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Design of a Process for Production of Isopropyl Alcohol by Hydration of Propylene in a Catalytic Distillation Column

Yan Xu, Karl T Chuang and Alan ! "anger Department of Chemical and Materials Engineering University of Alberta Edmonton, Alberta Canada T6G 2G6

A#"T!ACT

A novel process flo

sheet has been developed for the application of catalytic distillation

technology to the prod!ction of isopropyl alcohol "#$A% by hydration of propylene& 'peration of the catalytic distillation col!mn has been sim!lated !sing both e(!ilibri!m)stage and e(!ilibri!m)reaction models& *igh p!rity #$A "++&+vol,% is prod!ced as a li(!id prod!ct stream from a catalytic distillation col!mn having d!al catalyst bed, operating at 2M$a&

Key words: catalytic distillation; propylene; hydration; isopropyl alcohol; simulation

I$T!%D&CTI%$

Isopropyl Alcohol Production

#sopropyl alcohol "#$A% has been called the first modern synthetic petrochemical& .eca!se #$A has physical characteristics compatible ith those of alcohol, ater, and

hydrocarbons, it is a versatile and ine/pensive solvent !sed cosmetics ind!stries& Unli0e ethanol, #$A is s!b1ect to fe

idely in the chemical and

government reg!lations, and no

special ta/es are levied on cons!mption of #$A& #$A is !sed as feedstoc0 for the man!fact!re of acetone and other compo!nds& #$A is !sed idely as an antiseptic and disinfectant for

home, hospital, and ind!stry applications "*ancoc0-, 2rosch it32%& 4everal methods are available for man!fact!re of #$A& The methods !sed most idely are direct hydration and indirect hydration of propylene "2rosch it3 2%& .oth processes !se propylene and ater as ra materials& #ndirect hydration is based on a t o)stage process in hich an ester is formed and then

hydroly3ed to the corresponding alcohol& Diisopropyl ether "D#$E% is the principal by) prod!ct& Acid)cataly3ed direct hydration of propylene to #$A is reversible and e/othermic "E(!ation -%& D#$E is again the principal by)prod!ct "E(!ation 2%& *ydration5
CH 6 CH = CH 2 + H 2 O "CH 6 % 2 CHOH

"-%

*7)890:;mol ")-20cal;mol%

Etherification5
2"CH 6 % 2 CHOH H 2 O + ""CH 6 % 2 CH % 2 O

"2%

There are three propylene direct hydration processes in commercial operation5 vapor) phase hydration over a fi/ed)bed catalyst "2rosch it3 2%< mi/ed vapor)li(!id)phase hydration !sing strongly acidic proton )e/change resin catalyst "=eier and >eollner 6%< and li(!id)phase hydration in the presence of a homogeneo!s catalyst "'no!e et al&?%& The p!rity of #$A prod!ct re(!ired depends on the intended application& The @A t, #$A a3eotrope prod!ced is sold as s!ch or is dehydrated by a3eotropic distillation to prod!ce an anhydro!s prod!ct& Minor imp!rities are removed and the odor of #$A is improved by !se of either intense a(!eo!s e/tractive distillation, or post)treatment by a fi/ed)bed absorption process !sing activated carbon, molec!lar sieves or metals and ;or metal o/ides of Gro!p #., B#. and B### of the $eriodic Table "4avini8%& Essence grade #$A is prod!ced by distillation of dehydrated #$A) ater a3eotrope in nonferro!s e(!ipment& A typical process scheme for direct hydration of propylene is sho n in Cig!re -& The principal difference bet een the direct and indirect processes is that m!ch higher press!re is re(!ired for the direct hydration process& The slate and distrib!tion of prod!cts and by) prod!cts from each process are similar, and systems for refining #$A are essentially the same& Direct hydration of propylene is the preferred process for prod!ction of #$A beca!se it avoids some corrosion and environment problems enco!ntered !sing indirect hydration processes& #mprovements to the hydration process have been made in recent years& *o ever, c!rrent processes still re(!ire the !se of comple/ distillation col!mns to recover #$A from the prod!ct stream& 4eparation of #$A from the a3eotropic mi/t!re is technically diffic!lt and e/pensive& >e ill no sho that catalytic distillation is a simpler and less e/pensive

alternative to conventional processes for prod!ction of #$A&

Catalytic Distillation

Catalytic distillation "CD% comprises the processes of heterogeneo!s catalytic reaction and m!ltistage distillation carried o!t sim!ltaneo!sly in a single vessel& A CD col!mn replaces the separate fi/ed)bed reactor and a series of distillation col!mns, thereby red!cing the n!mber of process vessels and materials transfer and control e(!ipments re(!ired& Th!s, capital costs are red!ced "DeGarmo et al&6%& CD is a viable option hen the temperat!re and press!re of a process are s!ch that the

rate of reaction is s!fficiently high !nder conditions for separation of prod!cts by distillation& E(!ilibri!m)limited reactions are e/cellent candidates for catalytic distillation< by contin!o!sly separating prod!cts from reactants hile the reaction is in progress, the reaction

can proceed to a m!ch higher level of conversion than is attainable !sing a conventional process "Doc0A, 4hoema0er and :ones @%& C!rrently, the largest !sers of reactive distillation technology are f!el)ether prod!cing !nits& A variety of ethers can be prod!ced by reacting olefins having fo!r, five, or si/ carbon atoms ith methanol or ethanol "$odrebarac and =g +%&

Application of CD to Production of IPA

$ropylene hydration to #$A is an e/cellent candidate for application of CD technology, for the follo ing reasons5 "-% Direct hydration of propylene is an e(!ilibri!m)limited reaction "E(!ations - and 2%&

"2% *ydration can ta0e place in the li(!id phase< catalyst pellets etted& "6% The reaction

ill remain completely

ill be cond!cted at a temperat!re and press!re e(!ivalent to the boiling ill be carried o!t sim!ltaneo!sly in the

point of the li(!id prod!ct< distillation and reaction same col!mn&

"?% *ydration is e/othermic< the heat of reaction separation of the reaction mi/t!re by distillation& "8% D!rable heterogeneo!s hydration catalysts

ill provide energy re(!ired for

ith s!itable physical properties are

commercially available "2!o and Chen-9, 4onnemans --, 4onnemans -2, 'dios, et al&-6%& "6% #n a CD hydrolysis process, and an #$A)rich stream ater ill be contin!o!sly cons!med by fresh propylene, ill have a

ill be contin!o!sly prod!ced& *ence, the prod!ct stream

higher #$A content than prod!ct streams !sing conventional processes& A ma1or advantage of catalytic distillation over conventional fi/ed)bed reactors is the red!ction in capital investment "=g and Dempel -?, $odrebarac and =g +, Doc0 et al&A%& The chemical reaction and distillation are carried o!t in the same vessel, th!s simplifying the process and red!cing the costs, as disc!ssed above& #n addition, operating costs for prod!ction of #$A are red!ced, as there is essentially no need to cool or heat the reactor& >e ill sho

that other benefits accr!e from !se of CD techni(!e, incl!ding s!bstantially complete cons!mption of ater and improved selectivity to #$A& 4afety and catalyst performance are

also enhanced by !se of CD technology, as the ris0 of formation of hot spots is lo er in a CD system than in a conventional hydration reactor& >e ill no describe a model for an #$A prod!ction process based on the CD

technology&

'%D() %* A CD P!%C("" *%! IPA P!%D&CTI%$

4im!lation has become an essential component of reactive distillation process design, and is even more important for CD process design than for design of conventional distillation systems& The interaction bet een sim!ltaneo!s reaction and distillation processes increases the comple/ity of CD systems compared ith systems comprising conventional reactors hen

follo ed by distillation systems& Modeling methods are of even greater importance

there is no available satisfactory shortc!t or empirical methods for the determination of 0ey parameters "$ilavachi-8%& Deliable sim!lation soft are allo s a ne CD process to be

modeled !sing 0no n thermodynamic and 0inetic data& Bal!es for 0ey design parameters can be identified ith a high degree of confidence& 4im!lation can also be applied to an e/isting

process to st!dy the effect of varying 0ey parameters, and thereby provide g!idelines for f!rther optimi3ation of the process&

"imulation #asis

Software

4im!lation in this st!dy is based on e(!ilibri!m stage and e(!ilibri!m reaction models !sing validated e/perimental data& ME4* "material balance, vapor)li(!id e(!ilibri!m, mole fraction s!mmations and heat balance% e(!ations for systems in vapor)li(!id and chemical e(!ilibri!m are !sed& Even tho!gh no reactive distillation process ill ever operate !nder total e(!ilibri!m conditions, an e(!ilibri!m)based model provides theoretical limits of achievable separation& Constant plate)to)plate press!re drop is ass!med in the present model& This

ass!mption introd!ces no significant error for steady)state sim!lations& #n the first stage of the development of the model, propylene direct hydration to #$A as the only reaction ta0en into

acco!nt, since the propylene hydration catalyst "3eolite or proton)e/changed resin% has high selectivity to ard the desired prod!ct "E+8 t, Eg!chi, et al& -6% in the operating temperat!re range& *o ever, no catalyst has yet been developed that selectively cataly3es conversion of propylene to #$A itho!t also forming D#$E& Therefore the present model incl!des #$A and

D#$E as e(!ilibri!m prod!cts of the hydration reaction& The al0ene)alcohol) ater)ether system is non)ideal& Conse(!ently, the selection of physical property ro!tines is of great importance& The U=#CAC method has been !sed s!ccessf!lly to predict li(!id phase activity coefficients and e(!ilibri!m constant e/pressions of similar non)ideal systems in sim!lation of ET.E, ME.E, and DAA "diacetone alcohol% prod!ction processes "$odrebarac et al&-A, 4neesby et al&-@%& U=#CAC also has been !sed to acc!rately model the vapor)li(!id behavior of the #$A) ater system& The U=#CAC method therefore has been sho n to be s!itable for the calc!lation of the li(!id phase activity coefficients and e(!ilibri!m constants re(!ired for the present st!dy& The Dedlich)2 ong e(!ation of state has been !sed to predict the non)ideal vapor phase behavior of the system& The res!lts obtained !sing the $eng)Dobinson e(!ation of state are s!bstantially the same for all aspects of the model& Commercial sim!lation programs most commonly !sed for the design of CD process incl!des5 $D'##, Aspen$l!s, and *ysis& Aspen$l!s has been !sed s!ccessf!lly on the sim!lation of several catalytic distillation processes "Eldarsi and Do!glas -+, =i1h!is et al&29%& #t as also fo!nd that it is m!ch easier to obtain converged res!lts for the propylene hydration

CD process by !sing Aspen$l!s& DadCrac distillation !nit b!ilt into Aspen$l!s obtain the data reported herein&

as !sed to

Catalytic Distillation Column

The core of the CD process is the catalytic distillation col!mn "Cig!res 2 and 6%& A col!mn in hich propylene hydration is to be performed has three ma1or sections& The

reaction occ!rs over one or more catalyst beds mo!nted in the middle section of the col!mn& Dectification of the volatile components of the reaction mi/t!re occ!rs in the top section& Fi(!id prod!cts are recovered from the bottom of a lo er stripping section& *erein e ill

describe CD col!mns having either a single catalyst bed "Cig!re 2% or d!al catalyst beds "Cig!re 6%& Deaction of propylene hydration to #$A and #$A etherification to D#$E over the catalyst in the middle section proceed sim!ltaneo!sly ith distillation in the rectifying and

enriching sections of the col!mn& Unreacted volatiles rise from the reaction 3one to the rectifying section and are separated from heavier components before being removed from the top of the col!mn& Condensed materials fall as li(!id from the reaction 3one into the stripping section& >e ill sho that in the present model, an a3eotropic mi/t!re of #$A, D#$E and

ater is concentrated at the top of the stripping section, and enriched #$A having a very lo ater content is gathered at the bottom of the stripping section& The a3eotrope carrier to lift ater and D#$E bac0 to the reaction 3one for or0s as a ith

ater to be f!rther reacted

propylene and D#$E to decompose to #$A& The #$A concentration in the prod!ct stream thereby e/ceeds the e(!ilibri!m limit for propylene) ater)#$A reaction by contin!o!s removal of prod!ct #$A from the reaction 3one&

"imulation !esults

Cirstly, for each col!mn config!ration, the effect of varying the press!re and temperat!re on the process as determined& Distillate flo rate and feed ratio ere ad1!sted to obtain

optim!m high p!rity prod!ct& Then the n!mber of plates in the rectifying 3one, above the catalyst bed"s%, and in the stripping 3one, belo the catalyst bed"s%, ere varied

independently, and the impact of the location of either a single catalyst bed or d!al catalyst beds as systematically e/amined& The optim!m config!ration has been determined >e ill sho that the optim!m config!ration is a col!mn having d!al catalyst beds, an

!pper rectifying section having 2 plates, and a lo er stripping section having 2- plates& The effect of changing each of the 0ey variables ill be described&

K(Y +A!IA#)("

4im!ltaneo!s operation of both reaction and distillation in a single vessel leads to different responses to changes in operating conditions compared ith those having t o

separate processes& #t is necessary to f!lly !nderstand the interaction bet een the processes to avoid s!boptimal performance res!lting from poor design& The dependence of CD col!mn performance on each variable or combination of variables ill no be disc!ssed&

%perating Pressure and Temperature

#n conventional distillation, the press!re range !sed is determined by the condenser coolant and reboiler heating media temperat!res& #n a CD process, the selection of operating press!re m!st ta0e into acco!nt the effect of press!re on the reaction 3one temperat!re, hich depends on the relative volatility of reactants, prod!cts and a3eotropes "DeGarmo et al&6%& #n a CD col!mn, the reaction 3one temperat!re is determined by the boiling point of the li(!id mi/t!re in the catalyst bed, hich in t!rn is determined by the composition of the li(!id and the operating press!re& *o ever, beca!se separation and reaction occ!r sim!ltaneo!sly in the col!mn, the composition of the li(!id phase is a f!nction of temperat!re and ratio of feed rates& Cor the present propylene) ater)#$A)D#$E system, the reaction 3one temperat!re increases ith increase in press!re& The propylene hydration reaction and #$A etherification ith an increase in reaction 3one ith an

are highly e/othermic& $ropylene conversion decreases

temperat!re& Conse(!ently, the content of #$A in the reaction mi/t!re is red!ced increase in col!mn press!re& *o ever, the reaction rate increases

ith increasing

temperat!re& Therefore, the preferred operating press!re is in a range in hich the temperat!re of the reaction 3one is s!fficiently high to give a fast rate of reaction, and s!fficiently lo afford a prod!ct stream rich in #$A& >ater, #$A and D#$E form lo boiling point a3eotrope ith each other ".erge, et al& 2-%& to

The compositions and boiling points of each a3eotrope are presented in Table -& The mole fraction of #$A in the #$A) ater a3eotrope varies ith press!re& The #$A content climbs from 9&66A9 at 9&9-2 M$a, passes thro!gh a ma/im!m val!e of 9&6+89 at 9&?96 M$a, and then declines to 9&6? at 6&86- M$a "Cran0 and Dodge22%&

-9

The relative volatility of reactants and prod!cts declines change in the relative volatility affect reaction and separation&

ith increasing press!re& The

ith press!re is grad!al and small, and does not significantly

The lo er limit of the operating press!re is set at conditions, reaction rate and the !se of CD col!mn

hich allo

a reasonable

ater as coolant in the condenser& The operating press!re of the

as varied in the range of 9&-)8 M$a& The coolant inlet temperat!re, reaction ater, and prod!ct p!rity have been !sed to

3one temperat!re, conversions of propylene and

determine the optim!m operating press!re range& Cor the present model, it has been fo!nd that the optim!m press!re for operation of a d!al catalyst bed CD col!mn is 2 M$a& #f a catalyst can be fo!nd that is selective for formation of #$A, and not D#$E, the operating press!re can be increased to ? M$a "Table 2% & )ocation of !eaction ,one

The location of the reaction 3one in the CD col!mn is determined by the relative volatility of reactants and prod!cts& Deactant propylene is the most volatile and prod!ct #$A is the least volatile component of the system higher than in the hen #$A concentration in the li(!id phase is

ater)#$A a3eotropic mi/t!re& Therefore the reaction 3one is located here a high concentration of propylene is present in the li(!id

to ard the top of the col!mn,

phase, thereby ens!ring a higher conversion of ater& The precise location of the catalyst beds depends on the optim!m n!mbers plates in each of the rectifying and stripping 3ones, in t!rn depend on the feed location locations and feed ratios, as ill no be disc!ssed& hich

--

*eed )ocation

The inlet to the col!mn for each feed has been located so as to ma/imi3e reactant concentration in the reaction 3one, itho!t hindering the separation process occ!rring in the

other parts of the col!mn& #n the optim!m d!al catalyst bed CD col!mn config!ration, li(!id ater is fed closely above the top of each of the catalyst beds, and propylene is fed immediately belo the lo er catalyst bed "Cig!re 6%& Alternative designs in hich feed streams are located higher in the stripping section or

lo er in the rectifying section give !nsatisfactory performance& Ceeding reactants to the stripping or the rectifying section leads to a red!ction in #$A concentration and an increase in ater concentration in the li(!id prod!ct& This effect is a conse(!ence of a lo er conversion of ater to #$A in the reaction 3one, and red!ced efficiency in separation in the stripping

section& 4imilarly, for the single catalyst bed CD col!mn, ater is fed closely above the catalyst

bed, and propylene immediately belo the catalyst bed "Cig!re 2%&

"toichiometric (-cess of Propylene

Cor an e(!ilibri!m)limited reaction, an e/cessive amo!nt of one reactant is !s!ally !sed to obtain a ma/im!m conversion of another reactant to a desired prod!ct& An ob1ect of the present st!dy is to obtain high p!rity #$A from the bottom o!tlet of CD col!mn& The boiling points of p!re compo!nds and a3eotropes of the propylene) ater)#$A)D#$E system are listed in Table -& D#$E and a3eotropes it forms are more volatile than propylene b!t less volatile

-2

than

ater and #$A, and more than @6 t, of each a3eotropes is D#$E& Therefore D#$E

concentrates in the middle of the CD col!mn "Cig!re ?%& Fi(!id mi/t!re in the stripping section of the CD col!mn comprises mainly ater, it ater and #$A& As #$A forms a3eotropes ith

ill only concentrate at the bottom of stripping section

hen the #$A concentration

in the total reaction mi/t!re is higher than the concentration of #$A in the a3eotrope "G9&6A mole fraction #$A%& >hen propylene and ater are fed to an e(!ilibri!m reactor of ?-92 at

-5- mole ratio, and chemical e(!ilibri!m is attained, the #$A molar ratio in the #$A and ater mi/t!re of li(!id o!tlet is only 9&-8, lo er than that in the ater and #$A a3eotrope ater

"sim!lation res!lt !sing e(!ilibri!m reactor model%& Therefore it is necessary that the

content of the li(!id mi/t!re is cons!med beyond the e(!ilibri!m limit attainable !sing a stoichiometric feed to prod!ce high p!rity #$A& This is achieved by feeding an e/cess of propylene into the reaction 3one& >hen the propylene; ater molar feed ratio is 2&+5-, conversion of propylene to #$A in the d!al catalyst bed CD col!mn is 68,, and the concentration of #$A in the bottom stream is as high as ++&+mol,& #n contrast, the e(!ilibri!m conversion to #$A of the same feed mi/t!re is only @&?mol, at the same temperat!re and press!re in a conventional reactor& At feed ratios belo 2&+5- and an operating press!re of

2M$a, #$A decomposition occ!rs on the !pper catalyst bed d!e to lo propylene li(!id phase concentration in the bed, res!lting in the increase of ater concentration and decrease of #$A

concentration in the li(!id prod!ct stream& At feed ratio above 2&+5-, there is no significant improvement in #$A concentration of li(!id prod!ct& *o ever, the amo!nt, and hence the cost of propylene recycle are increased& A conse(!ence of !sing a higher propylene; ater ratio is a higher recycle rate of !nreacted propylene& The e(!ilibri!m constant of the reaction depends on the temperat!re,

-6

hich in t!rn is a f!nction of the operating press!re& Conse(!ently, the amo!nt of propylene converted to prod!ct and the amo!nt of propylene recycled vary ith temperat!re& At 2M$a

and propylene; ater molar feed ratio is 2&+5-, the reaction temperat!re is ?982 in the !pper catalyst bed and ?-9 in the lo er catalyst bed, nearly -99, of propylene cons!med in reaction is converted to #$A& The optim!m val!es "2&+5-% for the feed ratio and the temperat!re of reaction at 2M$a provide for optim!m col!mn performance hich 0eeping the costs for recycling propylene at a reasonably lo val!e&

Distillate *lo. !ate

The distillate from the CD col!mn consists mainly of !nreacted propylene inerts carried by the propylene feed stream& $ropylene is separated from the ma1ority of the propane and other imp!rities in a separation !nit, and the propylene is recycled to the CD col!mn& Contin!o!sly feeding and recycling propylene serves to increase the propylene concentration in the reaction 3one, and thereby to drive the reaction beyond the e(!ilibri!m limitation& Decycling the propylene also avoids acc!m!lation of other imp!rities in the reaction 3one by contin!o!sly removing them from the CD col!mn& The model has been r!n !sing both +8 t, and ++ t, propylene& =o performance benefic accr!es from the !se of ++ t, propylene& Th!s the economic benefic from !sing +8 t, propylene ma0e it the preferred feed& #n a conventional distillation col!mn, a high distillate rate !s!ally leads to a lo prod!ct flo li(!id

rate, b!t a higher concentration of prod!ct in the li(!id stream& This is not

necessarily tr!e for a CD process& Changing the distillate flo rate affects the performance of the CD col!mn thro!gh the interaction bet een reaction and separation& The dependence of

-?

#$A concentration in the li(!id prod!ct stream on the ratio of distillate flo feed rate is sho

rate to propylene

in Cig!re 8& The concentration c!rve of #$A is volcano shaped& The #$A hen distillate;propylene

concentration in the li(!id prod!ct reaches highest "++&+ mol,%

feed molar ratio is 9&68@ "Table 6%& At the optim!m temperat!re and press!re, D#$E forms lo boiling point a3eotropes ith ater and #$A, and remains in the !pper part of stripping

section and the reaction 3one

hile high p!rity #$A gathers at the bottom of the col!mn

"Cig!re ?%& The compositions of different a3eotropes are listed in Table - ".erge et al& 28%& The high concentration of D#$E in the reaction 3one inhibits formation of additional D#$E, and propylene is hydrated to #$A& The li(!id mi/t!re flo ing do n from reaction 3one into the stripping section of the CD col!mn consists mainly of #$A as essentially all ater is

cons!med in the hydration reaction& #$A and ater form lo boiling point a3eotrope& The #$A concentration in the li(!id stream on the top of the stripping section is higher than the #$A content of a3eotropic mi/t!re& Therefore, #$A is collected at the bottom of the stripping section and the a3eotrope rises to the top of the stripping 3one& Unli0e conventional propylene hydration processes here e/tra col!mns are re(!ired to separate D#$E and ater from #$A, or0 as a

no s!ch col!mns are re(!ired for the CD process beca!se a3eotropes of the system carrier to lift D#$E and

ater !p to the reaction 3one and constrain them in the middle of the

CD col!mn& Etherification does not have a detrimental effect on #$A prod!ction in the CD process hen it is cond!cted at 2 M$a& >hen the distillate;propylene ratio is lo er, the conversion of propylene and ater in the reaction 3one m!st be higher as less propylene leaves from the top of the CD col!mn as volatile compo!nd& 4ignificant amo!nt of D#$E is prod!ced in the reaction 3one d!e to lo concentration of ater and high concentration of propylene in the catalyst beds& Cor e/ample,

-8

hen the distillate;propylene feed molar ratio 9&6-A, the #$A mole fraction in the li(!id prod!ct is only 9&@@ tho!gh total conversion of propylene is ?9&? mol,& Up to @&8 mol, of propylene forms by)prod!ct D#$E, and only 6-&+mol , propylene is converted to #$A& As distillate;propylene feed molar ratio increases, D#$E concentration in the li(!id prod!ct stream decreases hile #$A concentration increases "Cig!re 8%& >hen the distillate;propylene

feed molar ratio goes higher than the optim!m val!e, less propylene is cons!med in the reaction 3one& Therefore less #$A is formed and more !nreacted ater flo s into stripping

section& >ater concentration in the li(!id prod!ct goes !p& Th!s, it is necessary to caref!lly control the distillate flo rate to optimi3e the conversion of ater and p!rity of #$A prod!ced&

"ingle and 'ultiple Catalyst #ed CD Column The CD col!mn ith a single catalyst bed located on the 8 th plate as first modeled, the

potential benefits of having t o or more catalyst beds has also been determined& A higher conversion of propylene is attainable, depending on the location and the n!mber of catalyst bed& %& *igher conversion of #$A is achieved plate and hen the second reaction is located on the 6 rd

ater feed is split bet een 6rd and 8th plate& #$A concentration in the li(!id prod!ct

goes !p to ++&+mol, "Table 6%& The benefit res!lt from improvement in the separation in the rectifying section above the catalyst bed at the 8th plate& Additional propylene is hydrated in the second catalyst bed, hich o!ld other ise have been recycled& >hen a second catalyst

bed is located lo er than the first catalyst bed and propylene feed "on the + th plate%, and no other changes are made, no benefit is observed& A detrimental interaction occ!rs bet een the phase and chemical e(!ilibri!m, so the temperat!re of the catalyst bed on the 8th plate decreases to 62?2 and #$A concentration in li(!id prod!ct decreases to ++&6mol, "Table 6%&

-6

A CD col!mn

ith three catalyst beds each mo!nted on 6 rd, 8th, and +th plates

as also

st!died& Des!lt sho s the temperat!res of the !pper t o catalyst beds decrease too& Fo er temperat!re in the catalyst bed leads to lo reaction rate and larger amo!nt of catalyst to be

!sed, therefore avoided in the present design& The #$A concentration in the prod!ct stream of the single catalyst bed model increases to ++&+, hen the propylene; ater feed ratio is

increased to 6&@5-, b!t the conversion of propylene decrease to A?mol,& The CD col!mn of d!al catalyst beds mo!nted on the 6rd and 8th plates is the optim!m config!ration propylene conversion and s!itable catalyst bed temperat!re& ith highest

Theoretical "eparation Plates

*aving determined the re(!irements for location of the reaction 3one and the optim!m feed ratio, the n!mber of theoretical plates re(!ired for each of the rectifying and stripping sections can be determined& The d!al bed CD col!mn model has been r!n to determine the optim!m n!mber of plates in each section independently& The level of separation of the prod!ct !s!ally increases ith increasing theoretical plates& *o ever, as the n!mber of plate

increases, the benefit of adding another plate becomes progressively smaller& =o appreciable val!e accr!es from increasing the n!mber of plates in the stripping section above 2- "Cig!re 6%& 4imilarly, no benefit accr!es from increasing the n!mber of plates in the rectifying section above t o for the d!al catalyst bed CD col!mn or above fo!r for the single catalyst bed col!mn& Th!s, in each case the CD col!mn comprises 26 theoretical plates, of to 26 comprise the stripping section& hich plates 6

-A

(ffect of %ther %perating and Design +ariables

The reactor can be operated so that the reaction 3one is at the temperat!re at

hich the

catalyst is active& #on)e/changed resin, t!ngsten o/ide and 3eolite have been reported to have high activity for the li(!id phase hydration of propylene to #$A "Eg!chi, et al& -6, 2aiser, et al&26, $etr!s, et al&2?,%& >hen the reaction is in the range of 6262 to ?862, an acid ion) e/change resin catalyst "e&g& Amberlyst resin% can be !sed as the catalyst& The disadvantage for the application of ion)e/change resins as heterogeneo!s catalysts is the increasing thermal instability at elevated temperat!re "$etr!s, et al& 28%& Therefore, for high temperat!re hydration reactions it is necessary to !se acidic inorganic catalysts having high thermal stability& The feed temperat!re has only a slight effect on the operation of the process& *o ever, the reaction is highly e/othermic, and so feeds that are slightly cooler than the catalyst beds temperat!re have a beneficial effect in controlling reaction 3one temperat!re& #n an alternative model, a combination of a pre)reactor and a CD col!mn can be !sed& #f the rate of reaction is slo , a large amo!nt of catalyst is re(!ired& #n s!ch a case, !se of a pre) reactor allo s conversion of a ma1ority of the feed to a reaction mi/t!re containing #$A that can be fed to the CD col!mn to react ith additional propylene& The pre)reactor can also

contain a g!ard bed to remove poisons in the feed stream and thereby prolong the life of catalyst in the CD col!mn "4!ba alla and Cair26%&

#($(*IT" %* TH( CD P!%C("" 4im!lation of the steady)state CD process "Cig!re A% sho s that the ne process has

advantages over conventional processes "Cig!re -%& Table ? presents a detailed comparison of

-@

the state)of)the)art conventional processes and the ne

CD process& E(!ipment for ith cooling system

conventional propylene hydration processes !s!ally consists of reactors

and a series of separation col!mns& >ater is a large component of the li(!id prod!ct stream& Conse(!ently, e/cess ater has to be removed first thro!gh distillation to obtain the a3eotrope mi/t!re& Then, e/tractive distillation is applied to brea0 the a3eotrope& Cinally, the e/tractive agent remaining in the #$A has to be removed to meet the #$A prod!ct standards& Typically, fo!r distillation col!mns are re(!ired to treat the prod!ct stream from a conventional reactor to get high p!rity #$A "=eier and >oellner 6%& The proposed CD process consists of one col!mn having a catalyst bed in the middle section& *igh p!rity #$A "++&+mol,% is obtained directly from the col!mn& Clearly, the CD process is m!ch simpler to constr!ct and operate "Table ?%& C!rther, it is operated at a m!ch lo er press!re and temperat!re than conventional li(!id phase hydration processes& *ence, the capital and operating cost are red!ced dramatically, and operation is more straightfor ard& The CD process also offers red!ction in operating costs arising from reactor cooling, catalyst recycle, and compared ater recycle& A cost associate ith the ne process

ith conventional direct hydration processes having high propylene conversions is

the high propylene recycle ratio& An e/cess amo!nt of propylene is fed to the reaction 3one to ens!re the ma/im!m conversion of ater, close to -99,& The optim!m propylene to ater ater hile

feed ration ratio of 2&+5- ens!res both ma/im!m conversion of s!bstantially all minimi3ing costs for propylene recycle&

-+

C%$C)&"I%$"

A process for the prod!ction of #$A

ith a catalytic distillation col!mn has been

modeled& The !se of a CD process alleviates e(!ilibri!m limitation& The model sho s that high p!rity #$A "++&+mol,% can be prod!ced as a li(!id prod!ct stream containing virt!ally no ater, in contrast to conventional processes& The red!ction of ater content occ!rs by reaction ater content belo the

a3eotrope

ith a 2&+5- optim!m molar e/cess of propylene&

E/cess propylene is recycled& The e(!ilibri!m ether content of the reaction mi/t!re is retained in the reaction 3one& The optim!m operating press!re is 2)? M$a, and the col!mn temperat!re range is 686)8262, to allo sim!ltaneo!s reaction and separation of the reaction mi/t!re&

29

!(*(!($C("

-& *ancoc0, E&G&, -+A6, Propylene and Its Industrial Derivatives& 2& 2rosch it3, :& #&, -++-, 2ir0)'thmer Encyclopedia of Chemical Technology, 295 2-6)2?9& 6& =eier, >&, >oellner :&, -+A6, #sopropyl alcohol by Direct *ydration, CHE !ECH, 6"Ceb%5 +8)++& ?& 'no!e, H&, Mi3!tani, H&, A0iyama, 4&, #3!mi, H&, -+A@, *ydration CHE !ECH, @5 ?62)??9& 8& 4avini, C&, -+A@, Process for Improvin" Odor of Isopropanol# $ower %lcohols and Other O&y Derivatives of $ower %lcohols, U2 $atent =o A,@66,6@6& 6& DeGarmo, :& F&, $ar!le0ar, B& =&, $in1ala, B&, -++2, Consider Deactive Distillation, Chemical En"ineerin" Pro"ress, March5 ?6)89& A& Doc0, 2&, Gildert, G&, McG!ir0, T&, -++A, Catalytic Distillation, Chemical En"ineerin", :!ly5 A@)@?& @& 4hoema0er, :& D&, :ones, E& M&, -+@A, C!mene by Catalytic Distillation # Hydrocar'on Processin", :!ne5 8A)8+& +& $odrebarac, G& G&, =g, C& T& T&, -++A, More Uses for Catalytic Distillation, CHE !ECH, May5 6A)?8& -9& 2!o, H& C&, Chen, H& >&, -+++, #sopropyl Alcohol Dehydration over Chrominophosphate Catalysts)#& A 2inetic 4t!dy# () Chin) Inst) Chem) En"rs&, 695 ?2-)?2@& --& 4onnemanes, M& *& >&, -++6, *ydration and Etherification of $ropene over *)I4M)8& -& A 2inetic 4t!dy, Ind) En") Chem) *es&, 625 2896)28--& ith >ater,

2-

-2& 4onnemanes, M& *& >&, -++6, *ydration of $ropene over Acid Ieolites, %pplied Catalysis %: +eneral# +?5 2-8)22+& -6& 'dioso, D& C&, *en0e, A& M&, 4ta!ffer, *& C&, Crech, 2& :&, -+6-, Direct *ydration of 'lefins ith Cation E/change Desins, Industrial and En"ineerin" Chemistry, 86"6%5 29+) 2--& -?& =g, C& T& T&, Dempel, G& F&, -+++, Catalytic Distillation, Canadian Chemical ,ews, :!ly;A!g!st5 -+)29& -8& $ilavachi, $& A&, -++A, Modeling and 4im!lation of Deactive Distillation 'perations, Ind) En") Chem) *es&, 665 6-@@)6-+A& -6& Eg!chi, 2&, 2odiai, T&, Arai, *&, -+@A, *igh $ress!re Catalytic *ydration of 'lefins over $roton)E/changed Ieolites, %pplied Catalysis, 6?5 2A8)2@A& -A& $odrebarac, G& G&, =g, C& T& T&, Dempel, G& F&, -++@, The $rod!ction of Diacetome Alcohol ith Catalytic Distillation $art ##5 A Date).ased Catalytic Distillation Model for

the Deaction Ione, Chemical En"ineerin" Science, 865 -9AA)-9@@& -@& 4neeby, M& G&, Tade, M& '&, Datta, D&, 4mith, T& =&, -++A, ET.E 4ynthesis via Deactive Distillation& -& 4teady)4tate 4im!lation and Design Aspects # Ind) En") Chem) *es&, 665 -@88)-@6+& -+& Eldarsi, *& 4&, Do!glas, $& F&, -++@, Methyl tert).!tyl Ether Catalytic Distillation Col!mn $art #5 M!ltiple 4teady 4tates, !rans) I ChemE&, A6, 89+)82?& 29& =i1h!is, 4& A&, 2er0hof, C& $& :& M&, Ma0, A& =& 4&, -++6, M!ltiple 4teady 4tates D!ring Deaction Distillation of Methyl tert).!tyl Ether, Ind) En") Chem) *es&, 625 2A6A)2AA?& 2-& .erge, F&, Hang, I&, -++2, Separation of Propyl %lcohols from -ater 'y %.eotropic or E&tractive Distillation# United 4tates $atent =o 8,9@8,A6+&

22

22& Cran0, .& D&, Dodge, .& C&, -+8+, Bapor)Fi(!id E(!ilibri!m at *igh $ress!res, (ournal of Chemical and En"ineerin" Data, ?"2%5 -9A)-2-& 26& 2aiser, :& D&, .e!ther, *&, Moore, F& D&, 'dioso, D& C&, -+62, Direct *ydration of $ropylene over #on)E/change Desins, I/EC Product *esearch and Development, -"?%5 2+6)692& 2?& $etr!s, F&, De Doo, D& >&, 4tamh!is, E& :&, :oosten, G& E& *&, -+@?, 2inetics and E(!ilibria of The *ydration of $ropene over a 4trong Acid #on E/change Desin as Catalyst, Chemical En"ineerin" Science, 6+"6%5 ?66)??6& 28& $etr!s, F&, 4tamh!is, E& :&, :oosten, G& E& *&, -+@-, Thermal Deactivation of 4trong)Acid #on)E/change Desins in >ater, Ind) En") Chem) Prod) *es) Dev&, 295 666)6A-& 26& 4!ba alla, *, Cair, :& D&, -+++, Design G!idelines for 4olid)Cataly3ed Deactive Distillation 4ystems, Ind) En") Chem) *es)# 665 66+6)6A9+&

26

ADDDE44

Correspondence concerning this paper sho!ld be addressed to $rofessor 2&T& Ch!ang, Department of Chemical and Material Engineering, 866 Chemical and Material Engineering .!ilding, University of Alberta, Edmonton, Canada, T6G 2G6& $hone5 A@9)?+2)?6A6, Ca/5 A@9)?+2)2@@E)mail5 2arlT&Ch!angJUalberta&ca&

2?

DEACT'D

4E$ADAT'D AIE' C'FUM= F#G*T E=D C'FUM=

$D'$HFE=E

>ATED

#4'$D'$A='F

0i"ure 1) Clo diagram of To0yoyama C'FUM= isopropyl alcohol process&

DE*HDDAT#'=

DEC'BEDH C'FUM=

28

$ropylene Decycle

>ater feed $ropylene feed

0i"ure 2) Config!ration of single catalyst bed catalytic distillation col!mn& #$A prod!ct

26

$ropylene Decycle

>ater feed

>ater feed $ropylene feed

#$A prod!ct

0i"ure 3 Config!ration of d!al catalyst bed catalytic distillation col!mn&

2A

1 0.9 0.8 0.7 Mole Fraction 0.6 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
WATER PROPYLENE IPA PROPANE DIPE

Stage

Cig!re ?& Fi(!id phase composition profile of d!al catalyst bed CD col!mn "propylene; ater molar feed ratio72&+5-< plate - is condenser< plate 2@ is reboiler%

2@

0.14

1.02

0.12

1.00

0.98 0.10

Mole Fraction

0.96 0.08

D#$E
0.06

0.94

0.92 0.04

ater
0.02

0.90

0.88

0.00 0.61

0.62

0.63

0.64

0.65

0.66

0.67

0.68

0.69

0.86 0.70

Distillate/propylene

0i"ure 4) Effect of distillate flo rate on d!al catalyst bed CD col!mn performance "propylene; ater molar feed ratio7-52&+%&

2+

Mole Fraction

#$A

9&++-8

IPA 'ole *raction in )i/uid Product

9&++-9

9&++98

9&++99

9&+@+8 -9 -8 29 28 69 68

$umber of Plates in "tripping "ection

0i"ure 5& Effect of the n!mber of stripping plates on CD col!mn performance " ater;propylene molar feed ratio7-52&+< distillate;propylene molar ratio79&66%&

69

'lefin $8 Definery

$?

$ropylene

*igh $!rity #$A

CD

4-

$-

*-

>ater $6 *2

*igh $!rity #$A 46

0i"ure 6) Clo diagram of catalytic distillation isopropyl alcohol process& a& 4The line part of the diagram is incl!ded in the t o reaction)3one catalytic 2 dashed$2 distillation process CD catalytic distillation col!mn, *-, *2, *6 heat e/changes $-,$2,$6,$?,$8 p!mps 4-,42,46 storage tan0s

6-

!a'le1) A3eotropes of >ater)#$A)D#$E 4ystem&

compo!nd or a3eotrope ater #$A D#$E aterK#$A #$AKD#$E aterKD#$E aterK#$AKD#$E #$A5 isopropanol

boiling temperat!re of a3eotrope "2% 6A6&-6 688&68 6?2&-8 686&?8 66+&68 668&68 66?&A8 D#$E5 diisopropyl ether

composition of a3eotrope ater #$A D#$E t, t, t,

-2&6 9 ?&8 ?&A

@6&A -6&6 9 A&6

@6&A +8&8 @@&9

62

!a'le 2) Effect of Distillate;$ropylene Datio on CD Col!mn $erformance

distillate;propylene feed molar ratio #$A mole fraction in prod!ct stream total propylene conversion mol, ater conversion mol, propylene conversion to #$A mol, propylene converison to D#$E mol, L ater;propylene molar feed ratio7-52&+

0.6170

0.6580

0.6890

9&@@69
40.4036 0.9976 31.9373 8.4663

9&+++36.1801 0.9975 36.1529 0.0272

9&+9@6
32.8649 0.9060 32.8528 0.0121

66

!a'le 3) Comparison of M!ltiple and 4ingle Catalyst .ed CD Col!mn&

catalyst b !

catalyst b ! t "# $at%$ &'( 3$! #lat 5t0 #lat 409 410 324 322 405 324 410 409 409 9 t0 #lat

IPA )* l)+%)! #$,!%ct ",l 1$act),* 0.994 0.999 0.993 0.993 0.999

#$,#yl * -.at $ 1 ! ",la$ $at), 2.931 3.831 2.931 2.931 2.931

#$,#yl * c,*/ $s),* ",l2 34 26 34 34 35

1 1 2 3 2

6?

!a'le 7& Comparison of $ropylene *ydration $rocesses& direct hydration process $D' feed stream " t,%L catalyst catalyst regeneration reactor cooling of reactor distillation col!mn in process operating press!re "M$a% operating temperat!re "2% feed ratio " ater;$D'% $D' recycle;feed mole ratio ater recycle;feed mole ratio conversion #$A selectivity L $D'7propylene fi/ed)bed tric0le)bed vapor phase mi/ed phase ++ +2 >'6)In';*6$'? ion)e/change resin no no yes yes yes yes ? ? 2&8)6&6 @)-9 8-6)826 ?96)?66 -5?)-9 -2)-85+?)+8, 28, ?9)@9, +?)+8, 8)6, $D' A8, $D' +6, +6, LL 3eolite or proton)e/changed resin

li(!id phase +8 a(!eo!s silicot!ngstate yes yes yes ? 29&6 8-6)866 69)?9, 69)A9, $D' +@)++,

catalytic distillation +8 LL no no no 2 6?6)826 -52&+ 68, 9 68, $D', E++, ater +8,

68