CHAPTER 1

INTRODUCTION
1.1 Isopropyl Alcohol Production
Isopropyl alcohol (IPA) has been called the first modern synthetic petrochemical.
With physical characteristics compatible with those of alcohol, water, and
hydrocarbons, IPA is a versatile and inexpensive solvent used widely in the chemical
and cosmetics industries. Unlie ethanol, IPA is sub!ect to few "overnment re"ulations,
and no special taxes are levied on its consumption. IPA is used as feedstoc for the
manufacture of acetone and other compounds, and is used widely as an antiseptic and
disinfectant for home, hospital, and industry applications (#ancoc, $%&'( )roschwit*,
$%%$).
In terms of production volume, IPA is about the fourth lar"est chemical. +otal $%%'
U.,. nameplate capacity for isopropyl alcohol production was -..-/$0
1
metric tons. +he
total world capacity is about 2.0/$0
%
metric tons. +he $%%1 U.,. prices were 30.1145
(32.$04"al) for refined %$vol 6 and 30.7245 (32.'74"al) for anhydrous alcohol, an
increase from the 30.$-45 (30.&04"al) avera"e price of $%&&. +he price of IPA is driven
by the price of propylene, the primary feedstoc, and by the price of ethyl alcohol, a
competin" solvent (5o"sdon and 5oe, $%%').
+he future demand for IPA is expected either to remain flat or to "row sli"htly. Its
main use as a chemical intermediate is "rowin", and this should offset the pressure on
use as a solvent from ti"hter volatile or"anic chemicals (89:) re"ulations.
$
+he first industrial ;uantities of IPA were produced in $%20 in the world<s first
petrochemical plant, owned by ,tandard 9il :ompany (=>>9?). +o date, various
methods for preparin" IPA and various catalysts have been developed. +he methods
used most widely are direct hydration and indirect hydration of propylene ()roschwit*,
$%%$). @oth processes use propylene and water as raw materials. 9ther potential
synthetic methods include fermentation of certain carbonhydrates, oxidation of propane,
hydro"enation of acetone, and hydrolysis of isopropyl acetate.
Indirect hydration is based on a twoAsta"e process in which an ester is formed and
then hydroly*ed to the correspondin" alcohol. Beaction can be conducted throu"h two
operational modelsC twoAstep stron" acid process( oneAstep wea acid process.
Diisopropyl ether (DIP=) is the principal byAproduct.
AcidAcataly*ed direct hydration of propylene to IPA is reversible and exothermic
(=;uation $.$).
#ydrationC
CHOH CH O H CH CH CH
k k
2 '
,
2 2 '
) (
$
$$ $$
+ =

($.$)
#EA10F4mol (A$2cal4mol, 2%-.$1), $atm)
DIP= is the principal byAproduct. +he overall formation reaction of the ether may either
be written asC
O CH CH O H CHOH CH
k k
2 2 ' 2
,
2 '
) ) (( ) ( 2
$
22 22
+

($.2)
#EA$1F4mol (A'.&cal4mol, 2%-.$1), $atm)
orC
2
O CH CH CHOH CH CH CH CH
k k
2 2 '
,
2 ' 2 '
) ) (( ) (
$
'' ''
+ =

($.')
+here are three propylene direct hydration processes in commercial operationC
vaporAphase hydration over a fixedAbed catalyst ()roschwit*, $%%$)( mixed vaporA
li;uidAphase hydration usin" stron"ly acidic protonAexchan"e resin catalyst (?eier and
Woellner, $%&')( and li;uidAphase hydration in the presence of a homo"eneous catalyst
(9noue et al., $%&-).
=conomic comparisons of the indirect and direct hydration processes show a cost
savin"s for use of the latter technolo"y. +he lar"est savin"s are in capital investment,
processin" and maintenance, all of which are necessitated by the troublesome sulfuric
acid reconcentration of the indirect process. Greater corrosion and pollution problems
are also associated with indirect hydration. #owever, drawbacs of direct hydration are
its hi"h ener"y usa"e and the need for hi"hly concentrated propylene feedstoc
(5o"sdon and 5oe, $%%').
+he re;uired purity of IPA product depends on the intended application. +he %$ vol
% IPA a*eotrope produced is sold as such or is dehydrated by a*eotropic distillation to
produce an anhydrous product. Hinor impurities are removed and the odor of IPA is
improved by use of either intense a;ueous extractive distillation, or postAtreatment by a
fixedAbed absorption process usin" activated carbon, molecular sieves or metals and 4or
metal oxides of Group I@, 8I@ and 8III of the Periodic +able (,avini, $%&-). =ssence
"rade IPA is produced by distillation of dehydrated IPAAwater a*eotrope in nonferrous
e;uipment.
'
A typical conventional process scheme for direct hydration of propylene is shown
in Ii"ure $.$. +he principal difference between the direct and indirect processes is that
much hi"her pressure is re;uired for the direct hydration process. +he slate and
distribution of products and byAproducts from each process are similar, and systems for
refinin" IPA are essentially the same.
1.2 Catalytic Distillation
Beactive distillation comprises the processes of catalytic reaction and multista"e
distillation carried out simultaneously in a sin"le vessel. A reactive distillation column
replaces the reactor and a series of distillation columns, thereby reducin" the number of
process vessels and materials transfer and control e;uipment re;uired. +hus, capital
costs are reduced (DeGarmo et al., $%%2).
+he concept of reactive distillation is not new. It was first applied to eaterification
process usin" homo"eneous catalysts in $%20<s. +he use of solid hetero"eneous catalyst
for reactive distillation is a more recent development, first described by ,ennewald et
al. ($%&$). +he advanta"es of usin" solid catalysts oveAr homo"eneous catalysts are
obviousC they are easy to separate from reaction mixtures, easy to handle and less waste.
,olid catalysts also offer the potential for superior effectiveness and environmental
inte"rity. #owever the column internals are more complicated when usin" solid
catalysts.
@ubbleAcap or sieve trays are common e;uipment used for homo"enous reactive
distillation processes. With hi"h weirs, they provide the necessary li;uid hold up and
.
residence time needed for the reaction. =;uipment for hetero"eneous reactive
distillation consists primarily of catalyst containin" pacin", which allows for
simultaneous reaction and mass transfer between vapor and li;uid phases. +he
hetero"eneous catalyst acts as distillation pacin" as well as catalyst, therefore,
hetero"eneous reactive distillation is often termed as catalytic distillation (:D) to
differentiate between the two processes (homo"eneous and hetero"eneous).
1.3 Applications o CD
:D is a viable option when the temperature and pressure of a process are such that
the rate of reaction is sufficiently hi"h under conditions for separation of products by
distillation. +he catalyst life must be lon" in order to avoid fre;uent startAup and shutA
down. =;uilibriumAlimited reactions are excellent candidates for catalytic distillation(
by continuously separatin" products from reactants while the reaction is in pro"ress, the
reaction can proceed to a much hi"her level of conversion than is attainable usin" a
conventional process (Boc et al., $%%&( ,hoemaer and Fones, $%-&).
:D is potentially attractive whenever a li;uid phase reaction must be carried out
with a lar"e excess of one reactant. Under such circumstances, conventional processes
incur lar"e recyclin" cost for the excess reactant. It may also be used for the separation
of difficult systems. Podrebarac ($%%&) "ave a comprehensive review of the various
uses for :D prior to the end of $%%7. A recent literature search revealed that a lar"e
number of patents were "ranted in the last few years on the use of :D on a variety of
chemical processes. +hese new :D processes are at various sta"es of development.
1
Boc et al. ($%%-) proposed a process for the improved sulfur removal from fluid
catalytic cracin" (I::) "asoline via :D. :onductin" hydrodesulfuri*ation (#D,) to
remove sulfur in a :D column offers the uni;ue advanta"e to attain hi"h sulfur
conversion with minimal octane loss. +his is due to the fact that the li"ht olefins are
concentrated at the top of the distillation column where the temperature is lower than
the bottom of distillation column. +his reduces the saturation of the li"ht olefins and at
the same time, li"ht sulfur components could still be desulfuri*ed at the top of the
column. +he hi"her molecular wei"ht sulfur containin" compounds under"o #D, at the
bottom of the distillation column where the hi"her temperature facilitates the #D,
process.
Another application of :D is the :D hydro"enation process, which combines
fractionation to"ether with hydro"enation. +he :D process operates at substantially
lower pressure than conventional hydrotreatin" processes due to the enhanced mass
transfer between the vapor and li;uid phases in the distillation process, which enables
hydro"enation at hi"h rates even at low hydro"en pressures.
A new :D application for the hydro"enation of ben*ene in reformate has been
commerciali*ed to produce "asoline that meets the ben*ene content specification (Boc,
et al., $%%&). 9ne application of this technolo"y is the simultaneous processin" of both
reformatted and li"ht, strai"htArun "asoline in a sin"le :D column. +his option "ives the
refiner the capability to reduce ben*ene in "asoline while increasin" the octane number.
7
:D was also applied to the remove of acetic acid from dilute acetic acid produced in
many chemical and petrochemical industrial applications. In the :D column, methanol
is introduced to react with acetic acid. +he reaction product, methyl acetate, is removed
from the top of the column and water is withdrawn from the bottom (>u et al., $%%&).
5ee et al. (2000) used an isomeri*ation reaction of 2Aphenylethanol to pAethylphenol
in a catalytic distillation column to circumvent the a*eotrope between pAethylphenol and
2Aphenylethanol. Placin" sufficient reaction on only two trays in the top section of the
column, the top operatin" line was shifted to below the .1 line. 9n lower nonreactin"
trays, the a*eotrope was circumvented. It was found that the column temperature
decreases from sta"es on the top of the column to those at the bottom of the column.
:urrently, the lar"est commercial users of :D technolo"y are fuelAether producin"
units. A variety of ether, for example methyl tertAbutyl ether (H+@=), tertAamyl methyl
ether (+AH=), ethyl tertAbutyl ether (=+@=), tertAamyl ethyl ether (+A==) and tertA
hexyl ethyl ether (+#==), can be produced by reactin" olefins havin" four, five, or six
carbon atoms with methanol or ethanol (Jhan" et al., $%%1( ,ubramaniam et al., $%-&(
Behfin"er et al., $%%0( Biho et al., $%%&( Podrebarac et al., $%%&( ?" et al., $%%%).
H+@= is the first chemical commercially manufactured usin" :D techni;ue.
1.! Pro"l#$ D#inition
&
Direct hydration of propylene is the preferred process for production of IPA
because it avoids some corrosion and environment problems encountered usin" indirect
hydration processes. Improvements to the hydration process have been made in recent
years on the operatin" conditions, catalyst, and extractive solvent (@ell et al., $%%7(
Atins, $%%&( @rown et al., $%%7( Bamachandran et al., $%%7( ,chmidt, $%-.).
#owever, current processes still re;uire the use of complex distillation columns to
recover IPA from the product stream, which leads to hi"h ener"y usa"e. ,eparation of
IPA from the a*eotropic mixture is technically difficult and expensive.
+he ob!ective of this thesis research is to investi"ate a novel approach for the
synthesis of IPA, catalytic distillation, as a simpler and less expensive alternative to
conventional processes for production of IPA.
+he research pro!ect consists of the followin" tassC
$. Hodelin" of the catalytic distillation process. Initial simulation of the catalytic
distillation was performed usin" a commercial simulation paca"e K Aspen Plus.
Impacts of ey desi"n parameters were examined systematically. An optimum
confi"uration of the catalytic distillation column has been determined.
2. Beaction inetic study. )inetics of propylene hydration and IPA etherification
were measured in a batch slurry reactor. +he research includesC screenin" solid acid
catalyst( eliminatin" internal and external mass transfer effects( studyin" effects of
temperature and reactant concentration on reaction rates( and derivin" inetic rate
e;uations.
-
'. Desi"n of :D column. A :D column for IPA production was si*ed and column
confi"uration was determined by incorporatin" the reaction inetics with the optimal
simulation results.
1.% Application o CD to Production o IPA
Propylene hydration to IPA is an excellent candidate for application of :D
technolo"y for the followin" reasonsC
$. Direct hydration of propylene is an e;uilibriumAlimited reaction (=;uations $.$A
$.').
2. #ydration taes place in the li;uid phase( catalyst pellets remain completely
wetted.
'. +he reaction occurs at a temperature and pressure e;uivalent to the boilin" point
of the li;uid product( thus distillation and reaction can be carried out simultaneously in
the same column.
.. #ydration is exothermic( the heat of reaction provides a portion of ener"y
re;uired for the separation of the reaction mixture by distillation.
1. Durable hetero"eneous hydration catalysts with suitable physical properties are
commercially available ()uo and :hen, $%%%( ,onnemans, $%%'( 9dioso et al., $%7$).
7. In a :D hydration process, water will be continuously consumed by fresh
propylene, and an IPAArich stream will be continuously produced. #ence, e;uilibrium
limitations will be overcome, and the product stream will have a hi"her IPA content
than product streams from conventional processes.
%
A ma!or advanta"e of catalytic distillation over conventional fixedAbed reactors is
the reduction in capital investment (?" and Bempel, $%%%( Podrebarac and ?", $%%&(
Boc et al., $%%&). In addition, operatin" costs for production of IPA are reduced, as
there is essentially no need to cool or heat the reactor. We will show that other benefits
accrue from use of :D techni;ue, includin" substantially complete consumption of
water and improved selectivity to IPA. ,afety and catalyst performance are also
enhanced by use of :D technolo"y, as the ris of formation of hot spots is lower in a
:D system than in a conventional vapor phase hydration reactor.
$0
1.& No$#nclatur#
# heat of reaction
1.' (it#ratur# Cit#d
Atins, H. P., $%%&, 9lefin #ydration Process, U, Patent, 1,7$7,-$1.
@er"e, 5., Lan", J., $%%2, ,eparation of Propyl Alcohols from Water by A*eotropic or
=xtractive Distillation, United ,tates Patent ?o 1,0-1,&'%.
@rown, ,. #., +rewella, F. :., $%%&, Gas Phase Process for the #ydration of Propylene,
U, Patent ?o, 1,.--,$-7.
#ancoc, =.G., $%&', Propylene and Its Industrial Derivatives, =. @enn, 5ondon.
)roschwit*, F. I., $%%$, )irA9thmer =ncyclopedia of :hemical +echnolo"y, 20, 2$7A
2.0.
)uo, L., :hen L., $%%%, Isopropyl Alcohol Dehydration over :hrominophosphate
:atalystsA$. A. )inetic ,tudy, F. :hin. :hem. =n"rs., '0(1), .2$A.2%.
5o"sdon, F. =., 5oe B. A., $%%', )irA9thmer =ncyclopedia of :hemical +echnolo"y.
?eier, W., Woellner F., $%&', Isopropyl alcohol by Direct #ydration, :#=H+=:#,
'(Ieb), %1A%%.
?", I. +. +., Bempel, G. 5., $%%%, :atalytic Distillation, :anadian :hemical ?ews,
Fuly4Au"ust, $%A20.
$$
9dioso, B. :., #ene, A. H., ,tauffer, #. :., Irech, ). F., $%7$, Direct #ydration of
9lefins with :ation =xchan"e Besins, Industrial and =n"ineerin" :hemistry, 1'('),
20%A2$$.
9noue, L., Hi*utani, L., Aiyama, ,., I*umi, L., $%&-, #ydration with Water,
:#=H+=:#, -, .'2A..0.
Podrebarac, G. G., ?", I. +. +., Bempel, G. 5., $%%-, +he Production of Diacetome
Alcohol with :atalytic Distillation Part IIC A BateA@ased :atalytic Distillation
Hodel for the Beaction Jone, :hemical =n"ineerin" ,cience, 1', $0&&A$0--.
Podrebarac, G. G., ?", I. +. +., $%%&, Hore Uses for :atalytic Distillation,
:#=H+=:#, Hay, '&A.1.
Bamachandran( B. D., 5oc, #., $%%7, Process for the Production of =thanol and
Iaopropanol, U, Patent ?o, 1,.--,$-1.
Behfin"er, A., #offmann, U., $%%0, )inetics of Hethyl +ertiary @utyl =ther 5i;uid
Phase ,ynthesis :atly*ed by Ion =xchab"e BesinA I. Intrinsic Bate =xpression in
5i;uid Phase Activities, :hemical =n"ineerin" ,cience, .1(7), $701A$7$&.
Biho, 5. )., )ivirantaAPaaonen, P. )., )rause, A. 9., $%%&, )inetic Hodel for the
=therification of Isoamylene with Hethanol, Ind. =n". :hem. Bes. '7, 7$.A72$.
Boc, )., Gildert, G., HcGuir, +., $%%&, :atalytic Distillation, :hemical =n"ineerin",
Fuly, &-A-..
,avini, :., $%&-, Process for Improvin" 9dor of Isopropanol, 5ower Alcohols and
9ther 9xy Derivatives of 5ower Alcohols, U) Patent &,-'','-7.
$2
,chmi, B. F., $%-., Process for :oproduction of Isopropanol and +ertiary butyl alcohol,
U, Patent, .,.-.,0$'.
,hoemaer, F. D., Fones, =. H., $%-&, :umene by :atalytic Distillation, #ydrocarbon
Processin", Fun, 1&A1%.
,neeby, H. G., +ade, H. 9., Datta, B., ,mith, +. ?., $%%&, =+@= ,ynthesis via Beactive
Distillation. $. ,teadyA,tate ,imulation and Desi"n Aspects, Ind. =n". :hem. Bes.,
'7, $-11A$-7%.
,onnemanes, H. #. W., $%%', #ydration and =therification of Propene over #AJ,HA1.
$. A )inetic ,tudy, Ind. =n". :hem. Bes., '2, 2107A21$$.
,uvramaniam, :., @hatia, ,., $%-&, +he :anadian Fournal of :hemical =n"ineerin", 71,
7$'A720.
Jhan", +., Datta, B., $%%1, =thers from =thanol. .. )inetics of the 5i;uidAPhase
,ynthesis of +wo tertA#exyl =thyl =thers, Ind. =n". :hem. Bes., '., 22.&A221&.
>u, J. P., Afacan, A., :huan", ). +., $%%%, Bemoval of Acetic Acid from Water by
:atalytic Distillation Part 2. Hodelin" and ,imulation ,tudies, +he :anadian
Fournal of :hemical =n"ineerin", &&, $A7.
$'
Ii"ure $.$ Ilow dia"ram of +oyoyama isopropyl alcohol process
$.
B=A:+9B ,=PABA+9B AJ=9 :95UH?
D=#LDBA+I9?
:95UH?
B=:98=BL :95UH?
PB9PL5=?=
5IG#+ =?D :95UH?
I,9PB9PA?95
WA+=B
CHAPTER 2
)I*U(ATION O+ A CD PROCE)) +OR IPA PRODUCTION
,imulation has become an essential component of catalytic distillation process
desi"n, and is even more important for :D process desi"n than for desi"n of
conventional reactor4distillation systems. +he interaction between simultaneous reaction
and distillation processes increases the complexity of :D systems compared with
systems comprisin" conventional reactors followed by distillation systems. Hodelin"
methods are of even "reater importance when there is no available satisfactory shortcut
or empirical methods for the determination of ey parameters (Pilavachi, $%%&).
Beliable simulation software allows a new :D process to be modeled usin" nown
thermodynamic and inetic data. 8alues for ey desi"n parameters can be identified
with a hi"h de"ree of confidence. ,imulation can also be applied to an existin" process
to study the effect of varyin" ey parameters, and thereby provide "uidelines for further
optimi*ation of the process.

2.1 )i$ulation ,as#s
,imulations in this study are based on e;uilibriumAsta"e and e;uilibriumAreaction
model usin" validated experimental data. H=,# (material balance, vaporAli;uid
e;uilibrium, mole fraction summations and heat balance) e;uations for systems in
vaporAli;uid and chemical e;uilibrium are used. +he set of e;uation for tray ! is as
followsC
$1
Haterial balance for component i
0
, , , $ , , $ ,
= + + +
+ j i j i j i j i j i j i
p f v v l l
(2.$)
8aporA5i;uid e;uilibrium for component i
0
, , ,
=
j i j i j i
x K y
(2.2)
,ummation e;uation for component i

=
=
n
i
j i
x
$
,
0 $
(2.')

=
=
n
i
j i
y
$
,
0 $
(2..)
=ner"y balance for component i
0
$ $ $ $
= + + +
+ + j
F
j j
V
j j
L
j j
V
j j
L
j j
Q h F h V h L h V h L
(2.1)
and :hemical e;uilibrium

= 0
, eq
v
j i
K c
i
(2.7)
=ven thou"h no reactive distillation process will ever operate under total
e;uilibrium conditions, an e;uilibriumAbased model provides theoretical limits of
achievable separation. :onstant plateAtoAplate pressure is assumed in the present model.
+his assumption introduces no si"nificant error for steadyAstate simulations at hi"h
pressures. +he present model includes IPA and DIP= as e;uilibrium products of the
hydration and etherification reaction.
+he aleneAalcoholAwaterAether system is nonAideal. :onse;uently, the selection of
physical property routines is of "reat importance. +he U?IIA: method has been used
$7
successfully to predict li;uid phase activity coefficients and e;uilibrium constant
expressions of similar nonAideal systems in simulation of =+@=, H=@=, +A==, and
DAA (diacetone alcohol) production processes (Podrebarac et al., $%%-( ,neesby et al.,
$%%&( 5inneosi et al., $%%&( Jhan" and Datta, $%%1( Delion et al., $%-&). U?IIA:
also has been used to accurately model the vaporAli;uid behavior of the IPAAwaterA
propyleneApropane system (Wyc*esany, $%%.). +he predicted boilin" points of
a*eotropes of IPAAwaterApropyleneADIP= system by U?II: have a standard error of
0.'A1.%6 comparin" to experimental data. 8aporAli;uid e;uilibrium data predicted by
U?IIA: is in "ood a"reement with the result of vaporAli;uid e;uilibrium experiment of
fourAcomponent mixture conducted in a batch reactor (:hapter '). +he U?IIA: method
therefore has been shown to be suitable for the calculation of the li;uid phase activity
coefficients based on binary experimental vaporAli;uid e;uilibrium data (Javaloy et al.,
$%%'( 5i and Hcetta, $%7'( :ope, $%77( @arrAdavid and Dod"e, $%1%( #ancoc, $%&'(
Fa, $%10). +he BedlichA)won" e;uation of state has been used to predict the nonAideal
vapor phase behavior of the system. =;uilibrium constants of the system were
calculated usin" literature thermodynamics data (Hafewse and Hare, $%'-( Petrus,
$%-7).
:ommercial simulation pro"rams most commonly used for the desi"n of :D
process includeC PB9II
+H
, AspenPlus
+H
, and #ysis Process. AspenPlus
+H
has been used
successfully on the simulation of several catalytic distillation processes (Abufares and
Dou"las, $%%1( >u et al., $%%&( =ldarsi and Dou"las, $%%-( ?i!huis et al., $%%'(
$&
Abufares and Dou"las, $%%1). It was found that AspenPlus
+H
was the pro"ram with
which conver"ed results were most readily obtained for the propylene hydration :D
process. +he BadIrac distillation unit built into AspenPlus
+H
can carry out calculation of
distillation and reaction (e;uilibrium or inetic model) simultaneously. It is used to
obtain the data reported herein.
2.2 Catalytic Distillation Colu$n
+he core of the :D process is the catalytic distillation column (Ii"ure 2.$). A
column in which propylene hydration is to be performed has three ma!or sections. +he
reaction occurs over one or more catalyst beds mounted in the middle section of the
column. Bectification of the volatile components of the reaction mixture occurs in the
top section. 5i;uid product is recovered from the bottom of a lower strippin" section.
We investi"ated :D columns with up to three catalyst beds. #ydration of propylene to
IPA and IPA etherification to DIP= proceed over the catalyst simultaneously with
distillation on the separation plates of the column. Unreacted volatiles rise from the
reaction *one to the rectifyin" section where they are separated from heavier
components before bein" removed from the top of the column. :ondensed materials fall
as li;uid from the reaction *one into the strippin" section. In the present model, an
a*eotropic mixture of IPA, DIP= and water is concentrated at the top of the strippin"
section, and enriched IPA havin" a very low water content is "athered at the bottom of
the strippin" section. +he a*eotrope vapor wors as a carrier to lift water and DIP= bac
to the reaction *one for water to be further reacted with propylene and for DIP= to
$-
e;uilibrate with IPA. +he IPA concentration in the product stream thereby exceeds the
e;uilibrium limit for the propyleneAwaterAIPA reaction by continuous removal of IPA
from the reaction *one.
2.3 )tudy o -#y D#si.n /aria"l#s
,imultaneous operation of both reaction and distillation in a sin"le vessel leads to
different responses to chan"es in operatin" conditions compared with production
systems havin" two separate processes. It is necessary to fully understand the
interaction between the processes to avoid suboptimal performance resultin" from poor
desi"n. +he dependence of :D column performance on each variable or combination of
variables is discussed in the followin" section.
2.3.1 Op#ratin. Pr#ssur# and T#$p#ratur#
In conventional distillation, condenser coolant and reboiler heatin" media
temperatures determine the pressure ran"e used. In a :D process, the selection of
operatin" pressure must tae into account the effect of pressure on the reaction *one
temperature, which depends on the relative volatility of reactants, products and
a*eotropes (DeGarmo et al., $%%2).
In a :D column, the reaction *one temperature is determined by the boilin" point
of the li;uid mixture in the catalyst bed, which in turn is determined by the composition
of the li;uid and the operatin" pressure. #owever, because separation and reaction
occur simultaneously in the column, the composition of the li;uid phase is a function of
$%
temperature and ratio of feed rates. Ior the present propyleneAwaterAIPAADIP= system,
the reaction *one temperature increases with increase in pressure. +he propylene
hydration reaction and IPA etherification reaction are hi"hly exothermic. Propylene
conversion decreases with an increase in reaction *one temperature. :onse;uently, the
content of IPA in the reaction mixture is reduced with an increase in column pressure.
#owever, the reaction rate increases with increasin" temperature. +herefore, the
preferred operatin" pressure is in a ran"e in which the temperature of the reaction *one
is sufficiently hi"h to "ive a fast rate of reaction, and sufficiently low to afford a product
stream rich in IPA.
Water, IPA and DIP= form twoAcomponent and threeAcomponent low boilin" point
a*eotropes (@er"e et al., $%%2). +he compositions and boilin" points of each a*eotrope
are presented in +able 2.$. +he mole fraction of IPA in the IPAAwater a*eotrope varies
with pressure. +he IPA content climbs from 0.77&0 at 0.0$2 HPa, passes throu"h a
maximum value of 0.7%10 at 0..07 HPa, and then declines to 0.7. at 7.1'$ HPa (Iran
and Dod"e, $%1%).
+he relative volatility of reactants and products declines with increasin" pressure.
+he chan"e in the relative volatility with pressure is "radual and small, and does not
si"nificantly affect reaction and separation.
+he lower limit of the operatin" pressure is set at conditions, which allow a
reasonable reaction rate and the use of water in a condenser for recovery of unreacted
propylene. +he operatin" pressure of the :D column was varied in the ran"e of 0.$A1
20
HPa. +he coolant inlet temperature, reaction *one temperature, conversions of
propylene and water, and product purity have been used to determine the optimum
operatin" pressure ran"e. Ior the present model, it has been found that the optimum
pressure for operation of a dual catalyst bed :D column is 2 HPa.
2.3.2 (ocation o R#action 0on#
+he location of the reaction *one in the :D column is determined by the relative
volatility of reactants and products. Beactant propylene is the most volatile component
and product IPA is the least volatile component of the system when IPA concentration in
the li;uid phase is hi"her than in the waterAIPA a*eotropic mixture. +herefore, the
reaction *one is located toward the top of the column, where a hi"h concentration of
propylene is present in the li;uid phase, thereby ensurin" a relatively hi"h conversion of
water. +he precise location of the catalyst beds depends on the optimum numbers of
plates in each of the rectifyin" and strippin" *ones, which in turn depend on the feed
locations and feed ratios, as will now be discussed.
2.3.3 )in.l# and *ultipl# Catalyst ,#d CD Colu$ns
+he :D column with a sin"le catalyst bed optimally located at the 1
th
plate was
modeled first, and then the potential benefits of havin" two or more catalyst beds were
determined. A hi"her conversion of propylene is attainable usin" two spaced apart
catalyst beds, the amount of the increase dependin" on the location and the number of
catalyst beds. #i"her conversion to IPA is achieved when a second bed is located at the
2$
'
rd
plate, and the water feed is divided into two streams that are then fed above each of
the two beds. +he IPA concentration in the li;uid product thereby can be increased up to
%%.% mol% (+able 2.2). +he benefit results from improvement in the separation and
reaction of propylene in the rectifyin" section above the catalyst bed at the 1
th
plate.
Additional propylene is hydrated in the second catalyst bed, which would otherwise has
been recycled. When a second catalyst bed is located instead at a position lower than the
first catalyst bed and propylene feed, for example on the %
th
plate, and no other chan"es
are made, no benefit is observed. Instead, it was found that a detrimental interaction
occurs between the phase and chemical e;uilibria, so the temperature of the catalyst bed
on the 1
th
plate decreases to '2.) and the IPA concentration in li;uid product decreases
to %%.' mol% (+able 2.2). A :D column with three spaced apart catalyst beds mounted
at the '
rd
, 1
th
, and %
th
plates was also modeled. Inclusion of the third bed at the %
th
plate
a"ain caused the temperatures of the upper two catalyst beds to decrease. 5ower
temperatures in the catalyst beds led to a lower reaction rate. When the temperature is
reduced, a lar"er amount of catalyst must be used, with a conse;uent decrease in
efficiency and an increase in costs. +he IPA concentration in the product stream of the
sin"le catalyst bed model increases to %%.% mol% when the propylene4water feed ratio is
increased to '.-C$, but the conversion of propylene decreases to 276. +he :D column
with dual catalyst beds mounted at the '
rd
and 1
th
plates is the optimum confi"uration,
havin" the hi"hest level of propylene conversion and catalyst bed temperatures
conferrin" "ood reaction rates.
22
2.3.! +##d (ocation
+he inlet to the column for each feed has been located so as to maximi*e reactant
concentration in the reaction *one, without hinderin" the separation process occurrin" in
the other parts of the column. In the optimum dual catalyst bed :D column
confi"uration, li;uid water is fed closely above the top of each of the catalyst beds, and
propylene is fed immediately below the lower catalyst bed (Ii"ure 2.$).
Alternative desi"ns in which feed streams are located lower in the strippin" section
or hi"her in the rectifyin" section "ive unsatisfactory performance. Ieedin" reactants to
the strippin" or the rectifyin" section leads to a reduction in IPA concentration and an
increase in water concentration in the li;uid product. +his effect is a conse;uence of a
lower conversion of water to IPA in the reaction *one, and reduced efficiency in
separation in the strippin" section.
2.3.% )toichio$#tric E1c#ss o Propyl#n#
Ior an e;uilibriumAlimited reaction, an excessive amount of one reactant is usually
used to obtain a maximum conversion of another reactant to a desired product. An
ob!ect of the present study is to obtain hi"h purity IPA from the bottom outlet of the :D
column. +he boilin" points of pure compounds and a*eotropes of the propyleneAwaterA
IPAADIP= system are listed in +able 2.$. DIP= and a*eotropes that it forms are less
volatile than propylene but more volatile than water and IPA, and more than -' wt% of
each DIP= a*eotrope is DIP=. +herefore DIP= concentrates in the middle of the :D
column (Ii"ure 2.2). +he li;uid mixture in the strippin" section of the :D column
2'
comprises mainly water and IPA. +he IPAAwater a*eotrope will only concentrate at the
top of the strippin" section when the IPA concentration in the total reaction mixture is
hi"her than the concentration of IPA in the a*eotrope (M0.7& mole fraction IPA). When a
$C$ molar ratio of propylene and water is fed to an e;uilibrium reactor of .$0), and
chemical e;uilibrium is attained, the IPA molar ratio in the IPA and water mixture of the
li;uid outlet is only 0.$1, lower than that in the water and IPA a*eotrope (simulation
result usin" e;uilibrium reactor model). +herefore it is necessary that the water content
of the li;uid mixture is consumed beyond the e;uilibrium limit attainable usin" a
stoichiometric feed in order to produce hi"h purity IPA. +his is achieved by feedin" an
excess of propylene into the reaction *one. When the propylene4water molar feed ratio
is 2.%C$, conversion of propylene to IPA in the dual catalyst bed :D column is '16,
conversion of water is substantially $006, and the concentration of IPA in the bottom
stream is as hi"h as %%.% mol%. In contrast, the e;uilibrium conversion of the same feed
mixture is only -.. mol% at the same temperature and pressure in a conventional
reactor. At feed ratios below 2.%C$ and the same operatin" pressure of 2HPa, IPA
dehydration to propylene occurs on the upper catalyst bed due to low propylene li;uid
phase concentration in the bed, resultin" in an increase of water concentration and
decrease of IPA concentration in the li;uid product stream. At feed ratios above 2.%C$,
there is no si"nificant improvement in IPA concentration in the li;uid product.
#owever, the amount and hence the cost of propylene recycle are increased.
2.
A conse;uence of usin" a hi"her propylene4water ratio is a hi"her recycle rate of
unreacted propylene. +he e;uilibrium constant of the reaction depends on the
temperature, which in turn is a function of the operatin" pressure. :onse;uently, the
amount of propylene converted to product and the amount of propylene recycled vary
with pressure. At 2 HPa and propylene4water molar feed ratio 2.%C$, the reaction
temperature is .01) in the upper catalyst bed and .$0) in the lower catalyst bed. Under
these conditions, essentially all propylene consumed is converted to IPA. +hese values
for the feed ratio and the temperature of reaction at an operatin" pressure of 2 HPa
provide for optimum column performance while minimi*in" the costs for recyclin"
propylene.
2.3.& Distillat# +lo2 Rat#
+he distillate from the :D column consists mainly of unreacted propylene and
inerts carried by the propylene feed stream. Propylene is separated from the ma!ority of
propane and other impurities in a separation unit, and recycled to the :D column.
:ontinuously feedin" and recyclin" propylene serves to increase the propylene
concentration in the reaction *one, and thereby to drive the reaction beyond the
e;uilibrium limitation. Becyclin" the propylene also avoids accumulation of impurities
in the reaction *one by continuously removin" them from the :D column. +he model
has been run usin" both %1 wt% and %% wt% propylene. ?o performance benefit accrues
from the use of %% wt% propylene. +hus the economic benefit from usin" %1 wt%
propylene maes it the preferred feed.
21
In a conventional distillation column, a hi"h distillate rate usually leads to a low
li;uid product flow rate, but a hi"her concentration of product in the li;uid stream. +his
is not necessarily true for a :D process. :han"in" the distillate flow rate affects the
performance of the :D column throu"h the interaction between reaction and separation.
+he dependence of IPA concentration in the li;uid product stream on the ratio of
distillate flow rate to propylene feed rate is show in Ii"ure 2.'. +he concentration curve
of IPA is volcano shaped. +he IPA concentration in the li;uid product reaches the
hi"hest value (%%.% mol%) when the distillate4propylene feed molar ratio is 0.77 (+able
2.'). At the optimum temperature and pressure, DIP= forms low boilin" point
a*eotropes with water and IPA, and remains in the upper part of strippin" section and
the reaction *one while hi"h purity IPA "athers at the bottom of the column (Ii"ure
2.2). +he hi"h concentration of DIP= in the reaction *one inhibits formation of
additional DIP=, and propylene is hydrated to IPA. +he li;uid mixture flowin" down
from the reaction *one into the strippin" section of the :D column consists mainly of
IPA, as essentially all water is consumed in the hydration reaction. IPA and water form a
low boilin" point a*eotrope. +he IPA concentration in the li;uid stream at the top of the
strippin" section is hi"her than the IPA content of the a*eotropic mixture. +herefore,
IPA is collected at the bottom of the strippin" section and the a*eotrope rises to the top
of the strippin" *one. Unlie conventional propylene hydration processes where extra
columns are re;uired to separate DIP= and water from IPA, no such columns are
re;uired for the :D process because a*eotropes of the system wor as a carrier to lift
27
DIP= and water up to the reaction *one and to constrain them in the middle of the :D
column. =therification does not have a detrimental effect on IPA production in the :D
process when it is conducted at 2 HPa.
When the distillate4propylene ratio is lower than the optimum ratio, the conversion
of propylene and water in the reaction *one must be hi"her, as less propylene leaves
from the top of the :D column as volatile compound. A si"nificant amount of DIP= is
produced in the reaction *one due to the low concentration of water and hi"h
concentration of propylene in the catalyst beds. Ior example, when the
distillate4propylene feed molar ratio is 0.7$&, the IPA mole fraction in the li;uid product
is only 0.--, even thou"h total conversion of propylene is .0.. mol%. Up to -.1 mol%
of propylene forms byAproduct DIP=, and only '$.% mol% propylene is converted to
IPA. As the distillate4propylene feed molar ratio increases, DIP= concentration in the
li;uid product stream decreases while IPA concentration increases (Ii"ure 2.'). When
the distillate4propylene feed molar ratio is hi"her than the optimum value, less
propylene is consumed in the reaction *one. +herefore less IPA is formed and more
unreacted water flows into the strippin" section. :onse;uently, the water concentration
in the li;uid product is hi"her when the distillate4propylene ratio is hi"her than the
optimum value. +hus, it is necessary to carefully control the distillate flow rate to
optimi*e both the conversion of water and the purity of IPA produced.
2&
2.3.' Nu$"#r o Th#or#tical Plat#s
#avin" determined the re;uirements for location of the reaction *one and the
optimum feed ratio, the number of theoretical plates re;uired for each of the rectifyin"
and strippin" sections has been determined. +he dual bed :D column model has been
run to determine the optimum number of plates in each section independently. +he
level of separation of the product usually increases with increasin" theoretical plates.
#owever, as the number of plates increases, the benefit of addin" another plate becomes
pro"ressively smaller. ?o appreciable value accrues from increasin" the number of
plates in the strippin" section above 2$ (Ii"ure 2..). ,imilarly, no benefit accrues from
increasin" the number of plates in the rectifyin" section above two for the dual catalyst
bed :D column. +hus, the dual bed :D column comprises 27 theoretical plates, of
which plates $ and 2 comprise the rectifyin" section( plates 7 to 27 comprise the
strippin" section. :atalyst beds are located on the '
rd
and 1
th
plates with one distillation
plate inAbetween.
2.3.3 E#ct o oth#r Op#ratin. and D#si.n /aria"l#s
+he :D column can be operated so that the reaction *one is at the temperature at
which the catalyst has optimum activity. IonAexchan"ed resin, tun"sten oxide and
*eolite have each been reported to have hi"h activity for li;uid phase hydration of
propylene to IPA ()aiser et al., $%71( Petrus et al., $%-.). When the reaction is in the
temperature ran"e '2') to .1'), an acid ionAexchan"e resin catalyst (e.. Amberlyst
resin) can be used as the catalyst. +he disadvanta"e for the application of ionAexchan"e
2-
resins as hetero"eneous catalysts is the increasin" thermal instability at elevated
temperature (Petrus et al., $%-$). +herefore, for hi"h temperature hydration reactions it
is necessary to use acidic inor"anic catalysts havin" hi"h thermal stability.
+he feed temperature has only a sli"ht effect on the operation of the process.
#owever, the reaction is hi"hly exothermic, and so feeds that are sli"htly cooler than the
operatin" temperature of the catalyst beds have a beneficial effect in controllin" the
reaction *one temperature.
2.! )i$ulation R#sults
Iirstly, for each column confi"uration, the effect of varyin" the pressure and
temperature on the process was determined. Distillate flow rate and feed ratio were
ad!usted to obtain optimum hi"h purity product. +hen the number of plates in the
rectifyin" *one, above the catalyst bed(s), and in the strippin" *one, below the catalyst
bed(s), were varied independently, and the impact of the location of catalyst beds were
examined systematically. +he optimum confi"uration has been determined. +he
optimum confi"uration is a column havin" spaced apart dual catalyst beds, an upper
rectifyin" section havin" two plates, and a lower strippin" section havin" 2$ plates.
2 .% ,#n#its o th# CD Proc#ss
,imulation of the steadyAstate :D process (Ii"ure 2.1) shows that the new process
has advanta"es over conventional processes (Ii"ure $.$). +able 2.. presents a detailed
comparison of the stateAofAtheAart conventional processes and the new :D process.
2%
=;uipment for conventional propylene hydration processes usually consists of reactors
with coolin" system and a series of separation columns. Water is a lar"e component of
the li;uid product stream. :onse;uently, excess water has to be removed first throu"h
distillation to obtain the a*eotrope mixture. +hen, extractive distillation is applied to
brea the a*eotrope. Iinally, the extractive a"ent remainin" in the IPA has to be
removed to meet the IPA product standards. +ypically, four distillation columns are
re;uired to treat the product stream from a conventional reactor to "et hi"h purity IPA
(?eier and Woellner, $%&'). +he proposed :D process consists of one column havin"
two catalyst beds in the middle section. #i"h purity IPA (up to %%.% mol%) is obtained
directly from the column.
:learly, the :D process is much simpler to construct and operate (+able 2..).
Iurther, it is operated at a much lower pressure and temperature than conventional
li;uid phase hydration processes. #ence, the capital and operatin" cost are reduced
dramatically, and operation is more strai"htforward. +he :D process also offers
reduction in operatin" costs arisin" from reactor coolin", catalyst recycle, and water
recycle. A minor cost associated with the new process when compared with
conventional direct hydration processes havin" hi"h propylene conversions is the hi"h
propylene recycle ratio. An excess amount of propylene is fed to the reaction *one to
ensure the maximum conversion of water, close to $006. +he optimum propylene to
water feed ration ratio of 2.%C$ ensures conversion of substantially all water to IPA
while minimi*in" costs for propylene recycle.
'0
2.& -in#tically Controll#d CD
+he optimum confi"uration and operation condition of the :D process for IPA
production throu"h propylene hydration were determined in the previous simulation.
,imulation results showed that the :D process was practical and it had economic
potential. +he amount of catalyst re;uired to achieve economic conversion has to be
determined. )inetic reaction rate e;uations are needed to calculate the hei"ht of reaction
section and the si*e of the :D column. Besearch then proceeded to the study of inetic
of the reactions. :atalyst to be used in the :D process (Amberlyst '-) was selected. +he
inetic of propylene hydration and its side reactionAIPA etherification over Amberlyst
'- were experimentally measured. Beaction rate e;uation was found to follow =leyA
Bideal model (e;uations '.2&, '.2-, '.'$A'.'7). +he reaction rate e;uations of propylene
hydration and IPA etherification were then incorporated into the simulation pro"ram of
a :D process with a capacity of 7/$0
.
tons4year. +he column was desi"ned accordin" to
the optimum confi"uration. In the previous simulation of e;uilibrium sta"e and
e;uilibrium reaction model, separation on each tray was assumed to reach mass transfer
e;uilibrium and reactions in reaction *one were assumed to reach chemical reaction
e;uilibrium. In the inetic controlled model, inetic reaction rate e;uation were used to
calculate reaction rate in the catalyst reaction *one. Beactions were assumed to reach
%06 of e;uilibrium conversion on the reaction trays and a typical tray efficiency of 0.&
was applied to all separation trays. +he process (Iin"er 2.1) was then simulated to
determine the si*e of the :D column.
'$
,imulation result showed that a :D column of 27 separation sta"es and two
reaction *ones was needed to produce %%.% mol% IPA. ,ta"e '
rd
and 1
th
are the reaction
sta"es with catalyst loaded on them. Propylene stream of %1 vol% purity is fed above
the 7
th
sta"e at a flow rate of '.- mol4hr. Inert of the propylene feed stream is
represented by propane. +wo streams of water are fed into column separately on the '
rd
and 1
th
sta"e at '0mol4hr and %0mol4hr. Under 2 HPa, the temperature of condenser
and reboiler are '1') and .-%) respectively, while the temperature of the upper
reaction sta"e and the lower reaction sta"e are .0-) and .$-). IPA li;uid product
stream "athered from the bottom of the :D column is of %%.% mol% purity. +he li;uid
product flow rate is $$- mol4hr. +he column diameter is 1.1 meter. +he catalyst bed
hei"ht of the upper reaction sta"e is found to be 0.-m( the hei"ht of the lower reaction
sta"e is 2.$m. With 0.7$m spacin" for each separation sta"e, the hei"ht of the :D
column would be $-.&m (Ii"ure 2.7). ,imulation pro"ram and stream table of the
process was attached in appendix.
2.' Conclusions
:atalyst distillation techni;ue was applied to IPA production throu"h propylene
direct hydration. ,teady state simulation of the process was carried out and a process
flow sheet was developed. +he optimum operatin" parameters for the catalytic
distillation column for the production of IPA were determined usin" a computer model.
+he simulation result indicated that the use of :D process overcomes chemical and
vaporAli;uid e;uilibrium limitations. +he model showed that hi"h purity IPA (up to %%.%
'2
mol%) can be produced as a li;uid product stream containin" virtually no water, in
contrast to conventional processes. +he reduction of water content below the a*eotrope
water content occurs by reaction of water with a 2.%C$ optimum molar excess of
propylene when usin" a :D column havin" two spaced apart catalyst beds. =xcess
propylene is recycled to remove impurities that may otherwise accumulate in the :D
column. +he e;uilibrium ether content of the reaction mixture is retained in the reaction
*one, which reduces the effect of side reaction. +he optimum operatin" pressure is
2HPa for the :D column havin" two spacedAapart catalyst beds. ,imulation of the :D
column of the above confi"uration and operation condition with reaction rate controlled
by inetic e;uations was also carried out to si*e the column. +he separation try
efficiency was assumed to be 0.&. +he result showed the column was $-.&m hi"h, with
0.-m hi"h upper catalyst bed and 2.$m hi"h lower catalyst bed.
''
2.3 No$#nclatur#
c component concentration in li;uid phase, mol45
f component feed flow rate, mol4hr
I total feed flow rate, mol4hr
h component molar enthalpy, F4mol
)e; reaction e;uilibrium constant
l component tray li;uid flow rate, mol4hr
5 total tray li;uid flow rate, mol4hr
P component tray formation rate, mol4hr
y component molar vapor fraction
x component molar li;uid fraction
v component tray vapor flow rate, mol4hr
8 total tray vapor flow rate, mol4hr
N tray heat withdraw, F4hr
)u"scripts
i compoment
! distillation tray
)up#rscripts
I feed
5 li;uid phase
'.
8 vapor phase
v stoichiometric coefficient
'1
2.4 (it#ratur# Cit#d
Abufares,A.A., Dou"las, P.5., $%%1, Hathematical Hodelin" and ,imulation of an
H+@= :atalytic Distillation Process Usin" ,peedup and Aspenplus, :hemical
=n"ineerin" Besearch and Desi"n, &'(A$), 'A$2.
@arrAdavid, I., Dod"e, @. I., $%1%, 8aporAli;uid =;uilibrium at #i"h Pressures, F.
:hem. =n". Data, ., $0.A$$0.
@er"e, 5., Lan", J., $%%2, ,eparation of Propyl Alcohols from Water by A*eotropic or
=xtractive Distillation, United ,tates Patent ?o 1,0-1,&'%.
:ope, :. ,., $%77, =;uilibria in the #ydration of Propylene and @utylenes, F. :hem.
=n". Data, $$, '&%A'-'.
DeGarmo, F. 5., Parulear, 8. ?., Pin!ala, 8., $%%2, :onsider Beactive Distillation,
:hemical =n"ineerin" Pro"ress, Harch, .'A10.
Iran, @. D., Dod"e, @. I., $%1%, 8aporA5i;uid =;uilibrium at #i"h Pressures, Fournal
of :hemical and =n"ineerin" Data, .(2), $0&A$2$.
Gon*ale*, F. :., ,ubawalla, #., Iair, F. B., $%%&, Preparation of +ertAAmyl Alcohol in A
Beactive Distillation :olumn, Ind. =n".:hem. Bes., '7, '-.1A'-1'.
#ancoc, =.G., $%&', Propylene and Its Industrial Derivatives, =. @enn, 5ondon.
)aiser, F. B., @euther, #., Hoore, 5. D., 9dioso, B. :., $%72, Direct #ydration of
Propylene over IonA=xchan"e Besins, IO=: Product Besearch and Development,
$(.), 2%7A'02.
'7
5i, :. :., Hcetta, F.F., $%7', 8aporAli;uid =;uilibrium in the PropyleneAwater ,ystem,
F. :hem. =n". Data, -, 2&$A2&1.
Hafewsi, I. )., Hare, 5. I., $%'-, #ydration of Propylene under Pressure, !n"#$t%ial
an" &ninee%in Chemi$t%y, '0, 20'A2$0.
?eier, W., Woellner F., $%&', Isopropyl alcohol by Direct #ydration, :#=H+=:#,
'(Ieb), %1A%%.
?", I. +. +., Bempel, G. 5., $%%%, :atalytic Distillation, :anadian :hemical ?ews,
Fuly4Au"ust, $%A20.
?i!huis, ,. A., )erhof, I. P. F. H., Ha, A. ?. ,., $%%', Hultiple ,teady ,tates Durin"
Beaction Distillation of Hethyl tertA@utyl =ther, Ind. =n". :hem. Bes., '2, 2&7&A
2&&..
Petrus, 5., De Boo, B. W., ,tamhuis, =. F., Foosten, G. =. #., $%-., )inetics and
=;uilibria of +he #ydration of Propene over a ,tron" Acid Ion =xchan"e Besin as
:atalyst, :hemical =n"ineerin" ,cience, '%('), .''A..7.
Petrus, 5., ,tamhuis, =. F., Foosten, G. =. #., $%-$, +hermal Deactivation of ,tron"A
Acid IonA=xchan"e Besins in Water, Ind. =n". :hem. Prod. Bes. Dev., 20, '77A'&$.
Pilavachi, P. A., $%%&, Hodelin" and ,imulation of Beactive Distillation 9perations,
Ind. =n". :hem. Bes., '7, '$--A'$%&.
Podrebarac, G. G., ?", I. +. +., Bempel, G. 5., $%%-, +he Production of Diacetome
Alcohol with :atalytic Distillation Part IIC A BateA@ased :atalytic Distillation
Hodel for the Beaction Jone, :hemical =n"ineerin" ,cience, 1', $0&&A$0--.
'&
Podrebarac, G. G., ?", I. +. +., $%%&, Hore Uses for :atalytic Distillation,
:#=H+=:#, Hay, '&A.1.
Wye*esany, A., $%%., ?ostoichimetric Al"orithm of :alculation of ,imultaneous
:hemical and Phase =;uilibria, Ind. =n". :hem. Bes., '', $%&$A$%&-.
>u, J. P., Afacan, A., :huan", ). +., $%%%, Bemoval of Acetic Acid from Water by
:atalytic Distillation Part 2. Hodelin" and ,imulation ,tudies, +he :anadian
Fournal of :hemical =n"ineerin", &&, $A7.
Jabaloy, H. ,., et al., $%%', Isothermal 8aporAli;uid =;uilibrium data for the @inaries
PropaneA2Apropanol and PropyleneA2Aprppanol, F. :hem. =n". Data, '-, .0A.'.
'-
Ii"ure 2.$ :onfi"uration of dual catalyst bed catalytic distillation column
'%
Propylene Becycle
IPA product
Propylene feed
Water feed
Water feed
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Plate
M
o
l
e

F
r
a
c
t
i
o
nWATER
PROPYLENE
IPA
PROPANE
DIPE
Ii"ure 2.2 5i;uid phase composition profile of dual catalyst bed :D column
(propylene4water molar feed ratioE2.%C$)
.0
Beboiler
:ondenser
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.61 0.62 0.63 0.64 0.65 0.66 0.67 0.68 0.69 0.70
Distillate/propylene
M
o
l
e

F
r
a
c
t
i
o
n
,

D
I
P
E

o
r

W
a
t
e
r
0.86
0.88
0.90
0.92
0.94
0.96
0.98
1.00
M
o
l
e

f
r
a
c
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Ii"ure 2.' =ffect of distillate flow rate on dual catalyst bed :D column performance
(propylene4water molar feed ratioE2.%C$)
.$
IPA
Water
DIP=
0.%-%1
0.%%00
0.%%01
0.%%$0
0.%%$1
$0 $1 20 21 '0 '1
Nu$"#r o Plat#s in )trippin. )#ction
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Ii"ure 2.. =ffect of the number of strippin" plates on :D column performance
(water4propylene molar feed ratioE$C2.%( distillate4propylene molar
ratioE0.7&)
.2
Ii"ure 2.1 Ilow dia"ram of catalytic distillation isopropyl alcohol process
:D catalytic distillation column
#$, #2, #' heat exchan"ers
,$, ,2, ,' stora"e tans
P$ pump
:$ compressor
.'
:D
:$ ,$
#2
#$
,'
,2
P$
#'
#i"h Purity IPA
Water
Propylene
9lefin
Befinery
Ii"ure 2.7 ,i*e of a :D column
..
IPA $$- mol4hr
Propylene
'.- mol4hr
Water 70 mol4hr
water '0mol4hr
'1')
.$-)
.0-)
.-%)
22$mol4hr
2.$m
0.7m
0.-m
1.1m
$.2m
$.m
+able 2.$ A*eotropes of WaterAIPAADIP= ,ystem
compound boilin" temperature composition of a*eotrope
or a*eotrope of component and a*eotrope water IPA DIP=
()) wt6 wt6 wt6
propylene 221..'
water '&'.$'
IPA '11.71
DIP= '.2.$1
waterPIPA '1'..1 $2.7 -'.& 0
IPAPDIP= ''%.'1 0 $7.' -'.&
waterPDIP= ''1.'1 ..1 0 %1.1
waterPIPAPDIP= ''..&1 ..& &.' --.0
IPAC isopropanol DIP=C diisopropyl ether
+able 2.2 :omparison of Hultiple and ,in"le :atalyst @ed :D :olumn
catalyst catalyst bed temperature ()) IPA mole fraction propylene4water propylene conversionQ
bed 'rd plate 1th plate % th plate in li;uid product feed molar ratio mol6
$ .0% 0.%%. 2.%C$ '.
$ .$0 0.%%% '.-C$ 27
2 '2. .0% 0.%%' 2.%C$ '.
' '22 '2. .0% 0.%%' 2.%C$ '.
2 .01 .$0 0.%%% 2.%C$ '1
Q '16 conversion of propylene is e;uivalent to $006 conversion of water when the propylene4water
feed molar ratio is 2.%C$
.7
+able 2.' =ffect of Distillate4Propylene Batio on :D :olumn Performance
distillate4propylene feed molar ratio 0.7$& 0.71- 0.7-%
IPA mole fraction in product stream 0.--' 0.%%% 0.%0%
total propylene conversion mol6 .0..0 '7.$- '2.-7
water conversion mol6 %%.-0 %%.-0 %0.70
propylene conversion to IPA mol6 '$.%. '7.$1 '2.-1
propylene converison to DIP= mol6 -..77 0.02& 0.0$2
Qwater4propylene molar feed ratioE$C2.%
.&
+able 2.. :omparison of Propylene #ydration Processes
direct hydration fixedAbed
process vapor phase li;uid phase catalytic distillation
PB9 feed stream (wt6)Q %% %1 %1
catalyst W9'AJn94#'P9. a;ueous silicotun"state QQ
catalyst re"eneration no yes no
reactor yes yes no
coolin" of reactor yes yes no
distillation column in process . . $
operatin" pressure (HPa) 2.1A7.7 20.' 2
operatin" temperature ()) 1$'A12' 1$'A17' '2'A.70
feed ratio (water4PB9) $C.A$0 ?.A. $C2.%
PB9 recycle4feed mole ratio %.A%16 '0A.06 716
water recycle4feed mole ratio .0A-06 ?.A. 0
conversion 1A76 PB9 70A&06 PB9 '16 PB9, R%%6 water
IPA selectivity %76 %-A%%6 R%%.%6
Q PB9Epropylene QQ for example, *eolite or protonAexchan"ed resin
.-