Cumene Uses and Market Data 09 December 2010 14:58 [Source: Chemical Report] Around 98 o!

cumene i" u"ed to produce phenol and it" co#product acetone$ %o&e'er( the outloo) !or cumene i" lar*el+ dependent on the per!ormance o! phenol," deri'ati'e" &hich ha'e re"ulted in health+ *ro&th rate" !or cumene$ -he lar*e"t phenol deri'ati'e i" bi"phenol#A ./0A1 &hich "upplie" the *ro&in* pol+carbonate .0C1 "ector$ 0C re"in" are con"umed in automoti'e application" in place o! traditional material" "uch a" *la"" and metal"$ 2la3in* and "heet u"e"( "uch a" architectural( "ecurit+ and *la3in* outlet"( are al"o important 0C application"$ -he third lar*e"t u"e !or 0C i" optical media "uch a" compact di"c" .CD"1 and di*ital 'er"atile di"c" .D4D"1$ 0C re"in" con"umption ha" "lo&ed &ith the "o!tenin* o! the automoti'e "ector$ -he "tron* *ro&th in optical media ha" dri'en the 0C mar)et but *ro&th in thi" mar)et ha" been "lo&in* and e5pected to *o into decline a" it become" replaced b+ 607 pla+er"( hi*h internet band&idth and 8S/ dri'e"$

0C pla"tic bottle" containin* hot li9uid" ha'e attracted the attention o! en'ironmentali"t" in that /0A can be relea"ed !rom the bottle" leadin* to health concern"$ A" a re"ult( "ome 0C bottle" !or bab+ !ood" ha'e been remo'ed !rom "upermar)et" althou*h thi" i" a "mall mar)et !or pol+carbonate$

/0A," other main deri'ati'e i" epo5+ re"in" &hich are u"ed in hi*h per!ormance coatin*"( electrical#electronic laminate"( adhe"i'e"( !loorin* and pa'in* application"( and compo"ite"$ 2ro&th in the"e mar)et" i" clo"e to 2D0 le'el"$

0henol," other deri'ati'e" include phenolic re"in" &hich are lar*el+ u"ed a" durable binder" and adhe"i'e" in "tructural &ood panel" and a" binder" in mineral &ool in"ulation$ Demand here i" tied clo"el+ to the home con"truction mar)et$

Another phenol deri'ati'e i" caprolactam &hich i" u"ed mainl+ to ma)e n+lon :$ ;t i" mainl+ the en*ineerin* re"in "ector o! the n+lon mar)et that i" "eein* *ro&th$

-he )e+ dri'er" in the acetone mar)et are meth+l methacr+late .66A1 and /0A$ <earl+ all 66A i" u"ed to ma)e homopol+mer" and copol+mer" &ith electronic application" "uch a" !lat "creen -4" and li9uid cr+"tal di"pla+" pro'idin* *ro&th opportunitie"$ %o&e'er( a "i*ni!icant outlet !or acetone i" the "ol'ent "ector &here mar)et *ro&th i" "ta*nant$ Accordin* to 8S#ba"ed con"ultant" De=itt > Co( the con"umption o! cumene !ell in relation to other ben3ene deri'ati'e" in 2009$ 0henol demand in 2009 &a" 8 belo& the pea) in 200? &ith the !all concentrated in @urope and the 8S$ %o&e'er( A"ia operate" clo"e to capacit+ and &ill be "hort o! product in the ne5t three +ear" i! *ro&th i" "u"tained$ @urope could pro!it !rom the ti*htne"" in A"ia to increa"e operatin* rate"$

-he 8S &ill al"o increa"e phenol e5port" but &ithout a "i*ni!icant pic)#up in dome"tic demand( it ma+ "ee rationali3ation( add" De=itt$ -he 8S prop+lene ad'anta*e i" declinin* &ith lo&er re!iner+ operatin* rate" and 8S ben3ene i" li)el+ to remain e5pen"i'e$

Cumene i" lin)ed clo"el+ to the phenol and acetone mar)et"$ 0lea"e "ee phenol u"e" and outloo) and acetone u"e" and outloo)$

Updated: October 2010

Source: DeWitt & Co World Petrochemical Conference, 24 2! "arch 2010

0rop+lene treater" are u"ed to remo'e Sul!ur compound"( Ar"ine and 0ho"phine !rom 0rop+lene !eed be!ore admittin* it to Al)+lation Reactor becau"e the"e are poi"on to the Al)+lation catal+"t$ ;t u"e" /ASA R7#12 a" catal+"t$ -hi" i" a mi5ture o! CuB( CnB and Al2B7$ -reater" are u"ed in "erie" &ith lead and la* po"ition"$ @ach -reater catal+"t ha" a total li!e o! 2 +ear" &ith !ir"t +ear in lead po"ition and "econd +ear in la* po"ition$ -otal Sul!ur at the outlet o! 0rop+lene -reater "hould be 0$015 ppm

Cla+ -reater" are u"ed to remo'e /a"ic <itro*en compound" !rom !re"h /en3ene !eed$ ;t u"e" @n*lehard A#25 Acti'ated cla+ a" catal+"t$ @ach -reater catal+"t ha" a total li!e o! : month" &ith 7 month" in lead po"ition and ne5t 7 month" in la* po"ition$ /a"ic <itro*en at the outlet o! Cla+ -reater" "hould be le"" than 0$07 ppm

Secondar+ /en3ene -reator" are u"ed to remo'e polar <itro*en compound" !rom the Rec+cle /en3ene "tream &hich are poi"onou" to the Ceolite catal+"t$ @ach treator i" !illed &ith the a "in*le bed o! t+pe 17D 6olecular "ie'e ad"orbent$ @5pected li!e o! the catal+"t i" 7 month" in the lead po"ition and 7 month" in the la* po"ition ba"ed on a polar nitro*en concentration in the !re"h ben3ene at 0$5 ppm& -otal <itro*en at the outlet o! Secondar+ ben3ene -reater "hall be 0$07 ppm$

MOR-type zeolite has been proved an effective catalysts for cumene production [5355, 63 ! "he advanta#e of MOR catalysts is the hi#h adsorption selectivity of benzene in benzene$propene mi%tures due to the uni&ue porous structure! MOR consists of t'elve-membered main channels that connect to side poc(ets that are accessible throu#h ei#ht-membered rin#s! "he ei#htmembered channel that connects the t'elve- embered channels is tortuous and most hydrocarbon molecules cannot pass throu#h! "herefore, MOR is considered as a one-dimensional structure! )s the heat of adsorption of aromatics is much lar#er than for propene in the main channels, the adsorption selectivity of benzene is hi#h enou#h to prevent propene oli#omerization and multiple al(ylation in main channels! *o'ever, the one-dimensional structure hinders the accessibility and transport of #uest molecules inside MOR! +ealumination is often applied to modify the MOR frame'or( into a three-dimensional porous system! ,vidence e%ists that 'ith hi#hly dealuminated MOR the ei#ht-membered 'indo's and side poc(ets do not contain )l atoms [6-66 ! .n other 'ords, the acid sites are e%clusively located in the main channels! /urthermore, studies by researchers from +o' 0hemical [63, 61, 62 have sho'n that dealumination si#nificantly modifies the pore topolo#y of MOR! .n addition to to mesopores that shorten the effective diffusion len#th of the main channels, also the nature of the micropores has chan#ed as has been deduced from lo'-pressure nitro#en physisorption studies! .t is speculated that a three-dimensional frame'or( of MOR comprises a modified ei#htmembered channel system that allo's propene to pass from one main channel to another! .n such a MOR crystal the diffusion of reactants could ta(e place in t'o directions, i!e! benzene$cumene e%clusively via the main channels and propene lar#ely via the ei#ht-membered channel system, see /i#! 3!1! "his diffusion behavior corresponds to the hypothesis of molecular

traffic control [64, 15 ! "his concept su##ests a simultaneously feed of t'o types of reactants into zeolites via 'ell-defined channels of different size 'ithout counter-diffusion! "he feasibility to adopt this speculative concept for cumene production is 'orth studyin# further

6ummary

"his thesis deals 'ith the application of zeolite catalysis for the production of cumene via benzene al(ylation 'ith propene! .n particular, the 'or( 'ill be focused on Mordenite 7MOR-type zeolite8! "he first step is to understand the effect of non-frame'or( cations on the adsorption and diffusion of #uest molecules adsorbed in MOR! .n chapter 9, this effect is studied for al(anes in :a-MOR! "he influence of the )l distribution is investi#ated! "he simulations sho' that about one third of the frame'or( )l is located in the four-membered rin#s of the side poc(ets, 'hile the remainin# )l is in the main channels of MOR! "his distribution a#rees 'ell 'ith other e%perimental and simulation results! :aMOR models 'ith various 6i$)l ratios are used to compute the adsorption and diffusion behavior of al(anes! "he simulations sho' a stron# increase in the adsorption of al(anes for an increasin# :a concentration! ) direct correlation 'as found bet'een the number of )l in the main channels and the &uantities such as the adsorption isotherm, *enry coefficients, diffusion coefficient and micropore volume! /or e%ample, for a #iven 6i$)l ratio, the adsorption isotherm correspondin# to any )l M$6 ratio 7the ratio of )l in the main channel and in the side poc(et8, can be directly calculated usin# t'o precalculated reference isotherms that correspond to the ma%imum fraction of frame'or( )l in the main channel and in the side poc(et, respectively! ;e e%pect that this 'ill also be applicable to molecules li(e benzene, propene and cumene! .t is e%pected that the presence of non-frame'or( cations 7or the <r=nsted acid sites8 'ill si#nificantly enhance the adsorption of benzene and propene, 'hile the saturation loadin#s may decrease to some e%tent due to the occupancy of void micropore volume by nonframe'or( cations! +iffusion of both benzene and propene 'ill be slo'ed do'n as #uest molecules stron#ly interact 'ith <r=nsted acid sites! .n chapter 3, a ne' method is introduced to compute the heat of adsorption for molecules in zeolite frame'or(s containin# non-frame'or( cations! "his method is more accurate and efficient than either the conventional ;idom>s test particle method or the conventional method based on ener#y differences! .n addition, 'e have sho'n that for studyin# adsorption in zeolites, the ,'ald summation is superior to the recently proposed ;olf method both in accuracy and speed! )part from non-frame'or( cations, the adsorption selectivity of benzene in benzene$propene mi%tures is attributed to the micropore structure of zeolites! ;hen the size of the micropores are

close to the (inetic diameter of benzene, the heat of adsorption of benzene 'ill be lar#er than that of propene! "herefore, benzene 'ill be preferentially adsorbed in these zeolites! ?eolite catalysts suitable for benzene al(ylation are MOR, <eta, zeolite @ and M0M-99! .n order to understand the effect of the microporosity on the adsorption selectivity, in chapter - molecular simulations have been conducted for all-silica MOR, <eta, zeolite @ and M0M-99! "he simulations sho' that for all four zeolites, the hi#h selectivity to'ards benzene in e&ual molar benzene$propene mi%tures can be obtained under various conditions! 6imulation snapshots indicate that althou#h the zeolites have different micropore topolo#ies, the sizes of all the micropores are close to the (inetic diameter of benzene! .n this 'ay, a hi#h adsorption selectivity of benzene is #uaranteed! "herefore, potential zeolite catalysts for benzene al(ylation need to have micropores of similar sizes as benzene! +ealumination is an important treatment to improve the catalytic performance of *-MOR! )s the dimensions of the zeolite micropores are the crucial factor for the hi#h selectivity of benzene, the chan#e of the microporosity durin# dealumination is a crucial issue! .n chapter 5, a simulation method is developed to characterize the zeolite porosity in terms of the pore size distribution, the pore volume and the pore topolo#y! "his method is able to provide us 'ith the hi#h-resolution pore size distribution! .n chapter 6 the dealumination process is modeled usin# Ainetic Monte 0arlo simulations! "he essential reactions of dealumination are identified as the removal of frame'or( )l atoms and the mi#ration of 6i atoms, and the self-healin# of the silanol vacancies! "his simulation scheme is Bustified by comparin# to different e%periments such as 946i :MR, CR+, :9 physisorption and :on Docal +ensity /unction "heory 7:D+/"8 analysis usin# e%perimental )r adsorption isotherms! "he simulations indicate that the frame'or( )l is e%tracted from the four-membered rin#s of the side poc(ets and the internal surface of the main channels! "he void volumes of both re#ions can thus mer#e to#ether to form lar#e secondary pores! "he size of the secondary pores is sli#htly lar#er than that of the main channels! *o'ever, the openin# of the side poc(et only ta(e place locally, and they cannot form interconnected side channels for the transport of propene! .n other 'ords, the main channels are still separated by the ei#ht-membered channels 'ithout interconnection! "his observation conflicts 'ith the concept of molecular traffic control postulated earlier! MOR is a special zeolite compared to others such as the M/.-type zeolite! /or instance, the synthesis of MOR re&uires a hi#h )l content! <y comparin# to siliceous zeolites, the reason for this may be that MOR precursors can only be 'ell-connected by the stabilization of )l atoms durin# the nucleation process, leadin# to a favorable )l-O-6i-O-)l lin(a#e in the four-membered rin#s! Do' )l concentrations durin# synthesis may cause a lar#e fraction of stac(in# faults

domains formed in MOR frame'or(s! "hese domains are constructed by MOR unit cells 'ith mismatched four-membered rin#s! )ccordin#ly, the often observed disordered structure of the stac(in# faults is caused by the shift of MOR unit cells by half a unit cell alon# the z crystallo#raphic a%is! "he stac(in# fault domains 'ill be transformed into mesopores durin# dealumination! <ased on the (no'led#e of the adsorption, diffusion and reaction of benzene and propene in MOR, several criteria can be proposed for the potential candidates for benzene al(ylationE F "he zeolite frame'or( should at least have one type of micropores of size 6 G 2 H, 'hich matches the (inetic diameter of benzene or cumeme! Micropores lar#er than 2 H may have a lo'er adsorption selectivity for benzene and cumene! ?eolites 'ith a multi dimensional pore structure may also be suitable for benzene al(ylation! F "he zeolite frame'or( should have a lo' )l content, especially in fourmembered rin#s! .n this 'ay, the zeolite is supposed to have a hi#h siliceous structure 'ith ne#li#ible crystalline impurities! .n this case, bloc(in# effects are minimized! F "he zeolite should have a small crystal size or it could be modified into small crystals 'ithout dama#in# the micropores! ) hi#h surface area is crucial for the accessibility of zeolites as 'ell as the diffusivity of #uest molecules! Isin# the the .?) database of zeolite structures, another possible zeolite catalyst could be the M";-type frame'or(! ?6M-39 7M";-type8 has a onedimensional structure consistin# of strai#ht channels of 6 H! 6ince the secondary buildin# units of ?6M-39 do not need a hi#h )l composition for nucleation, a hi#h siliceous structure can be synthesized easily 'ithout much crystalline impurities! .n this 'ay, aromatics are able to diffuse freely in the channels of ?6M-39! 0ompared to MOR, the narro' channels in ?6M-39 may suppress the formation of side products li(e multiple al(ylated benzene! 0ompared to zeolite <eta 'hich has been 'idely commercialized for cumene production, the &uality of the final product is also e%pected to be hi#h as ?6M-39 has an one-dimensional channel system 'ithout intersections 'hich is actually present in zeolite <eta! "herefore, it is reasonable to speculate that ?6M-39 has a lar#er probability to lo'er the feed benzene$propene ratio than zeolite <eta and MOR! "he additional effort can be made to enlar#e the surface area of ?6M-39 by either synthesis or treatment such as acid leachin# and base leachin#!