu e 5 – Wo ldwide Maleic Anhyd ide P oduc ion o he yea s 2000, 2005, 2009 (3) (7) (11)
Tigh ma ke condi ions, as well as ising eeds ock bu ane cos , ha e d i en up MAN p ices abou 50% du ing
2004. Supply was also igh in Eu ope and Asia because high benzene cos s had o ced benzene-based MAN
p oduce s o ei he shu down plan s o cu back p oduc ion.
Excep o A ica which no da a has been ound, be ween he yea s 2005 and 2009, he p oduc ion o MAN ell
sligh ly in mos cases. Tom Fishe , Vice-P esiden Maleic anhyd ide and comme cial licensing a Hun sman,
s a ed: “The demand o UPR has slumped due o he signi ican ly slowe housing, au o and ma ine ma ke s”
(7). Howe e , demand o he p oduc ion o MAN copolyme s was p ojec ed o g ow, speci ically o p oduc s
ha aim o a be e sus ainabili y p o ile.
Focusing on a ela i ely local example o he yea 2007, CEPSA’s Gib al a -San Roque pe ochemical plan
p oduced abou 5,300 ons o maleic anhyd ide oughly p iced a 2,13 US $ pe on. O all pe ochemicals
p oduced a said e ine y, MAN is anked hi d- o-leas –me a-xylene and uma ic acid– in e ms o p oduc ion
in compa ison wi h benzene (205,000 ) o oluene (125,000 ) (4).
The ma ke was igh un il abou mid-2007, bu he slowdown has made he ma ke p edominan ly long in 2009.
Supply was s able and new en an s we e no expec ed in he US. Al hough, globally he e has been
0 500 1000 1500 2000
No h Ame ica
Sou h and Cen al Ame ica
Eu ope
Asia
A ica
To al
k /y
Wo ldwide maleic anhyd ide p oduc ion
2000
2005
2009
T
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
6
consolida ion wi h olde smalle plan s, especially in Eu ope and Asia (7).
Global MAN demand is expec ed o g ow by a leas 4% pe yea , a li le abo e- o ecas ed GDO a es. El i a
G eine , consul an a SRI Consul ing (Menlo Pa k, CA) s a ed ha “As long as he economy does well, demand
om UPR and BDO segmen s should con inue o d i e MAN demand” (11). E en oday, he mos impo an
ma ke s a e in Eu ope, The US, and Japan. O e all, i is possible o ex apola e an inc ease wi h ime in he
maleic anhyd ide global ma ke .
2.2 P ocess ou es
This compound was i s p epa ed in he 1830s bu i s comme cial manu ac u e did no begin un il a cen u y
la e . The i s indus ial p ocess was based on benzene oxida ion as eeds ock and anadium oxide ca alys in
1933 by he Na ional Aniline and Chemical Co., Inc. In 1962, Denka began p oducing maleic anhyd ide by
con e ing n-bu enes and a decade la e , Monsan o began p oduc ion by con e ing n-bu ane. Nowadays, he e
a e h ee main ways o p oduce maleic anhyd ide indus ially as seen in Figu e 6 (3).
Figu e 6 – Maleic anhyd ide p ocess ou es (12)
2.2.1 Benzene oxida ion
As men ioned be o e, he main p ocess ou e o maleic anhyd ide was ca ied ou by means o pa ial ca aly ic
oxida ion o benzene in apo phase:
(10)
6 6 2 4 2 3 2 2
922
2
C H O C H O CO H O
(1.1)
Benzene, al hough easily oxidized – e y exo he mic eac ion, -1,848 kJ/mole – o maleic anhyd ide wi h high
selec i i y is an ex emely ine icien eeds ock due o he excess o ca bon a oms be ween he eeds ock and he
end p oduc . The e o e, wo o ca bon a oms o benzene ha e o be emo ed by o ming ca bon dioxide (3)
(10).
This p ocessing ou e emains in companies wi h no al e na i e eeds ock. The echnology is qui e simila o
ixed bed n-bu ane plan s. Thusly, some companies e o i ed hei benzene plan s o use n-bu ane (13).
Besides maleic anhyd ide, he majo by-p oduc s o benzene oxida ion a e maleic acid, uma ic acid, ca bon
monoxide and wa e . Du ing maleic anhyd ide manu ac u e, small amoun s o benzoquinone ha e been ound
in eac ion p oduc s, husly conside ing i an in e media e p oduc . In addi ion o benzoquinone, o maldehyde,
diphenyl, phenol, and hyd oquinone a e also epo ed o be p oduced in small amoun s (14).
Maleic anhyd ide
Ph alic anhyd ide
by-p oduc
Linea C4
hyd oca bons
Benzene
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
7
2.2.2 Linea C4 hyd oca bon eeds ock
Rapid inc eases in he p ice o benzene and he ecogni ion o benzene as a haza dous ma e ial made he p ocess
obsole e. The e o e, he sea ch o al e na i e p ocess echnology in ensi ied. Since he 1960s, he numbe o
p oduc ion plan s wi h n-bu ane as a eeds ock has inc eased s eadily. Howe e , ea ly bu ane-based ca alys s
we e no ac i e and selec i e enough o allow he con e sion o benzene-based plan s wi hou signi ican loss o
namepla e capaci y. La e ad ances in ca alys echnology, inc eased egula o y p essu es, and con inuing cos
ad an ages o bu ane o e benzene ha e led o a apid con e sion o benzene- o-bu ane-based plan s. Nowadays,
he pa ial oxida ion o n-bu ane is he p edominan p ocess ou e o maleic anhyd ide (3) (10).
The p oduc ion o maleic anhyd ide by means o pa ial oxida ion o a linea C4 hyd oca bon can be gene ally
exp essed by he ollowing eac ion:
(10)
4 y 2 4 2 3 2
y
C H + 1+ O 1
42
y
C H O H O
(1.2)
whe e he amoun o hyd ogen in he hyd oca bon y equals 10 o n-bu ane and 8 o n-bu ene. This eac ion is
also e y exo he mic – -1,236kJ/mole – al hough i is lowe han he benzene eeds ock p ocess ou e. A ac ion
o he oxygen a oms is inco po a ed in he hyd oca bon molecule. All bu wo o he hyd ogen a oms in he
hyd oca bon ha e o be emo ed. This is achie ed by means o oxida i e dehyd ogena ion esul ing in he
o ma ion o wa e . Mos o he p o ided oxygen a oms a e used o his pu pose (10) (13).
The na u e o by-p oduc s is qui e di e en om hose o benzene. Among hem a e he lowe monoacids
(ace ic, ac ylic…) and he co esponding aldehydes. Some o hese a e p oduced in amoun s oo small o make
an economic eco e y possible. In ei he si ua ion, ni ogen, wa e , and he ca bon oxides a e en ed o he ai
a e eco e y o p oduc s and hyd oca bons (14).
N-bu ane is p esen in some ypes o na u al gas and in c ude oil and can be eco e ed by dis illa ion. I is also
p oduced by a numbe o e ine y c acking and e o ming p ocesses. Cases whe e maleic anhyd ide plan s a e
no nea n-bu ane sou ces, anspo cos s o he eeds ock could be a eason o u ning o o he s which a e
p esen a he chemical plan 's si e. Possible eeds ocks could be he a ious componen s o C4 s eams ob ained
by s eam c acking (10).
2.2.3 By-p oduc o ph halic anhyd ide
Besides chemical con e sion o sui able hyd oca bons, especially linea C4 hyd oca bons, maleic anhyd ide may
also be ob ained as a by-p oduc o ph halic anhyd ide p oduc ion in quan i ies o abou 5 - 6% in ela ion o he
p oduced ph halic anhyd ide. Du ing he manu ac u e o ph halic anhyd ide om naph halene and o-xylene,
small amoun s o maleic and ci aconic anhyd ide, as well as benzoic acid, a e cop oduced. In some cases, a e
he emo al o ph halic anhyd ide h ough condensa ion, he exhaus gases a e sc ubbed wi h wa e . In many
cases, he aqueous solu ion o maleic acid is eco e ed in he o m o uma ic acid. Since he boiling poin o
maleic anhyd ide and ci aconic anhyd ide a e 199 ºC and 213 ºC, espec i ely, a small amoun o ci aconic
anhyd ide always accompanies he dis illed maleic anhyd ide, lowe ing i s mel ing poin sligh ly (10) (14).
2.3 Technologies
Se e al echnologies exis o he p oduc ion o maleic anhyd ide which can mainly be classi ied in o h ee
ca ego ies depending on he ype o eac o ha is used: mul i- ubula ixed bed, luidized bed, and anspo bed
eac o s (8).
2.3.1 Mul i- ubula ixed bed eac o s
Like o he highly exo he mic oxida ion eac ions, he pa ial oxida ion o hyd oca bons o maleic anhyd ide
canno be ca ied ou in a simple ixed bed o ca alys pelle s. The ca alys bed mus be cooled e icien ly o
p e en high empe a u es which a e de imen al o eac o pe o mance and des oy he ca alys . The e o e,
mul i- ubula eac o s a e used (10).
Indus ial ixed bed eac o s no mally consis o app oxima ely 30,000 indi idual ubes which illed wi h ca alys
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
8
pelle s. These ubes ypically measu e be ween 3.5 o 6 m in leng h and ha e inne diame e s o abou 20 o 35
mm. Mol en sal lowing h ough he shell side is used o cool he ubes as men ioned be o e. The low o he
mol en sal is di ec ed pe pendicula o he ubes by ba les o op imum hea ans e om he ube insides o
he sal . The hea is emo ed om he ci cula ing sal ba h by gene a ing high-p essu e s eam. The maximum
capaci y o a single, mul i ubula ixed bed eac o is limi ed o abou 20,000 me ic ons pe yea (3) (10).
The hyd oca bons usually en e he eac o om he op and a e in ensi ely mixed wi h a sepa a e ai s eam by
s a ic mixe s. The esul ing mix u e hen en e s he eac o ubes. Due o he sepa a e eeding o hyd oca bons
and oxygen, long esidence imes wi h condi ions abo e he explosion limi a e a oided. The p oduc s lea e he
eac o a he bo om. Because o his di ec ion o low, no luidiza ion can occu and he ca alys pelle s emain
in hei posi ions. The eac o o -gas mus be incine a ed o des oy un eac ed bu ane and by-p oduc s be o e
being en ed o he a mosphe e. Typically, he eac ions a e ca ied ou a empe a u es be ween 350 and 450 ºC
and a sligh ly ele a ed p essu es o 2 – 3 ba . Fo he p oduc ion o maleic anhyd ide, hese eac o s ope a e a
a maximum o 2.5 % n/n o n-bu ane in he inle eed. The bu ane- o-maleic anhyd ide eac ion ypically eaches
i s maximum e iciency (maximum yield) a abou 85 % bu ane con e sion (3) (10).
As gases a e ed in o he eac o ubes, hey a e gene ally coole han he mixed sal s in he hea exchange which
leads o a cooling e ec o he sal mix u e in he hea exchange . A mo e signi ican p oblem would be he gas
empe a u e in he eac o ubes is g ea e han he sal mix u e in he hea exchange . Unde his scena io, a ho
spo can be gene a ed in he ca alys ubes. I no con olled, hese ho spo s can nega i ely a ec he ca alys li e
and eac o main enance husly dec easing he eac o yield. Ope a ional con ol o he empe a u e is
challenging because he e a e no mally housands o ubes and only a ew poin s o empe a u e measu emen .
I is impo an o highligh he ac ha ho spo s may also lead o possible unaway p ocess condi ions. Fo
addi ional sa e y, he eac o s a e equipped wi h up u e disks a bo h he eac o inle and exi a eas in case o a
unaway e en (6).
Al hough he ixed-bed con igu a ion is well known and has been in p ac ice o se e al yea s, i can also be
scaled-up e y easily. Howe e , limi ed hyd oca bon inle concen a ions due o explosion haza ds, possible ho
spo s and ca alys ins abili y, as well as i s egene a ion, ha e been among he majo conce ns acing his
echnology (3) (10).
2.3.1.1 Hun sman
Du ing he ea ly 90’s Hun sman Chemical Co po a ion acqui ed Monsan o’s maleic anhyd ide business which
main eeds ock is C4 hyd oca bon including n-bu ane o bu ene. I is impo an o poin ou he ac ha his
p ocess mainly ocuses on he eco e y and pu i ica ion s ages o maleic anhyd ide a he han he eac ion s age.
To be e unde s and his p ocess, a basic p ocess low diag am has been included in his wo k – Figu e 7– (6).
Using his echnology, maleic anhyd ide is p epa ed comme cially by con ac ing a eed gas comp ising
molecula oxygen and he a o emen ioned C4 hyd oca bon wi h a anadium-phospho us-oxygen (VPO) ca alys
o pa ially oxidize he hyd oca bon in a ixed bed eac o . The eac ion p oduc gas which is p oduced con ains
maleic anhyd ide oge he wi h oxida ion by-p oduc s such as CO, CO2, wa e apo , ac ylic and ace ic acids
and o he by-p oduc s, explained in p e ious sec ions, along wi h ine gases p esen in he ai when used as a
sou ce o molecula oxygen.
Due o inc eased p oduc yields, he p e e ed me hod o eco e y comp ises selec i ely abso bing he maleic
anhyd ide in a sui able sol en and subsequen ly s ipping he maleic anhyd ide om he esul ing abso p ion
liquo o ob ain c ude p oduc .
Maleic anhyd ide is ex ac ed om he eac o e luen s eam using a sol en ex ac ion p ocess. The sol en
en e s h ough he op o he column while he ex ac ed gaseous s eam is en ed h ough he op and he ich
sol en con aining maleic anhyd ide is wi hd awn h ough he bo om. The ich sol en is hen in oduced in o a
s ipping column which ypically ope a es a below a mosphe ic p essu e and a s eam o c ude maleic anhyd ide
may be ex ac ed as a gas o a liquid.
In cases whe e c ude maleic anhyd ide is ex ac ed as a gas, i may be condensed o yield a liquid s eam. In
o he cases, he s ipping column is e luxed by condensing an o e head s eam and e u ning a po ion o he
condensa e o he op o he s ipping column o may e en be o ally e luxed.
The sol en en e s a eboile whe e i is hea ed by a hea exchange , a e wa d, i is cooled, and ecycled o
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
9
he abso be column. The ecycled sol en may also be il e ed and s o ed in a s o age ank. In he e en o
sol en decomposi ion wi hin he p ocess, esh sol en may be added o he s o age ank.
E luen eac o componen s wi h low boiling poin s ha a e ex ac ed in o he sol en in he abso be column
o p oduced as byp oduc s o he ex ac ion p ocess a e en ed om he s ipping column.
Maleic anhyd ide ha exi s h ough he en line is eco e ed by sol en ex ac ion in a sc ubbe a condi ions
simila o hose in he condense , and he sc ubbed sol en s eam con aining maleic anhyd ide is e u ned o he
abso be column h ough a sc ubbed sol en line. The low boiling componen s no emo ed by he sc ubbe exi
he p ocess h ough a sc ubbe en line. The sol en used o he sc ubbing p ocess is ed o he sc ubbe di ec ly
om he sol en s o age ank (15)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
10
Figu e 7 – Hun sman basic p ocess low diag am o maleic anhyd ide manu ac u e (3) (15)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
17
Figu e 12 – BASF maleic anhyd ide p ocess low diag am (14)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
18
2.3.2 Fluidized bed eac o s
As men ioned be o e, he p oduc ion o maleic anhyd ide is highly exo he mic he e o e his ype o eac o also
equi es e icien hea emo al by cooling coils loca ed inside he luidized bed and gene a ing high-p essu e
s eam inside he coils. The apid mixing o he ca alys pa icles in he luidized bed p e en s local ho spo s,
he e o e, achie ing a uni o m empe a u e h oughou he bed wi h p ecise empe a u e con ol. Yield losses
associa ed wi h said ho spo s a e a oided husly inc easing he ca alys li e. The use o ine ca alys pa icles
esul s in be e u iliza ion o he pa icle su ace and in educed empe a u e and concen a ion g adien s wi hin
he pa icles. Howe e , due o an ab up ly changing mo ion o he pa icles, he mal and e en chemical s esses
may cause a i ion esul ing in loss o ca alys (3) (10).
Loading and unloading o he ca alys s a e much easie in he luidized bed sys ems compa ed o ixed-bed
sys ems. These eac o s a e scalable o e y la ge diame e allowing economies o scale and capaci ies anging
abou 40,000 me ic ons pe yea p o ing lowe in es men pa icula ly o a la ge-scale (17).
In his case, apo ized hyd oca bons a e injec ed di ec ly in o he luidized ca alys bed and he ai is ed om
he bo om o he eac o lowing upwa ds wi h eloci ies high enough o allow luidiza ion husly keeping in
suspension he ca alys powde . The p oduc s eam con ains bo h gases and undesi able solids which a emo ed
by using ei he cyclones, il e s, o a combina ion. A e wa d, he p oduc gas s eam mus be cooled be o e
being sen o he collec ion and e ining sys em.
Like ixed bed eac o s, he eac ions a e ypically ca ied ou a empe a u es below 450 ºC a p essu es anging
be ween 2 and 4 ba . The n-bu ane ac ion in he inle eed is abou 4 – 5% n/n. o p oduce maleic anhyd ide.
The hea capaci y o he ca alys and he apid hea ans e by he mo emen o he pa icles p e en s he
o ma ion o a lame on , he e o e, allowing no iceably highe hyd oca bon concen a ions compa ed o ixed-
bed eac o echnologies. Con e sion le els a e usually abo e 80% and mola yields o maleic anhyd ide ange
be ween 50% and 55% (3) (10).
Recapping, he main ad an ages o his ype o eac o a e:
High hea ans e coe icien .
Ease o empe a u e con ol and elimina ion o ho spo s.
High C-4 concen a ions in he eed.
Howe e , he e a e also disad an ages ha mus be poin ed ou :
Possible ca alys losses due o a i ion.
Yield losses associa ed wi h back mixing in he eac o .
Some scale-up unce ain ies due o he changes in eac o size making i di icul o p edic he eac o ’s
pe o mance including poo e gas-solid con ac , longe gas esidence ime dis ibu ion and inc eased
back mixing.
2.3.2.1 Mi subishi
A p ocess diag am has been a ached o a be e unde s anding o his echnology – Figu e 13. This p ocess
came in o use in 1970 by o me Mi subishi Kasei – cu en ly Mi subishi Chemical Co po a ion (18) – p ocess
uses c ude C4 ac ion om a naph ha c acke as a eed hence can use n-bu ane o n-bu ene con aining bu adiene
and isobu ylene. In he eac o sec ion, he C-4 ac ion is ed wi h ai in o he eac o o con e sion o maleic
anhyd ide in con ac wi h he luidized ca alys . The hea o eac ion is emo ed by cooling coils in he eac o
gene a ing high p essu e (430-710 psi) s eam. The eac ed gas con aining maleic anhyd ide is abso bed by wa e
in a quench owe so ha an aqueous solu ion o maleic acid is o med. O -gas om he quench owe ,
con aining a small numbe o byp oduc s, is incine a ed in he was e gas combus ion chambe gene a ing mo e
high-p essu e s eam. In he dehyd a ion/pu i ica ion sec ion, maleic acid is concen a ed and dehyd a ed by a
p ocess which ope a es e ec i ely in a sho ime. The c ude maleic anhyd ide is pu i ied by simple dis illa ion
o mee equi ed speci ica ions. The p ocess is conside ed easible and economical, especially when cheap and
ich C-4 hyd oca bons a e a ailable om a naph ha c acke and when a la ge amoun o su plus high-p essu e
s eam can be used a he same si e (14)(17).
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
19
Figu e 13 – Mi subishi maleic anhyd ide p ocess low diag am (17)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
20
2.3.2.2 ALMA
In ea ly 1984, Alusuisse I alia/Lummus C es (ALMA) implemen ed a maleic anhyd ide p ocess in ol ing a
luid-bed eac o . A low diag am o he ALMA P ocess is shown in Figu e 14. In his eac o con igu a ion, C4
and ai a e ed sepa a ely o he luidized bed eac o o gi e abou 4 mola pe cen n-bu ane concen a ion. The
eac o is ypically ope a ed a 360 – 460 ºC. The hea gene a ed du ing he oxida i e p ocess is emo ed om
he eac o ia s eam coils ha a e in in ima e con ac wi h he luidized solid ma e ials. An in e es ing
componen o his p ocess is he abili y o change ca alys du ing ope a ion by in e mi en ly adding a i gin
ca alys o main ain s able ac i i ies and pa icle size dis ibu ions.
Pa i ioning o he solids is achie ed by cyclone and il e sepa a ion. Once sepa a ed, he p oduc gas s eam is
cooled p io o he collec ion and e ining s ages. As in he ixed-bed p ocesses, any ail gases a e incine a ed
p io o en ing.
The p ocess employs sol en adso p ion using an o ganic sol en o selec i ely emo e maleic anhyd ide om
he cooled eac o e luen . Typically, he sol en is a cycloalipha ic acid dialkyl es e such as
dibu ylhexahyd oph hala e which ha e a highe boiling poin han maleic anhyd ide. The exclusion o wa e
elimina es byp oduc o ma ion expe ienced wi h an aqueous eco e y sys em. I allows he en i e maleic
anhyd ide p oduc ion o be sepa a ed om he eac o e luen in a single abso p ion s ep.
F om he e, he maleic anhyd ide sol en mix u e is pumped o he s ippe whe e c ude maleic anhyd ide is
sepa a ed as dis illa e. This ma e ial is ed o he ligh ends column whe e small amoun s o impu e ligh ends
a e emo ed and incine a ed. The emaining ma e ials a e ed o he p oduc column whe e he maleic anhyd ide
p oduc is eco e ed as dis illa e and esiduals a e pumped back o he s ippe . The e is also a sol en
pu i ica ion loop o p e en he buildup o impu i ies in he sol en . P ocess impu i ies ypically consis o ca bon
monoxide and ace ic and ac ylic acids (3) (6).
2.3.2.3 Badge
Badge de eloped hei p ocess wi h Denka Chemical Co po a ion. A low diag am o he Badge P ocess is
shown in Figu e 15. In which, a subs an ial ac ion o maleic anhyd ide is condensed and eco e ed as a liquid
by cooling he eac o e luen while he es o he p oduc is abso bed in wa e as maleic acid.
The acid is dehyd a ed o anhyd ide p e e ably using a wa e -en aining agen such as xylene. This p ocess has
claimed ha he luidized bed ca aly ic oxida ion o n-bu ane using he Badge P ocess p oduces maleic
anhyd ide a good yields wi h educed u ili ies equi emen s and wi h a subs an ially lowe ed capi al in es men .
This is a ibu ed o disco e y and de elopmen o a i ion esis an ca alys whose pe o mance does no change
wi h ime, oge he wi h an op imum luidized bed eac o design (17).
2.3.2.4 BP-UCB
In 1987, BP acqui ed Sohio ou igh and made i he co ne s one o a new na ional ope a ion, BP Ame ica. Sohio
de eloped he oxida ion ca alys sys em while UCB ope a ed he eco e y and pu i ica ion sys em. A low
diag am o his p ocess is shown in Figu e 17. This p ocess claims ha he ca alys gi es o e 50 % yield o
maleic anhyd ide on a once- h ough basis. As wi h he Badge P ocess, up o abou 50% o he maleic anhyd ide
is con inuously condensed ou by cooling he e luen gases below he dew poin o he maleic anhyd ide, bu
abo e he dew poin o wa e . The specially designed condense ne e needs o be pu ou o se ice o washing.
The emaining p oduc is abso bed in wa e as maleic acid.
This p ocess chooses no o use any o ganic sol en as an en aine o he dehyd a ion s ep. Ins ead, he c ude
maleic acid solu ion is i s e apo a ed unde acuum, and a e wa d he mally ans o med o anhyd ide in a
dehyd a ion eac o specially de eloped o educe he isome iza ion o maleic acid o uma ic acid (17) (19).
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
21
Figu e 14 – ALMA maleic anhyd ide p oduc ion p ocess (14) (17)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
22
Figu e 15 – Badge maleic anhyd ide p ocess diag am (17)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
23
Figu e 16 – BP/UCB maleic anhyd ide diag am low (17)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
24
2.3.3 T anspo bed eac o s (CFB)
A new eac o concep o selec i e oxida ion o n-bu ane o maleic anhyd ide was c ea ed. This inno a ion
educes o elimina es mos o he nega i es o luidized bed eac o men ioned be o e while main aining i s
ad an ages. Fu he mo e, addi ional pe o mance ad an ages a e ob ained by sepa a ing wo s eps o he edox
p ocess (17).
In hese con ac ing egimes, solids ci cula e in and ou o he bed and mus be eplaced by using anspo bed
eac o s in con inuous ope a ions. Flow models a e e y ske chy o hese low egimes and esea ch is needed.
The su ace o he dense bed ades and solids a e ound inc easingly in he lean egion abo e he dense bed
(uppe mos pa ). The gas low in he dense egion is somewhe e be ween he bubble luidized bed, BFB, and
plug low. Un o una ely, no easonable low model has been de eloped o his egion being ha he pa ame e s
o easonable models a e unce ain; hence, he p edic ions based on hese models will likewise be unce ain
(20).
Vanadium Phospho us Oxide, VPO, ca alys is no mally used since i has he in e es ing ea u e ha i uses
la ice oxygen a oms o he selec i e oxida ion o n-bu ane o maleic anhyd ide. The e o e, no gas phase oxygen
is necessa y o he desi ed eac ion p o ided he ca alys is in an oxida ion s a e capable o ans e ing oxygen
a oms o he hyd oca bon. In he eac o ’s egene a o , he ca alys is hen eoxidized wi h oxygen closing husly
i s cycle h oughou he CFB (10).
A anspo bed eac o can be ega ded as a ube in which bo h, he hyd oca bon and he ca alys a e b ough
in o con ac en e ing and exi ing he eac ion zone in co-cu en low. The ca alys is ci cula ed con inuously
a ound he loop; be ween bo h eac o s. n-Bu ane is oxidized by he ca alys in he lean-phase ise sec ion which
has plug low cha ac e is ics. The ca alys is eoxidized in he dense phase luidized bed egene a o (10)(17).
The mos signi ican ea u e o his eac o is he sepa a e educ ion and oxida ion sec ions allowing much highe
n-bu ane concen a ions in he inle eed as well as highe maleic anhyd ide selec i i y while a oiding he
men ioned lammabili y anges. The hyd oca bon ac ion in he inle eed may each up o 50 % n/n. Due o an
oxygen- ee gas phase, he selec i i y o maleic anhyd ide can be inc eased by alues o abou 7 o 10%
compa ed o he con en ional use o a hyd oca bon in ai gas phase in he o he eac o con igu a ions. Toge he
wi h he a i ion esis an ca alys desc ibed ea lie , i is possible o achie e maleic anhyd ide yields highe han
70 % and e en 90 % selec i i y. Tempe a u e ope a ion anges be ween 360 – 420 ºC and ise op p essu e is
possible up o 4.1 ba . The a e o eoxida ion o he VPO ca alys is slowe han he a e o oxida ion o bu ane,
and consequen ly, esidence imes a e longe in he oxidize han in he anspo bed eac o . The e o e, he gas
esidence ime in he ise is abou 10 seconds while ca alys esidence ime anges om 30 seconds o 5 minu es.
Ca alys densi ies 80 - 60 kg/m3 in he anspo bed eac o a e subs an ially lowe han he ca alys densi y in a
ypical luidized-bed eac o 480 – 640 kg/m3 (3)(10)(21)(22).
The main gene al ad an ages o his eac o con igu a ion a e ecapped (22):
Sepa a e ca alys oxida ion and educ ion zones which lead o independen con ol o wo zones wi h
he ca alys in ansien cyclic s a e. The e o e, sepa a e op imiza ion o each eac ion zone is possible
(3).
High selec i i y is essen ially due o plug low o gases in he ise , op imized oxida ion s a e o he
ca alys , con olled low oxygen concen a ion in he ise zone and ope a ion a low single pass
con e sion wi h ecycling o uncon e ed n-bu ane.
Highly concen a ed p oduc s eams because o high hyd oca bon concen a ion in he inle eed and
p oduc gas sepa a e om he egene a o o -gas.
Low ca alys in en o y.
No explosi e isks.
Howe e , he majo limi a ion is he in insically low oxygen ans e capaci y o he anadyl py ophospha e
VPP ca alys which equi es ex emely high solid eci cula ion a es o p o ide adequa e oxygen o he eac ion
(21).
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
25
2.3.3.1 Du Pon ’s C-4 eeds ock
Al hough maleic anhyd ide is p oduced in he eac ion sec ion o he p ocess and could be eco e ed, i is no a
di ec p oduc o he p ocess. DuPon ’s echnology eco e s maleic anhyd ide as aqueous maleic acid o
hyd ogena ion o e ahyd o u an. In his con igu a ion, maleic anhyd ide p oduc i i y could be enhanced by
using ela i ely high concen a ions o n-bu ane as main eeds ock and e ec i e u iliza ion o ca alys la ice
oxygen. Howe e , in p ac ice, due o insu icien ca alys oxygen ans e om he egene a ion zone, molecula
oxygen has o be ed along wi h he educ ion eed o achie e he designed maleic anhyd ide p oduc ion a es
and o p e en ca alys o e - educ ion (10) (17).
DuPon ’s maleic anhyd ide echnology includes a wo-s ep p ocess as men ioned be o e. Fi s ly, no mal bu ane
is oxidized o maleic anhyd ide in a anspo bed eac o using an ab asion- esis an ca alys (VPO o VPP).
Maleic anhyd ide is hen eco e ed in an aqueous sys em whe e he esul ing maleic acid is con e ed o
e ahyd o u an in a hyd ogena ion eac o . The oxygen deple ed ca alys is hen e-oxidized in a sepa a e eac o
whe e he exo he mic hea o eac ion is emo ed by s eam coils. The e o e, Du Pon has buil a p oduc ion plan
comp ising a anspo bed eac o o he n-bu ane oxida ion and a luidized bed egene a o o he eoxida ion
o he VPO-ca alys (3) (10) (13).
The ca alys goes h ough an oxida ion/ educ ion cycle each ime i ci cula es a ound he loop. Mo eo e , he
nea plug low o gases in he ise allows he s aged addi ion o eac an s o con ol gas composi ion in he axial
di ec ion o op imal pe o mance. In o he wo ds, p e en ing he nega i e e ec o back mixing on he
eac ion’s selec i i y. The eac o concep allows independen con ol o he p ocess a iables o he wo s eps
o he edox ope a ion o de ining op imum condi ions o each s ep (3) (22).
The oxidized ca alys is ans e ed om he egene a o h ough a s andpipe o he bo om sec ion o he eac ion
essel ( as bed) which is in u bulen luidiza ion egime. The solids and gas mix u e a e hen ans e ed in an
upwa d low h ough a ise eac o . Reduced ca alys om he ise op is sepa a ed om he eac ion p oduc s
s eam by cyclones and is u he s ipped o p oduc s and eac an s in a sepa a e s ipping essel. A e p oduc
sepa a ion, he educed solids we e e u ned o he egene a o h ough ano he s andpipe o eoxida ion. Maleic
anhyd ide in he p oduc s eam is emo ed and con e ed o a maleic acid solu ion in a wa e sc ubbing sys em.
The maleic acid is sen o he hyd ogena ion eac o o p oduce THF, while he eac o o -gas a e sc ubbing
is sen o he ecycle comp esso . A small pu ge s eam is sen o incine a ion (3).
Figu e 17 – T anspo bed eac o (3)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
26
Figu e 18 – Du Pon anspo -bed p ocess (3)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
33
Figu e 22 – Abso be T-100 con igu a ion
Also en e ing he column is s eam 30, which comes om he bo om ou le o he second abso be (T-103) ha
is ecycled (RCY-3) in o main abso be T-100. This s eam con ains mos ly DBP, wa e , MAN and un eac ed
n-bu ane.
O e head s eam 15 is he p ocess’ main ecycle (RCY-2) which is a dis inguishing speci ica ion o Dupon ’s
echnology, as men ioned in Chap e 2. The e o e, he composi ion o his s eam is mainly ni ogen and n-
bu ane and in smalle pe cen ages he o he oxida ion p oduc s.
Lea ing he abso be h ough he bo om o he column is s eam 14 which is made up o o ganic sol en and
he abso bed maleic anhyd ide. This s eam becomes he inle liquid eed o he s ippe 12- ay column T-101
which ope a es a acuum (6.66 kPa and 11.87 kPa) and a e lux o 2.
Figu e 23 – S ippe T-101 con igu a ion
Since said column ope a es a acuum condi ions, a ecip oca ing pis on pump has been placed in he exi ing
liquid o ganic sol en s eam. This pump is a ype o posi i e displacemen pump which ope a es wi h s eam
d i e di ec ly h ough gea s o bel s and is sealed bo h in e nally and ex e nally. The ope a ion o his equipmen
is shown in Figu e 24. I mainly wo ks wi h an ini ial suc ion s oke ollowed by a discha ge s oke. The i s
s oke akes place when he pis on pulls ou o he cylinde whe e a low-p essu e acuum is c ea ed ha causes
he suc ion al e o open and he discha ge al e o close. On he e u n s oke, he suc ion al e is closed and
he luid is o ced ou o he discha ge. No mally hese pumps a e placed in pa allel in o de o educe low and
p essu e luc ua ions (27).
Figu e 24 – Recip oca ing pis on pump ope a ion (27)
F om column T-101, he e a e h ee s eams exi ing. S eam 16 is he gaseous p oduc lea ing he condense .
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
34
Which is mainly o med by he lowe boiling componen s. S eam 18 is he ecupe a ed o ganic sol en line
which is ecycled (RCY-4) back in o he main abso be , as men ioned be o e.
S eam 16 en e s sc ubbe T-103, wi h he objec i e o ex ac ing he MAN ha may ha e no been s ipped in
column T-101. This abso be is a 10- ay column ha ope a es a he same condi ions as T-100. F om T-103,
o e head gaseous s eam 28 is en ed. Bo oms (s eam 26) a e ecycled (RCY-3) back in o T-100 a e cooled,
as men ioned be o e. Liquid inle s eam 32 is made up o pu e o ganic sol en .
Figu e 25 – Sc ubbe T-103 con igu a ion
3.2.5 Pu i ica ion
Dis illa ion column T-104 is a 6- ay column condense ope a es a 6.66 and eboile a 11.87 kPa, a e lux o 1
and a MAN mola ac ion o 0.98 in s eam 39. S eam 17 is he liquid line exi ing he condense which is made
up o mos ly wa e and MAN. Since he pu i y o he end p oduc does no mee he speci ica ions, his s eam
en e s a dis illa ion column whe e MAN is concen a ed o 98 %n/n pu i y (s eam 39). Excess wa e (s eam
38) is ecupe a ed h ough he column’s o e head. S eams C2 and R2 a e ene gy s eams ha a e in ol ed in
column T-104 co esponding o he hea emo ed om he condense and hea added o he eboile .
Figu e 26 – Dis illa ion column T-104 con igu a ion
3.3 Modeling and p ocess simula ion
3.3.1 Componen s p esen in simula ion
The hyd oca bon used o he simula ion is pu e n-bu ane (s eam 1) which is inse ed in o he eac o CRV-100
along wi h ni ogen (s eam 4) in app oxima ely a 3 %n/n / 97 %n/n a io. Oxygen and helium (s eams 8 – 12)
a e also in oduced in o he eac o in o de o oxidize he VPO ca alys which ollows a edox cycle h oughou
he equipmen . The p oduc s o he eac ion a e maleic anhyd ide, ca bon dioxide, ca bon monoxide and wa e .
In o de o emo e he main p oduc om he es o componen s, he o ganic sol en used in he abso be s is
dibu yl ph hala e.
3.3.2 The modynamic aspec s
The he modynamic model chosen o his wo k has been he Non-Random Two Liquids (NRTL) based on
con as ed expe imen al da a ob ained om a esea ch pape a h ee gi en empe a u es: 140.05 ºC, 160.05 ºC,
and 180.05 ºC (23). Each igu e shows a compa ison be ween he bina y P-x(y) g aphs o DBP sol en and
MAN p o ided by Aspen HYSYS, loca ed on he le , and he eg ession ob ained by plo ing he expe imen al
da a, on he igh . The ac ha he bina y in e ac ion da a o he NRTL model MAN-DBP pai was inse ed
manually in HYSYS should be no ed since i was no o e ed by he so wa e.
These igu es show he bubble and dew cu es o he bina y mix u e men ioned be o e. The cu es ha apply
o his case aken om he esea ch pape a e he iangle indica o s and do ed line. Whe e he iangle indica o s
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
35
co espond o he expe imen al da a and he do ed line is he calcula ed da a. The e o e, a e compa ing bo h
g aphs o each empe a u e and con i ming he simila i y be ween each o he , i is possible o accep he use o
he NRTL he modynamic model o he liquid phase o his wo k. In addi ion, i has also been conside ed o
he apo phase since he model o ideal gas has been assumed.
Figu e 27 – P-x(y) cu es compa ison a T=140.05 ºC
Figu e 28 – P-x(y) cu es compa ison a T=160.05 ºC
Figu e 29 – P-x(y) cu es compa ison a T=180.05 ºC
The i e adjus able pa ame e s o he NRTL equa ion in HYSYS a e he aij (2,204.92 cal/mol), aji (-278.64
cal/mol), bij (0.233 cal/mol*K), bji (-0.898 cal/mol*K), and αij e ms (0.3). Whe e i is linked o he o ganic
sol en and j is linked o MAN. This is he co esponding da a ha was inse ed manually in HYSYS and
ob ained om he esea ch pape . Equia ion 1.7 ep esen s he NRTL equa ion in HYSYS:
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
36
11
1
1 1 1
ln
exp( )
nn
ji j ji nmj m mj
j j ij m
ij
n n n
j
kj ki k kj k kj
k k k
ij ij ij
ij ij
ij
xG xG
xG
x G x G x G
G
a b T
RT
(1.7)
Whe e:
γi = ac i i y coe icien o componen i
xi = mole ac ion o componen i
T = empe a u e (K)
n = o al numbe o componen s
aij = non- empe a u e dependen ene gy pa ame e be ween componen s i and j (cal/gmol),
bij = empe a u e dependen ene gy pa ame e be ween componen s i and j (cal/gmol-K),
αij = NRTL non- andomness cons an o bina y in e ac ion no e ha
αij = αji o all bina ies
Howe e , he modynamic bina y in e ac ion da a be ween he sol en DBP and he es o componen s in he
abso be (wa e , ni ogen, un eac ed bu ane, ca bon monoxide and dioxide) ha e no been ound in eliable
sou ces such as:
Sp inge Ma e ials which he Uni e si y o Se ille’s lib a y does no ha e access o.
DECHEMA’s DETHERM so wa e demo does no o e Vapo -Liquid Equilib ia (VLE)
he modynamic da a o he a o emen ioned bina y mix u e.
The DETHERM ab in ASPEN Plus has no been a ailable o his wo k and he NIST ab did no
p o ide any da a o said mix u e.
Jou nals o Da abases such as The Jou nal o Chemical Enginee ing Da a o Science Di ec possibly
could ha e o e ed ce ain da a h ough esea ch. Howe e , i would ha e jeopa dized he es ablished
deadlines o his wo k.
The e o e, he he modynamic bina y in e ac ion has been conside ed ideal mix u e.
3.3.3 Equipmen
In his subsec ion, he simula ion o each equipmen used in his wo k shall be explained. As seen in he a ached
PDF (Figu e 20), he ollowing equipmen ha e been included in he p oduc ion p ocess.
3.3.3.1 Reac o CVR-100
The simula ion o eac o CVR-100 has been ca ied ou by speci ying i s inle s eams (s eams 3 and 11), he
eac ions ha ake place, he desi ed empe a u e a which he eac ion occu s, con e sion and selec i i y.
3.3.3.2 Componen spli e X-100
This equipmen has been used in o de o sepa a e he oxygen exi ing he eac o in s eam 6 since he s ic
simula ion o a CFB eac o has no been ca ied ou in his wo k whe e i s inle s eam is pu in o con ac wi h
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
37
he oxidized ca alys .
The spli s we e in oduced manually by speci ying ha all o he oxygen p esen in s eam 6 shall be ans e ed
o s eam 8 and he es o gaseous p oduc s, un- eac ed n-bu ane and ni ogen a e sepa a ed in o s eam 7. In
o he wo ds, oxygen’s mola ac ion in s eam 8 is one and in s eam 7 is ze o.
3.3.3.3 Abso be s
3.3.3.3.1 T-100
Abso be T-100 has been simula ed by speci ying he inle s eams as well as he s age a which hey en e
(s eams 24, 13 and 30), he numbe o s ages, and he i s and las s age p essu e.
3.3.3.3.2 T-103
Sc ubbe T-103 is simula ed in he same manne as T-100. The inle s eams 16 and 32 we e speci ied as well
as he numbe o s ages and he p essu e o he i s and las s age.
3.3.3.4 Sho cu column
In o de o ob ain ini ial simula ion da a o he s ippe and dis illa ion column, wo sho cu columns ha e been
simula ed be o ehand.
3.3.3.4.1 T-102
Sho cu column T-102 has been simula ed o ob ain da a o he s ippe column T-101. As seen in Figu e 30,
h ee s eams a e in ol ed in his equipmen . Fi s ly, s eam 14 con aining a liquid mix u e o mos ly o ganic
sol en and maleic anhyd ide is in oduced in o he column. Secondly, s eams D1 (MAN and wa e ) and B1
(DBP) a e he dis illa e and bo oms exi ing he column. Las ly, s eams C1 and R1 a e he ene gy s eams linked
o he column’s condense and eboile .
Figu e 30 – Sho cu column T-102 con igu a ion
Fo such column, as seen in Table 1 he ollowing ini ial pa ame e s we e in oduced:
Ini ial pa ame e s
Ligh key in Bo oms (MAN) mole ac ion
0.0003
Hea y key in Dis illa e (DBP) mole ac ion
0.0003
Condense p essu e (kPa)
6.66
Reboile P essu e (kPa)
11.87
Ex e nal Re lux Ra io
1
Table 1– Sho cu Column T-102 ini ial pa ame e s.
These pa ame e s led o he ollowing simula ion da a (Table 2) ha was la e in oduced in he s ippe column
T-101:
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
38
Simula ion da a
Minimum numbe o ays
2,553
Condense empe a u e (ºC)
917.98
Reboile empe a u e (ºC)
240.5
Table 2 – Sho cu column T-102 simula ion da a.
3.3.3.4.2 T-105
Sho cu column T-105 has been simula ed o ob ain da a o he dis illa ion column T-104. As seen in Figu e
31, h ee s eams a e in ol ed in his equipmen . Fi s ly, s eam 17 composed o a liquid mix u e o wa e and
maleic anhyd ide is in oduced in o he column. Secondly, s eams D2 (wa e ) and B2 (MAN) a e he dis illa e
and bo oms exi ing he column. Las ly, s eams C2 and R2 a e he ene gy s eams linked o he column’s
condense and eboile .
Figu e 31 – Sho cu column T-105 con igu a ion
Fo such column, as seen in Table 3 he ollowing ini ial pa ame e s we e in oduced:
Ini ial pa ame e s
Ligh key in Bo oms (MAN) mole ac ion
0.0003
Hea y key in Dis illa e (DBP) mole ac ion
0
Condense p essu e (kPa)
6.66
Reboile P essu e (kPa)
11.87
Ex e nal Re lux Ra io
1
Table 3 – Sho cu Column T-105 ini ial pa ame e s.
These pa ame e s led o he ollowing simula ion da a (Table 4) ha was la e in oduced in he s ippe column
T-101:
Simula ion da a
Minimum numbe o ays
5.53
Condense empe a u e (ºC)
38.01
Reboile empe a u e (ºC)
132.10
Table 4 – Sho cu column T-105 simula ion da a.
3.3.3.5 S ippe T-101
The simula ion o a s ippe column is qui e a bi mo e complica ed han he abso be s. As men ioned be o e,
i s , a sho cu column is simula ed. Da a such as e lux a io, eboile empe a u e and dis illa e d aw a e is
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
39
ob ained om sho cu column T-102 and in oduced in o s ippe T-101. The inle s eam (s eam 14) is
speci ied, as well as, he numbe o s ages, i s and las s age p essu e and choice o condense ha is a pa ial
condense .
3.3.3.6 Dis illa ion column T-104
The e lux a io p o ided by sho cu column T-105 is in oduced in o s ippe T-101. Since he choice o
condense is a ull e lux condense , he e a e less deg ees o eedom conce ning inpu da a compa ed o s ippe
T-101. The inle s eam (s eam 17) is speci ied, as well as, he numbe o s ages and i s and las s age p essu e.
3.3.3.7 Hea exchange s
Th oughou he cou se o his wo k, six hea exchange s ha e been used. Table 5 e lec s, o each one o hese
equipmen , i s name, con igu a ion, s eams ha a e in ol ed, inle and ou le empe a u e in deg ees Celsius,
p essu e d op in kilo Pascals and a b ie explana ion. In he con igu a ion igu es (32 h ough 37), s eams E
p oceeded by a numbe co espond o he ene gy s eam in ol ed in ha speci ic hea exchange . The di ec ion
o hese ene gy s eams indica es whe he hea is added (inwa ds) o emo ed (ou wa ds) om he ma e ial
s eams.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
40
Name
Con igu a ion
Ma e ial s eams
in ol ed
Inle T
(ºC)
Ou le T
(ºC)
Del a P
(kPa)
B ie explana ion
E-101
Figu e 32 – Hea exchange E-101 con igu a ion
1 and 2
200
370
0
E-101 is used o hea he pu e hyd oca bon
s eam o inle eac o speci ica ions.
E-102
Figu e 33 – Hea exchange E-102 con igu a ion
9 and 10
229
370
0
E-102 is used o hea he pu e oxygen s eam
o inle eac o speci ica ions.
E-103
Figu e 34 – Hea exchange E-103 con igu a ion
7 and 40
374.5
55
0
E-103 is used o cool he exi ing spli e
componen s eam 7 in o de o mee
abso be T-100 inle empe a u e
speci ica ion.
E-104
Figu e 35 – Hea exchange E-104 con igu a ion
22 and 23
240
30
0
E-104 is used o cool he ecycled o ganic
sol en in o de o en e , a e being mixed
wi h esh sol en , abso be T-100 a a
speci ic empe a u e.
E-105
Figu e 36 – Hea exchange E-105 con igu a ion
29 and 30
148.6
60
0
E-105 is used o cool he s eam exi ing
sc ubbe T-103 ha is ecycled back in o
main abso be T-100.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
41
E-106
Figu e 37 – Hea exchange E-106 con igu a ion
36 and 37
86.89
370
0
E-106 is used o hea he main ecycle (RCY-
2) s eam in o de o be mixed wi h pu e
ni ogen.
Table 5 – Hea exchange s used in he simula ion
3.3.3.8 Comp esso s
In his simula ion, one comp esso s has been used. Table 6 p o ides in o ma ion including: name, con igu a ion, s eams in ol ed, inle and ou le p essu e and a b ie
explana ion. S eam K ollowed by a numbe is he ene gy s eam ha a e in ol ed in he equipmen ope a ion by supplying he comp esso wi h ene gy.
Name
Con igu a ion
S eams in ol ed
Inle P
(kPa)
Ou le P
(kPa)
B ie explana ion
K-101
Figu e 38 – Comp esso K-101 con igu a ion
35 and 36
113
150
K-101 is used o comp ess ecycled gases o p ocess
p essu e ope a ion.
Table 6 – Comp esso s used in he simula ion
3.3.3.9 Pump
The in o ma ion p o ided o he single pump used in his simula ion is shown in Table 7. As men ioned in he beginning o his chap e , his pump is a ecip oca ing pis on
pump which is used when wo king a acuum condi ions. S eam P0 is he ene gy supply o pump P-100.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
42
Name
Con igu a ion
S eams in ol ed
Inle P
(kPa)
Ou le P
(kPa)
B ie explana ion
P-100
Figu e 39 – Pump P-100 con igu a ion
18 and 19
11.87
113.3
P-100 is used o comp ess o ganic sol en liquid s eam
ha exi s column T-101 in o de o be ecycled back in o
column T-100.
P-101
Figu e 40 – Pump P-101 con igu a ion
26 and 27
11.87
113.3
P-101 is used o comp ess he liquid s eam exi ing
sc ubbe T-103 in o de o ecycle s eam 27 back in o
main abso be T-100
Table 7 – Pump used in he simula ion
3.3.3.10 Val e
Table 8 shows in o ma ion on he al e used in he simula ion co e ing aspec s such as name, con igu a ion, s eams in ol ed, inle and ou le p essu e and a b ie
explana ion.
Name
Con igu a ion
S eams in ol ed
Inle P
(kPa)
Ou le P
(kPa)
B ie explana ion
VLV-100
Figu e 41 – Val e VLV-100 con igu a ion
40 and 13
150
115
VLV-100 is used o elease s eam 40’s p essu e down
o abso be T-101 app op ia e inle p essu e.
Table 8 – Val e used in he simula ion
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
49
S eam
kg/h MAN
13
7,231.50
24
7.10
30
708.88
14
7,876.56
15
70.93
To al MAN mass low en e ing T-100 (kg/h)
7,947.48
MAN ecupe a ion (%)
99.10
Table 21 – T-100 MAN ecupe a ion
4.6 P oduc ecupe a ion in sc ubbe T-103
Table 24 o e s in o ma ion ela ed o he s eams in ol ed in he sc ubbe MAN ecupe a ion. The ecupe a ion
a e is de ined as he a io be ween MAN in p oduc s eam 26 and he o al MAN en e ing he column (s eam
16 and 32) imes 100, esul ing in 100 % in column T-103.
Exi Sc ubbe
P oduc Recupe a ion(%) *100
InSc ubbe
S eam26 *100
S eam16 S eam32
MAN
MAN
(1.16)
S eam
kg/h MAN
32
0.00
26
708.87
16
708.87
28
0
To al MAN mass low en e ing T-100 (kgmole/h)
708.87
MAN ecupe a ion (%)
100.00
Table 22 – T-103 MAN ecupe a ion
As o he o ganic sol en ecupe a ion, he s eams in ol ed in he sc ubbe conce ning DBP ecupe a ion a e
shown in Table 25. The sol en ecupe a ion a e is de ined he same as MAN a e, esul ing in his case a
pe cen age o 99.97 in column T-103.
Exi Sc ubbe
P oduc Recupe a ion(%) *100
InSc ubbe
S eam26 *100
S eam16 S eam32
DBP
DBP
(1.17)
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
50
S eam
kg/h DBP
32
10,500.25
26
10,497.74
16
0
0
2.51
To al DBP mass low en e ing T-100
10,500.25
DBP ecupe a ion (%)
99.97
Table 23 – T-103 DBP ecupe a ion
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
51
Uni
1
2
3
4
5
Vapou F ac ion
1
1
1
1
1
Tempe a u e
C
200.00
370.00
363.57
300.00
363.46
P essu e
kPa
150.00
150.00
150.00
150.00
150.00
Mola Flow
kgmole/h
100.00
100.00
33,190.54
3,233.00
33,090.54
Mass Flow
kg/h
5,812.40
5,812.40
923,283.47
90,566.03
917,471.07
Comp Mole Flow (H2O)
0
0
1,835.36
0
1,835.36
Comp Mole Flow (MaleicAnhyd )
0
0
0
0
0
Comp Mole Flow (DiiBPh hla e)
0
0
0
0
0
Comp Mole Flow (Ni ogen)
0
0
30,670.73
3,233.00
30,670.73
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
0
0
198.75
0
198.75
Comp Mole Flow (CO)
0
0
198.83
0
198.83
Comp Mole Flow (n-Bu ane)
100.00
100.00
286.13
0
186.13
Uni
6
7
8
9
10
Vapou F ac ion
1
1
1
1
1
Tempe a u e
C
441.55
469.50
300.00
229.00
370.00
P essu e
kPa
150.00
150.00
150.00
150.00
150.00
Mola Flow
kgmole/h
40,368.93
33,586.00
6,782.93
670.00
670.00
Mass Flow
kg/h
1,150,791.28
933,737.38
217,053.90
21,440.00
21,440.00
Comp Mole Flow (H2O)
2,192.19
2,192.19
0
0
0
Comp Mole Flow (MaleicAnhyd )
73.75
73.75
0
0
0
Comp Mole Flow (DiiBPh hla e)
0
0
0
0
0
Comp Mole Flow (Ni ogen)
30,670.73
30,670.73
0
0
0
Comp Mole Flow (Oxygen)
6,782.93
0
6,782.93
670.00
670.00
Comp Mole Flow (CO2)
224.50
224.50
0
0
0
Comp Mole Flow (CO)
224.58
224.58
0
0
0
Comp Mole Flow (n-Bu ane)
200.15
200.15
0
0
0
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
52
Uni
11
12
13
14
15
Vapou F ac ion
1
1
1
0
1
Tempe a u e
C
306.65
300.00
58.26
62.21
65.75
P essu e
kPa
150.00
150.00
115.00
115.00
113.32
Mola Flow
kgmole/h
7,109.62
6,439.62
33,586.00
499.13
33,349.12
Mass Flow
kg/h
227,507.81
206,067.81
933,737.38
78,597.90
923,619.32
Comp Mole Flow (H2O)
0
0
2,192.19
175.73
2,028.76
Comp Mole Flow (MaleicAnhyd )
0
0
73.75
80.33
0.72
Comp Mole Flow (DiiBPh hla e)
0
0
0
242.64
0.12
Comp Mole Flow (Ni ogen)
0
0
30,670.73
0
30,670.47
Comp Mole Flow (Oxygen)
7,109.62
6,439.62
0
0
0
Comp Mole Flow (CO2)
0
0
224.50
0
224.48
Comp Mole Flow (CO)
0
0
224.58
0
224.58
Comp Mole Flow (n-Bu ane)
0
0
200.15
0
200.00
Uni
16
17
18
19
20
Vapou F ac ion
1
0.00
0
0
0
Tempe a u e
C
60.63
60.63
240.80
240.87
240.87
P essu e
kPa
6.66
6.66
11.87
113.30
113.30
Mola Flow
kgmole/h
150.90
105.51
242.72
242.72
243.62
Mass Flow
kg/h
3,305.99
7,745.49
67,546.42
67,546.42
67,796.04
Comp Mole Flow (H2O)
143.23
32.49
0
0
0
Comp Mole Flow (MaleicAnhyd )
7.23
73.02
0
0
0
Comp Mole Flow (DiiBPh hla e)
0
0
242.64
242.64
243.54
Comp Mole Flow (Ni ogen)
0
0
0
0
0
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
0
0
0
0
0
Comp Mole Flow (CO)
0
0
0
0
0
Comp Mole Flow (n-Bu ane)
0
0
0
0
0
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
53
Uni
21
22
23
24
25
Vapou F ac ion
0
0
0
0
0
Tempe a u e
C
240.87
240.87
30.00
29.46
35.00
P essu e
kPa
113.30
113.30
113.30
113.30
113.30
Mola Flow
kgmole/h
16.44
227.17
227.17
205.01
22.16
Mass Flow
kg/h
4,576.23
63,219.81
63,219.81
57,051.35
6,168.45
Comp Mole Flow (H2O)
0
0
0
0
0
Comp Mole Flow (MaleicAnhyd )
0
0
0
0
0
Comp Mole Flow (DiiBPh hla e)
16.44
227.10
227.10
204.94
22.16
Comp Mole Flow (Ni ogen)
0
0
0
0
0
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
0
0
0
0
0
Comp Mole Flow (CO)
0
0
0
0
0
Comp Mole Flow (n-Bu ane)
0
0
0
0
0
Uni
26
27
28
29
30
Vapou F ac ion
0
0
1
0
0
Tempe a u e
C
84.60
84.68
66.58
84.67
60.00
P essu e
kPa
11.87
113.30
6.66
113.30
113.30
Mola Flow
kgmole/h
57.24
57.24
131.38
57.24
57.24
Mass Flow
kg/h
11,428.15
11,428.15
2,378.10
11,428.48
11,428.48
Comp Mole Flow (H2O)
12.30
12.30
130.94
12.30
12.30
Comp Mole Flow (MaleicAnhyd )
7.23
7.23
0
7.23
7.23
Comp Mole Flow (DiiBPh hla e)
37.71
37.71
0
37.72
37.72
Comp Mole Flow (Ni ogen)
0
0
0
0
0
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
0
0
0
0
0
Comp Mole Flow (CO)
0
0
0
0
0
Comp Mole Flow (n-Bu ane)
0
0
0
0
0
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
54
Uni
31
32
33
34
35
Vapou F ac ion
0
0
1
1
1
Tempe a u e
C
35.00
35.00
65.75
65.75
65.82
P essu e
kPa
113.30
113.30
113.32
113.32
113.32
Mola Flow
kgmole/h
15.56
37.72
3,334.91
30,014.21
29,857.54
Mass Flow
kg/h
4,331.81
10,500.26
92,361.93
831,257.38
826,905.04
Comp Mole Flow (H2O)
0
0
202.88
1,825.88
1,835.36
Comp Mole Flow (MaleicAnhyd )
0
0
0
0
0
Comp Mole Flow (DiiBPh hla e)
15.56
37.72
0
0
0
Comp Mole Flow (Ni ogen)
0
0
3,067.05
27,603.42
27,437.73
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
0
0
22.45
202.03
198.75
Comp Mole Flow (CO)
0
0
22.46
202.12
198.83
Comp Mole Flow (n-Bu ane)
0
0
20.00
180.00
186.13
Uni
36
37
38
39
40
Vapou F ac ion
1
1
1
0
1
Tempe a u e
C
101.98
370.00
38.08
121.40
60.00
P essu e
kPa
150.00
150.00
6.66
11.87
150.00
Mola Flow
kgmole/h
29,857.54
29,857.54
31.00
74.51
33,586.00
Mass Flow
kg/h
826,905.04
826,905.04
558.55
7,186.93
933,737.38
Comp Mole Flow (H2O)
1,835.36
1,835.36
31.00
1.49
2,192.19
Comp Mole Flow (MaleicAnhyd )
0
0
0
73.02
73.75
Comp Mole Flow (DiiBPh hla e)
0
0
0
0
0
Comp Mole Flow (Ni ogen)
27,437.73
27,437.73
0
0
30,670.73
Comp Mole Flow (Oxygen)
0
0
0
0
0
Comp Mole Flow (CO2)
198.75
198.75
0
0
224.50
Comp Mole Flow (CO)
198.83
198.83
0
0
224.58
Comp Mole Flow (n-Bu ane)
186.13
186.13
0
0
200.15
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
55
Uni
B1
B2
D1
D2
Vapou F ac ion
0
0
1
0
Tempe a u e
C
240.53
132.09
97.98
38.01
P essu e
kPa
11.87
11.87
6.66
6.66
Mola Flow
kgmole/h
242.64
73.04
256.49
32.47
Mass Flow
kg/h
67,510.29
7,160.47
11,087.61
585.01
Comp Mole Flow (H2O)
0
0.02
175.73
32.47
Comp Mole Flow (MaleicAnhyd )
0
73.02
80.18
0
Comp Mole Flow (DiiBPh hla e)
242.49
0
0
0
Comp Mole Flow (Ni ogen)
0
0
0
0
Comp Mole Flow (Oxygen)
0
0
0
0
Comp Mole Flow (CO2)
0
0
0
0
Comp Mole Flow (CO)
0
0
0
0
Comp Mole Flow (n-Bu ane)
0
0
0
0
Table 24 – Maleic anhyd ide p oduc ion wo kbook.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
56
5 CONCLUSIONS
The mo i a ion o his p esen wo k was he documen a ion o se e al maleic anhyd ide p oduc ion echnologies.
This disse a ion’s goal was o selec a speci ic echnology ha p oduced MA ia n-bu ane pa ial oxida ion and
simula e i wi h Aspen HYSYS so wa e.
The simula ion’s objec i e was success ully achie ed by ob aining a plan capable o p oducing 36,800 cubic
me e s pe yea o maleic anhyd ide a a pu i y o 98 % n/n. and a global p oduc ecupe a ion o up o 99.10 %.
Un- eac ed n-bu ane has been ecycled limi ing he losses o abou 20 %. Fu he mo e, alues highe han 99 %
p oduc eco e y om he abso be and sc ubbe ha e been ob ained o bo h MAN and DBP ecupe a ions.
This wo k has no aken in o conside a ion he ac ha maleic anhyd ide eac s eadily wi h wa e o p oduce
i s acid and uma ic acid as well. Fo u u e wo ks, is an in e es ing poin o in oduce hese eac ions in he
abso p ion and pu i ica ion sec ions o he p ocess plan . Since his p ocess has such an exo he mic eac ion, i
does equi e p ecise empe a u e con ol. Thusly aspec s conce ning p ocess con ol would also be e y
in e es ing o pe o m. Las ly, ma e s ha his wo k has no conside ed such as igo ous equipmen modelling,
ene gy in eg a ion and economic s udies a e o he aspec s o be aken in o accoun o u u e wo ks.
Aspen HYSYS Simula ion o Maleic Anhyd ide P oduc ion om n-Bu ane ia Pa ial Oxida ion
57
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