Production of Phenol and Acetone from Propylene and Benzene through Cumene Process
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Arban L. Legaspi , Edrian A. Mañalong , Myke Vivienne F. Salvacion , Engr. Marlon O. Martinez 1 !e"ical Engineering, Malayan olleges Lag#na, ab#yao ity $%2&, '!ilippines arbanlegaspi(ya!oo.co" , arbanlegaspi(ya!oo.co" , edrianz1%(g"ail.co" edrianz1%(g"ail.co",, salvacion"yke(ya!oo.co" 2 ollege o) Arts and Science, Malayan olleges Lag#na, ab#yao ity $%2&, '!ilippines "o"artinez("cl.ed#.p!
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Abstract: Abstract: *!e ai" o) t!is +ork is t!e intensi)ication o) an ind#strialscale prod#ction process o) p!enol and acetone )ro" propylene propylene and benzene t!ro#g! t!ro#g! t!e c!eapest and "ost reliable reliable tec!nology, tec!nology, t!e c#"ene process, process, to obtain !ig!er pro)itabil pro)itability ity and red#ce t!e energy re-#ire"ents o) t!e process. n t!e )irst step, t!e de"and and s#pply o) t!e prod#cts and ra+ "aterials o) t!e process is analyzed analyzed and t!e capital re-#ire"ents re-#ire"ents o) t!e plant plant is obtained obtained #sing t!e class & esti"ate. *!e *!e )ollo+ing )ollo+ing stage stage co"prises co"prises o) t!e si"#lation o) t!e "ain process and #tilities #sing AS'E/ 0SS version .%. 'ara"etric opti"ization +as carried o#t to ad3#st t!e process para"eters and obtain an e))icient and econo"ically )easible process. onsec#tively, S4L and OS4L e-#ip"ent +ere sized and t!eir cost +ere deter"ined #sing t!e "et!ods presented by *o+ler. *!e concl#ding stage co"prises o) a class 5 esti"ation o) t!e econo"ic )easibility o) t!e pro3ect. *!e capital invest"ent o) t!e pro3ect re"ained al"ost intact, aro#nd $.& billion '0'. *!e 66 is 278 and t!e ret#rn o) invest"ent is e9pected at year 7 starting )ro" t!e constr#ction period. Overall, t!e designers )ind t!e pro3ect )easible and t!ey reco""end to contin#e t!e pro3ect to its proc#re"ent, co""issioning, and operational p!ase. Keywords: #"ene process, Econo"ic Analysis, '!enol, Acetone, Alkylation
Introduction Finding a con)ig#ration and operational conditions o) a process in +!ic! a c!e"ical is "an#)act#red in a reliable and econo"ical "anner, considering several )actors s#c! as lo+ energy cons#"ption, lo+ initial capital invest"ent, lo+ or negligible environ"ental i"pact, and !ig! prod#ct yield is t!e "ain goal o) designing t!is plant +!ic! can prod#ce p!enol and acetone )ro" propylene and benzene t!ro#g! c#"ene process. Opti"ization o) t!e process involved is cond#cted +!en t!e )lo+ s!eet o) t!e base case and detailed !eat and "aterial balances o) t!e process are available. F#rt!er"ore, t!e econo"ic aspects o) t!e plant, incl#ding t!e sizing o) all t!e e-#ip"ent ;S4L and OS4L<, capital invest"ent, and #tility re-#ire"ents, s!o#ld be considered and eval#ated t!oro#g!ly. n t!is paper, t!e opti"ization o) t!e process t!at involves t!e alkylation o) propylene +it! benzene to prod#ce p!enol p!enol and acetone t!ro#g! t!e reno+ned reno+ned c#"ene process +as carried o#t to "ake t!e process process "ore e))ective, reliable, reliable, and t!#s "ore pro)itable. As co"pared to ot!er processes available, c#"ene process !as t!e lo+est cost o) prod#ction ;*y"an, 1==><. #rrently, t!e #"ene process is #niversally )avored in t!e ?nited @ingdo" ;?@< and ?nited States o) A"erica ;?S< beca#se o) its lo+er cost and !ig!er prod#ct yield, t!#s t!is process +ill be adapted in t!is pro3ect. *!e !#ge "a3ority o) c#"ene "an#)act#red +orld+ide is #tilized in t!e prod#ction o) p!enol and acetone ;Sc!"idt, 2%%&<. 6eactions occ#r in t!e presence o) vario#s catalyst. n t!is pro3ect, #sed catalysts catalysts are zeolites zeolites )or t!e alkylation alkylation o) benzene benzene +it! propylene propylene ;/oro#zi, ;/oro#zi, 0asani, 0addadiSisak!t 0addadiSisak!t,, Mosto#)i, 2%1$<, copper o9ide ;#O< nanoparticles )or t!e o9idation o) c#"ene to prod#ce c#"ene 0ydropero9ide 0ydropero9ide ;0'< ; 0'< ;B!ang, Cang, 0ongbing, C#, Beng, 2%%7<, and s#l)onic acid resins )or t!e cleaving o) 0ydropero9ide to prod#ce p!enol and acetone ;0#ang, 0an, Cang, Din, 2%%2<. *!e )ollo+ing e-#ations describes t!e reactions involved in t!e process:
! ! " # "## $%& %! %!' ' "## ## "# # # # '!%! ( )*+
;1< ;2< ;5< ;$<
*!e )irst license )or c#"ene prod#ction belongs to a corporation called ?O'. *!eir process involves reactions t!at occ#rs in gas p!ase +it! t!e presence presence o) S'A catalyst ;Ste)anidaki ;Ste)anidakiss +yn, 1=77<. 1=77<. Anot!er Anot!er license belongs belongs to Monsanto and and @ellogg, @ellogg, +!ic! #ses a "i9t#re o) All5 and 0l as t!e catalyst in a !o"ogeneo#s li-#idp!ase reaction o) benzene and propylene. *!e transalkylation o) ''4 is also possible in t!is process. *!#s, t!is process !as a !ig! yield. 0o+ever, corrosion o) pipes and e-#ip"ent are still a proble" proble" ;an)ield, o9, Mcart!y, 1=><. Li-#idp!ase and zeolitebased catalytic processes +ere
already developed by *ec!, Mobil4adger, and ?O' to prod#ce c#"ene ;/oro#zi, 0asani, 0addadiSisak!t, Mosto#)i, 2%1$<. #"ene can be )#rt!er processed to prod#ce "ore val#able prod#cts, p!enol and acetone t!ro#g! t!e c#"eneG!ock process. *!is process deals +it! t!e o9idation o) c#"ene 0ydropero9ide ;0'<, and is considered to be t!e key reaction o) ind#strial p!enol prod#ction process. Since t!e 1=7%Hs, "any invest"ents +ere "ade )or c#"ene o9idation. For all t!ese catalyst syste"s, copper co"po#nds +ere e9cellent catalysts not only +it! regard to t!e reaction activity b#t also +it! regard to t!e 0' selectivity ;B!ang, Cang, 0ongbing, C#, Beng, 2%%7<. At present, abo#t =$.&8 o) p!enol in t!e c!e"ical "arket is "an#)act#red by c#"ene deco"position, +!ic! +as developed in t!e 1=&%s. Si9 types o) catalysts t!at can be #sed )or 0' deco"position. *!ese are FreidelIra)ts catalysts s#c! as All5, inorganic and organic acids, silicates, "etallic o9ides s#c! as Al2O5 and *iO2, p!osp!oro#s co"po#nds s#c! as 'l5, 'l& and 'Ol5, and s#l)onated p!enol )or"alde!yde resins and s#l)onated styrene resins. *!e solid acid catalysts !ave so"e i"portant advantages incl#ding ade-#ate catalytic activity, less byprod#cts, no erosion, easy separation o) catalysts and prod#cts and easy catalyst recovery and recycling. 0' deco"position catalyzed by s#l)onic acid resins o))ers conversion greater t!an ==8 and selectivity over =8 ;0#ang, 0an, Cang, Din, 2%%2<. n t!e present +ork, t!e p!enolacetone prod#ction plant is si"#lated #sing t!e Aspen 0ysys V.%. *!e te"perat#re and ot!er relevant para"eters are obtained by opti"ization. *!e opti"ized val#e obtained can provide a lot o) insig!t be)ore t!e act#al plant co""issioning is done. F#rt!er"ore, sizing and eval#ating t!e econo"ics o) t!e plant )ollo+s +it! a de)initive class 5 esti"ate. Method
n t!e )irst stage o) t!e plant design, a class & esti"ate +as #sed to deter"ine t!e )easibility o) t!e pro3ect. *!e acc#racy o) t!e esti"ate is typically , +!ic! is based on t!e costs o) si"ilar processes and it re-#ires essentially no design in)or"ation ;*o+ler Sinnott, 2%%<. *!is esti"ate is to be started by t!e deter"ination o) t!e capital cost o) an e9isting p!enol plant. Ot!er )actors t!at a))ected t!e )easibility o) t!e pro3ect incl#des t!e de"and and s#pply o) t!e ra+ "aterials and prod#cts and t!e location o) t!e plant.
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DI#B" &en'ene
Benzene
Propylene
Alkylation Reactor (FIXED BED)
Distillation Columns
(Zeolite catalyst)
Cumene Cumene Oxidation Tower
Air
(CuO nanoparticle catalyst)
Cumene %droeroxide (C#)
Acetone Distillation Columns
Cleavage Reactor (Sulfonic resin ca talyst)
OSB! Steam generator" Cooling $ater S%stem
#ower
generator"
$aste
$ater
Phenol Treatment
Facilit%"
Figure 1. Block Flow Diagram for Phenol and Acetone production through Cumene Process
A)ter proven to be )easible, !eat and "aterial balances +ere created #sing a reliable and +idely #sed so)t+are )or process si"#lation, Aspen 0ysys version .%. Fig#re 1 depicts t!e process )lo+ o) t!e c#"ene process. n general, t!e "ain process involved is t!e alkylation o) benzene +it! propylene to prod#ce c#"ene, )ollo+ed by a separation process t!ro#g! distillation to recover c#"ene, t!en o9idation o) c#"ene to prod#ce c#"ene 0ydropero9ide ;0'<, to be )ollo+ed by 0' cleaving to prod#ce p!enol and acetone, and t!en )inally a separation process t!ro#g! distillation to recover eac! o) t!e prod#ct separately. A)ter !eat and "aterial balances +ere generated, t!e designers !ave #sed t!e data as +ell as vario#s ind#stry codes and standards to b#ild "argins into t!eir designs. onsec#tively, creation o) plans and speci)ications and t!e prediction o) t!e )inancial o#tco"e i) t!e plans +ere i"ple"ented are obtained, in order to eval#ate t!e )easibility o) t!e pro3ect t!ro#g! class 5 esti"ate.
Results and Discussion A class & esti"ate st#dy o) t!e econo"ics o) t!e pro3ect s!o+s t!at t!e S4L ape9 and OS4L ape9 o) t!e plant is aro#nd >. and 5.$ 4 '!p. *!e total ape9 o) t!e plant is aro#nd 11.2 4 '!p, +!ic! incl#des t!e contingency plan )or t!e pro3ect, esti"ated
to be 1%8 o) t!e total S4L and OS4L ape9 o) t!e plant ;*o+ler Sinnott, 2%%<. iven t!e ann#al operating e9pense and ann#al reven#e o) t!e pro3ect to be aro#nd 5 and $.2 4 '!p, t!e payback period is aro#nd 5 years +it! an internal rate o) reven#e ;66< o) 2&8. 4ased on t!e preli"inary econo"ic eval#ation, it is !ig!ly reco""ended to p#rs#e t!e FrontEnd Engineering esign ;FEE< o) t!is plant. Once, t!e FEE p!ase is co"plete, it is reco""ended to per)or" a "ore detailed econo"ic analysis to eval#ate i) t!e pro3ect s!all be contin#ed to etail Engineering, 'roc#re"ent and onstr#ction ;E'< p!ase. A !eat and "aterial balance o) t!e plant +as obtained t!ro#g! t!e #se o) t!e so)t+are, Aspen 0ysys V.%. *!e process si"#lation +ill be solely based on t!e prescribed process description o) t!e designers. *!e )irst process involves t!e prod#ction o) c#"ene t!ro#g! t!e alkylation o) benzene +it! propylene, and is ac!ieved t!ro#g! Freidelra)ts 6eaction. n Freidelra)ts reaction, 4enzene is alkylated +it! propylene ;propene< in t!e li-#id or gas p!ase, in t!e presence o) a solid catalyst ;*y"an, 1==><. *!e reactions +ill occ#r in a li-#id p!ase at a partic#lar te"perat#re range and press#re t!at +ill res#lt to eit!er !ig! or co"plete conversion o) propylene as +ell as "aintain t!e reactants in t!e li-#id p!ase, t!ro#g!o#t t!e reactor. nd#strially, alkyl gro#ps can be s#bstit#ted into a benzene ring #sing a variant on Freidelra)ts alkylation. Beolite based catalysts s#c! as , , BSM12, and MM22 can be #sed in t!e li-#id p!ase alkylation o) benzene +it! propylene to prod#ce c#"ene ;/oro#zi, 0asani, 0addadiSisak!t, Mosto#)i, 2%1$<.#ring t!e alkylation reaction, side reactions occ#r +!ic! prod#ces '4 ; <. *!is res#lts to additional cons#"ption o) ra+ "aterials t!at negatively a))ects t!e econo"ics o) t!e process. n order "ini"ize t!e prod#ction o) t!e side prod#ct and increase t!e selectivity o) t!e "ain reaction over t!e '4 reaction, an e9cess a"o#nt o) benzene is introd#ced in t!e reactor. *!e 4enzene to propylene "ole ratio +as "aintained at "ore t!an $ in t!e reactor ;'erego ngallina, 2%%2<. *!e e9cess a"o#nt o) benzene +ill absorb t!e !eat generated by t!e e9ot!er"ic reaction in t!e reactor to keep t!e selectivity o) t!e #"ene reaction !ig! and s#ppress #ndesirable reactions bet+een propylene "olec#les to )or" !ig!er linear !ydrocarbons.
0
!
*able 1 Kinetics of alkylation and tr ansalkylation reactions
*'E
6EA*O/
6A*E O/S*A/*S
Alkylation
#"ene 6eaction
12 3 4.5-% 6.7.48 9: ; 1< 3 8.-% 6..--9: ;
'4 6eaction Re f erence: Dimian and Bil dea, 2008
*!e alkylation reactions )ollo+s t!e Eley6ideal kinetic "odel, +!ic! "eans t!at t!e adsorption o) propylene on t!e catalyst is t!e ratedeter"ining step ;or"a, MartinezSoria, Sc!noeveld, 2%%%<. *!e reactor in t!e syste" consist o) a )i9ed bed o) catalysts pellets +it! an inlet te"perat#re range o) 1&% to 2%% . *!e press#re in t!e reactor is "aintained !ig! eno#g! bet+een 2.& to 5.& M'a to ens#re t!at t!e boiling point o) t!e sol#tion is at least 2% !ig!er t!an t!e te"perat#re else+!ere in t!e reactor ;/oro#zi, 0asani, 0addadiSisak!t, Mosto#)i, 2%1$<. A)ter t!e reactor, t!e li-#id prod#ct is sent to t!e benzene distillation col#"n +!ic! is operated at at"osp!eric press#re. Most o) t!e benzene +ill be obtained as t!e distillate and #sed as recycle. *!e botto" li-#id "i9t#re is t!en p#"ped at b#bble point to t!e #"ene distillation col#"n, +!ere t!e side prod#ct '4 is obtained at t!e botto" and recycled. #"ene at t!e distillate is sent to t!e ne9t process.
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=
*!e ne9t process involved t!e li-#id p!ase air o9idation o) #"ene, called #"ene pero9idation process, to prod#ce #"ene pero9ide at t!e proper reaction te"perat#re o) 5&@ ;B!ang, Cang, 0ongbing, C#, Beng, 2%%7<. #"ene is contin#o#sly )ed to t!e o9idation vessel ;)l#idized bed< #ntil to percent o) t!e #"ene is o9idized. *!e "i9t#re )ro" t!e o9idizer s!o#ld be aro#nd >%8 to by +eig!t #"ene pero9ide, +!ic! +ill t!en be )ed to a reactor )or t!e cleaving o) 0' to p!enol and acetone. *!e cleavage "ec!anis" is an e9a"ple o) s!i)t )ro" carbon to o9ygen ;Speig!t, 2%%2<. n #"ene o9idation, #"ene is o9idized in air +!ic! re"oves t!e tertiary benzylic !ydrogen )ro" #"ene and !ence )or"s a #"ene radical. *!is #"ene radical t!en bonds +it! an o9ygen "olec#le to give #"ene 0ydropero9ide radical, +!ic! in t#rn )or"s #"ene 0ydropero9ide by abstracting benzylic !ydrogen )ro" anot!er #"ene "olec#le. *!is latter #"ene converts into #"ene radical and )eeds back into s#bse-#ent c!ain )or"ations o) #"ene 0ydropero9ides. n t!e process si"#lation )or o9idation, t!e te"perat#re is set to 51@ and t!e press#re to 1at" to ac!ieve a conversion o) 178, selectivity o) greater t!an ==8 t!ro#g! t!e #se o) t!e catalyst #O /anoparticle ;B!ang, Cang, 0ongbing, C#, Beng, 2%%7<.
>-/
5. 7.
5?7
A)ter o9idation process, t!e c#"ene 0ydropero9ide prod#cts are sent to a cleaving reactor. #"ene !ydropero9ide is t!en !ydrolysed in an acidic "edi#" ;t!e 0ock rearrange"ent< to give p!enol and acetone. n t!e )irst step, t!e ter"inal !ydropero9y o9ygen ato" is protonated. *!is is )ollo+ed by a step in +!ic! t!e p!enyl gro#p "igrates )ro" t!e benzyl carbon to t!e ad3acent o9ygen and a +ater "olec#le is lost, prod#cing a resonance stabilized tertiary carbocation. *!e res#lting carbocation is t!en attacked by +ater, a proton is t!en trans)erred )ro" t!e !ydro9y o9ygen to t!e et!er o9ygen, and )inally t!e ion )alls apart into p!enol and acetone. *!e opti"#" te"perat#re )or t!e cleaving reactor is bet+een 7& and & to ac!ieve a selectivity o) "ore t!an =8 and conversion o) "ore t!an ==8 t!ro#g! t!e #se o) s#l)onic resin catalyst. *!e prod#cts are t!en separated by distillation. Acetone is )irstly re"oved in t!e )irst col#"n. *!e botto" is vac##"ed distilled to send #nreacted #"ene over!ead.
=
*!e prod#ct is p#ri)ied t!ro#g! catalytic !ydrogenation t!ro#g! care)#l )ractionation. n t!e latter case, botto"s )ro" t!e vac##" are )#rt!er distilled to separate #"ene )ro" p!enol, p!enol being t!e over!ead prod#ct. *!e !eat and "aterial balances generated +ere t!en #sed to create pla#sible designs )or t!e process e-#ip"ent o) t!e pro3ect. onsec#tively, a class 5 esti"ate o) t!e econo"ics o) t!e plant +as obtained. *!e esti"ate s!o+s t!at t!e S4L and OS4L ape9 o) t!e plant is aro#nd 2.= and 1.2 M '!p. Ot!er i"portant econo"ic )actors s#c! as t!e contingency plan, co""issioning costs, "ini"#" re-#ired capital re-#ire"ent on bank, and environ"ental i"pact assess"ent )ees are considered, a"o#nting to aro#nd &5% M '!p. 4ased on class 5 esti"ate, t!e total capital e9pendit#re o) t!e plant is aro#nd $.& 4 '!p. *!e e9pected ret#rn o) invest"ent is to be at year 7, starting )ro" t!e constr#ction p!ase o) t!e plant. *!e internal rate o) reven#e o) t!e plant is 278, and t!e pro3ect is e9pected to gain &&8 interest )ro" its prod#ction cost t!ro#g! t!e reven#e o) t!e plant #sing breakeven analysis. ?sing Aspen 0ysys Econo"ic Eval#ator, a "ore acc#rate 66 o) 2>.$$&8 +as obtained )or t!e pro3ect.
Conclusion An opti"ized prod#ction process o) p!enol and acetone )ro" propylene and benzene t!ro#g! c#"ene process +as st#died )or intensi)ication o) an ind#strialscale prod#ction. A co"pre!ensive "odel t!at considers all in)l#ential )actors +as establis!ed )or t!e pro)itability analysis. ?sing establis!ed econo"ic "odels, t!e total invest"ent and yearly pro)it o) t!e pro3ect is $.& and 2.5 4illion 'esos, respectively, +!ic! yielded an 66 o) 278 and payback period o) 7 years. *!ere is a di))erence o) 2.%&8 )ro" t!e 66 obtained t!ro#g! t!e Aspen 0ysys Econo"ic Eval#ator, +!ic! is considered to be "ore acc#rate t!an t!e "an#al calc#lations done by t!e designers. n general, based on t!e econo"ic analysis o) t!e pro3ect #sing class 5 esti"ate, t!e pro3ect is concl#ded to be )easible since it is !ig!ly pro)itable.
References Anpo, M., Onaka, M., a"as!ita, 0. ;2%%5<. S tudies in S ur face S cience and Cat aly sis. *okyo, Dapan: Elsevier. an)ield, 6. ., o9, 6. ., Mcart!y, . M. ;1=><. MonsantoGL#""#s crest process prod#ces lo+est cost c#"en. Pr oceedings of the AIC hE 1988 Spring M eeting , N ew. or"a, A., MartinezSoria, V., Sc!noeveld, E. ;2%%%<. Alkylation o) benzene +it! s!ortc!ain ole)ins over MM22 zeolite: atalytic be!avior and kinetic "ec!anis". J. Cat al , 1>5175. i"ian, A. ., 4ildea, . S. ;2%%<. C hemical Pr ocess Design: Com puter- Aided Ca se S tudies. 0oboken, /.D.: CileyV0. 0#ang, ., 0an, M., Cang, D., Din, . ;2%%2<. atalytic deco"position process o) c#"ene !ydropero9ide #sing s#l)onic resins as catalyst. C hemical Engineering J ournal , 21&225. /oro#zi, 0. 6., 0asani, M. A., 0addadiSisak!t, 4., Mosto#)i, /. ;2%1$<. Econo"ic esign and Opti"ization o) Beolite 4ased #"ene 'rod#ction 'lant. C hemical Engineering Communications, 127%12=5. doi:1%.1%%G%%=>$$&.2%15.%>512 'erego, ., ngallina, '. ;2%%2<. 6ecent advances in t!e ind#strial alkylation o) aro"atics: /e+ catalysts and ne+ processes. Cat al . Tod ay, 522. Sc!"idt, 6. D. ;2%%&<. nd#strial catalytic processesJ'!enol prod#ction. A ppl . Cat al . A: Gen, =I1%5. Ste)anidakis, ., +yn, D. E. ;1=77<. Alkylation. Enc yclo pedia of C hemical Pr ocessing , 5&7. *o+ler, ., Sinnott, 6. ;2%%<. CH E MICAL E NGIN EE RING D E S IGN : Princi pl es , Pr actice , and Economics of P lant and Pr ocess Design. ali)ornia: Elsevier.
*y"an, D. ;1==><. S ynthetic and Natur al Phenol s. 6ose+ood rive, anvers, MA: Elsevier. B!ang, M., Cang, L., 0ongbing, D., C#, 4., Beng, K. ;2%%7<. #"ene Li-#id O9idation to #"ene 0ydropero9ide over #O /anoparticle +it! Molec#lar O9ygen ?nder Mild ondition. J ournal of Natur al Ga s C hemistr y, 5=55=.
