Appendix B Informtion for the Preliminry Design of Eleven

Chemicl Processes

The purpose of the process designs contined in this ppendix is to provide the reder with preliminry
description of severl common chemicl processes. The designs provided re the result of preliminry
simultion using the CHECAD process simultion softwre nd often contin simplifying ssumptions
such s idel column ehvior (shortcut method using the Underwood Gillilnd method) nd in some
cses the use of idel thermodynmics models (k-vlue = idel gs, enthlpy = idel). These designs re
used throughout the ook in the end-of-chpter prolems nd provide strting point for detiled design.
The uthors recognize tht there re dditionl complicting fctors, such s non-idel phse equilirium
ehvior (such s zeotrope formtion nd phse seprtion), feed strem impurities, different ctlyst
selectivity, side rection formtion, nd so on. The presence of ny one of these fctors my give rise to
significnt chnges from the preliminry designs shown here. Thus, the student, if sked to perform
detiled process design of these (or other) processes, should tke the current designs s only strting
point nd should e prepred to do further reserch into the process to ensure tht more ccurte nd
deeper understnding of the fctors involved is otined.

Following is list of the sections nd projects discussed in this ppendix.

B.1 Dimethyl Ether (DME) Production, Unit 200

B.2 Ethylbenzene Production, Unit 300

B.3 Styrene Production, Unit 400

B.4 Drying Oil Production, Unit 500

B.5 Production of Mleic Anhydride from Benzene, Unit 600

B.6 Ethylene Oxide Production, Unit 700

B.7 Formlin Production, Unit 800

B.8 Btch Production of L-Phenyllnine nd L-Asprtic Acid, Unit 900

B.9 Acrylic Acid Production vi the Ctlytic Prtil Oxidtion of Propylene

B.10 Production of Acetone vi the Dehydrogention of Isopropyl Alcohol

B.11 Production of Heptenes from Propylene nd Butenes

B.1 Dimethyl Ether (DME) Production, Unit 200

DE is used primrily s n erosol propellnt. It is miscile with most orgnic solvents, hs high
soluility in wter, nd is completely miscile in wter nd 6% ethnol [1]. Recently, the use of DE s
fuel dditive for diesel engines hs een investigted due to its high voltility (desirle for cold
strting) nd high cetne numer. The production of DE is vi the ctlytic dehydrtion of methnol
over n cid zeolite ctlyst. The min rection is

(B.1.1)

In the temperture rnge of norml opertion, there re no significnt side rections.

B.1.1 Process Description

A preliminry process flow digrm for DE process is shown in Figure B.1.1, in which 50,000 metric
tons per yer of 99.5 wt% purity DE product is produced. Due to the simplicity of the process, n
operting fctor greter thn 0.95 (8,375 h/yr) is used.

Figure B.1.1 Unit 200: Dimethyl Ether Process Flow Digrm

Fresh methnol, Strem 1, is comined with recycled rectnt, Strem 14, nd vporized prior to eing
sent to fixed-ed rector operting etween 250C nd 370C. The single-pss conversion of methnol
in the rector is 80%. The rector effluent, Strem 7, is then cooled prior to eing sent to the first of two
distilltion columns: T-201 nd T-202. DE product is tken overhed from the first column. The second
column seprtes the wter from the unused methnol. The methnol is recycled ck to the front end of
the process, nd the wter is sent to wste wter tretment to remove trce mounts of orgnic
compounds.

Strem summries, utility summries, nd equipment summries re presented in Tles B.1.1 B.1.3.

Tble B.1.1 Flow Tble for DME Unit 200

Tble B.1.2 Utility Summry Tble for Unit 200

Tble B.1.3 Mjor Equipment Summry for Unit 200

B.1.2 Rection Kinetics

The rection tking plce is mildly exothermic with stndrd het of rection, Hreac(25C) = 11,770
kJ/kmol. The equilirium constnt for this rection t three different tempertures is given elow:

The corresponding equilirium conversions for pure methnol feed over the ove temperture rnge is
greter thn 99%. Thus this rection is kineticlly controlled t the conditions used in this process.

The rection tkes plce on n morphous lumin ctlyst treted with 10.2% silic. There re no
significnt side rections t less thn 400C. At greter thn 250C the rte eqution is given y Bondier
nd ccche [2] s:

(B.1.2)
where k0 = 1.21 106 kmol/(m3ct.h.kP), E0 = 80.48 kJ/mol, nd pmethanol = prtil pressure of
methnol (kP)

Significnt ctlyst dectivtion occurs t tempertures greter thn 400C, nd the rector should e
designed so tht this temperture is not exceeded nywhere in the rector. The design given in Figure
B.1.1 uses single pcked ed of ctlyst, which opertes diticlly. The temperture exotherm
occurring in the rector of 118C is proly on the high side nd gives n exit temperture of 368C.
However, the single-pss conversion is quite high (80%), nd the low rectnt concentrtion t the exit of
the rector tends to limit the possiility of runwy.

In prctice the ctlyst ed might e split into two sections, with n intercooler etween the two eds.
This hs n overll effect of incresing the volume (nd cost) of the rector nd should e investigted if
ctlyst dmge is expected t tempertures lower thn 400C. In-rector cooling (shell-nd-tue design)
nd cold quenching y splitting the feed nd feeding t different points in the rector could lso e
investigted s vile lterntive rector configurtions.

B.1.3 Simultion (CHEMCAD) Hints

The DE-wter inry system exhiits two liquid phses when the DE concentrtion is in the 34% to
93% rnge [2]. However, upon ddition of 7% or more lcohol, the mixture ecomes completely miscile
over the complete rnge of DE concentrtion. In order to ensure tht this non-idel ehvior is
simulted correctly, it is recommended tht inry vpor-liquid equilirium (VLE) dt for the three pirs
of components e used in order to regress inry interction prmeters (BIPs) for UIQUAC/UIFAC
thermodynmics model. If VLE dt for the inry pirs re not used, then UIFAC cn e used to
estimte BIPs, ut these should e used only s preliminry estimtes. As with ll non-idel systems,
there is no sustitute for designing seprtion equipment using dt regressed from ctul (experimentl)
VLE.

B.1.4 References

1. DuPont Tlks out Its DE Propellnt, Aerosol Age (y nd June 1982).

2. Bondier, J., nd C. ccche, Kinetics of ethnol Dehydrtion in Deluminted H-

mordenite: odel with Acid nd Bsic Active Centres, Applied Catalysis 69 (1991):
139 148.

B.2 Ethylbenzene Production, Unit 300

The mjority of ethylenzene (EB) processes produce EB for internl consumption within coupled
process tht produces styrene monomer. The fcility descried here produces 80,000 tonne/yr of 99.8
mol% ethylenzene tht is totlly consumed y n on-site styrene fcility. As with most EB/styrene
fcilities, there is significnt het integrtion etween the two plnts. In order to decouple the opertion of
the two plnts, the energy integrtion is chieved y the genertion nd consumption of stem within the
two processes. The EB rection is exothermic, so stem is produced, nd the styrene rection is
endothermic, so energy is trnsferred in the form of stem.

B.2.1 Process Description [1, 2]

The PFD for the EB process is shown in Figure B.2.1. A refinery cut of enzene is fed from storge to n
on-site process vessel (V-301), where it is mixed with the recycled enzene. From V-301, it is pumped to
rection pressure of pproximtely 2,000 kP (20 tm) nd sent to fired heter (H-301) to ring it to
rection temperture (pproximtely 400C). The preheted enzene is mixed with feed ethylene just
prior to entering the first stge of rector system consisting of three ditic pcked-ed rectors (R-
301 to R-303), with interstge feed ddition nd cooling. Rection occurs in the gs phse nd is
exothermic. The hot, prtilly converted rector effluent leves the first pcked ed, is mixed with more
feed ethylene, nd is fed to E-301, where the strem is cooled to 380C prior to pssing to the second
rector (R-302), where further rection tkes plce. High-pressure stem is produced in E-301, nd this
stem is susequently used in the styrene unit. The effluent strem from R-302 is similrly mixed with
feed ethylene nd is cooled in E-302 (with genertion of high-pressure stem) prior to entering the third
nd finl pcked-ed rector, R-303. The effluent strem leving the rector contins products, y-
products, unrected enzene, nd smll mounts of unrected ethylene nd other noncondensle gses.
The rector effluent is cooled in two wste-het oilers (E-303 nd E-304), in which high-pressure nd
low-pressure stem, respectively, is generted. This stem is lso consumed in the styrene unit. The two-
phse mixture leving E-304 is sent to trim cooler (E-305), where the strem is cooled to 80C, nd
then to two-phse seprtor (V-302), where the light gses re seprted nd, ecuse of the high
ethylene conversion, re sent overhed s fuel gs to e consumed in the fired heter. The condensed
liquid is then sent to the enzene tower, T-301, where the unrected enzene is seprted s the overhed
product nd returned to the front end of the process. The ottoms product from the first column is sent to
T-302, where product EB (t 99.8 mol% nd contining less thn 2 ppm diethylenzene [DEB]) is tken
s the top product nd is sent directly to the styrene unit. The ottoms product from T-302 contins ll the
DEB nd trce mounts of higher ethylenzenes. This strem is mixed with recycle enzene nd psses
through the fired heter (H-301) prior to eing sent to fourth pcked-ed rector (R-304), in which the
excess enzene is rected with the DEB to produce EB nd unrected enzene. The effluent from this
rector is mixed with the liquid strem entering the wste-het oiler (E-303).

Figure B.2.1 Unit 300: Ethylenzene Process Flow Digrm

Strem summry tles, utility summry tles, nd mjor equipment specifictions re shown in Tles
B.2.1 B.2.3.

Tble B.2.1 Strem Tble for Unit 300

Tble B.2.2 Utility Summry for Unit 300

* Throttled nd desuperheted t exchnger

Tble B.2.3 Mjor Equipment Summry for Unit 300

B.2.2 Rection Kinetics

The production of EB tkes plce vi the direct ddition rection etween ethylene nd enzene:

(B.2.1)

The rection etween EB nd ethylene to produce DEB lso tkes plce:

(B.2.2)

Additionl rections etween DEB nd ethylene yielding triethylenzene (nd higher) re lso possile.
However, in order to minimize these dditionl rections, the molr rtio of enzene to ethylene is kept
high, t pproximtely 8:1. The production of DEB is undesirle, nd its vlue s side product is low.
In ddition, even smll mounts of DEB in EB cuse significnt processing prolems in the downstrem
styrene process. Therefore, the mximum mount of DEB in EB is specified s 2 ppm. In order to
mximize the production of the desired EB, the DEB is seprted nd returned to seprte rector in
which excess enzene is dded to produce EB vi the following equilirium rection:

(B.2.3)

The incoming enzene contins smll mount of toluene impurity. The toluene rects with ethylene to
form ethyl enzene nd propylene:

(B.2.4)

The rection kinetics derived for new ctlyst re given s

(B.2.5)

where i is the rection numer ove (B.2.i), nd the following reltionships pertin.

The units of ri re kmol/s/m3-rector, the units of Ci re kmol/m3-gs, nd the units of ko,i vry depending
upon the form of the eqution.

B.2.3 Simultion (CHEMCAD) Hints

A CHECAD simultion is the sis for the design. The thermodynmics models used were K-vl =
UIFAC nd Enthlpy = Ltent Het.

It should e noted tht in the simultion component seprtor ws plced fter the high-pressure flsh
drum (V-302) in order to remove noncondensles from Strem 16 prior to entering T-301. This is done
in order to void prolems in simulting this tower. In prctice, the noncondensles would e removed
from the overhed reflux drum, V-303, fter entering T-301.
As first pproch, oth towers were simulted s Shortcut columns in the min simultion, ut
susequently ech ws simulted seprtely using the rigorous TWER module. nce the rigorous
TWER simultions were completed, they were sustituted ck into the min flowsheet nd the
simultion ws run gin to converge. A similr pproch is recommended. The rigorous TWER
module provides ccurte design nd simultion dt nd should e used to ssess column opertion, ut
using the shortcut simultions in the initil trils speeds up overll conversion of the flowsheet.

B.2.4 References

1. Willim J. Cnnell, Xylenes nd Ethylenzene, Kirk-Othmer Encyclopedia of

Chemical Technology, on-line version (ew York: John Wiley & Sons, 2006).

2. Ethylenzene, Encyclopedia of Chemical Processing and Design, vol. 20, J. J.

cKett, ed. (ew York: rcel Dekker, Inc., 1984), 77 88.

B.3 Styrene Production, Unit 400

Styrene is the monomer used to mke polystyrene, which hs multitude of uses, the most common of
which re in pckging nd insulted Styrofom everge cups. Styrene is produced y the
dehydrogention of ethylenzene. Ethylenzene is formed y recting ethylene nd enzene. There is very
little ethylenzene sold commercilly, ecuse most ethylenzene mnufcturers convert it directly into
styrene.

B.3.1 Process Description [1, 2]

The process flow digrm is shown in Figure B.3.1. Ethylenzene feed is mixed with recycled
ethylenzene, heted, nd then mixed with high-temperture, superheted stem. Stem is n inert in the
rection, which drives the equilirium shown in Eqution (B.3.1) to the right y reducing the
concentrtions of ll components. Becuse styrene formtion is highly endothermic, the superheted stem
lso provides energy to drive the rection. Decomposition of ethylenzene to enzene nd ethylene, nd
hydrodelkyltion to give methne nd toluene, re unwnted side rections shown in Equtions (B.3.2)
nd (B.3.3). The rectnts then enter two ditic pcked eds with interheting. The products re
cooled, producing stem from the high-temperture rector effluent. The cooled product strem is sent to
three-phse seprtor, in which light gses (hydrogen, methne, ethylene), orgnic liquid, nd wter exit
in seprte strems. The hydrogen strem is further purified s source of hydrogen elsewhere in the
plnt. The enzene/toluene strem is currently returned s feed strem to the petrochemicl fcility. The
orgnic strem contining the desired product is distilled once to remove the enzene nd toluene nd
distilled gin to seprte unrected ethylenzene for recycle from the styrene product.

Figure B.3.1 Unit 400: Styrene Process Flow Digrm

(B.3.1)

(B.3.2)

(B.3.3)

The styrene product cn spontneously polymerize t higher tempertures. Becuse product styrene is sent
directly to the polymeriztion unit, experience suggests tht s long s its temperture is mintined t less
thn 125C, there is no spontneous polymeriztion prolem. Becuse this is less thn styrene s norml
oiling point, nd ecuse low pressure pushes the equilirium in Eqution (B.3.1) to the right, much of
this process is run t vcuum.

Strem tles, utility summries, nd mjor equipment summries re given in Tles B.3.1, B.3.2, nd
B.3.3, respectively.

Tble B.3.1 Strem Tbles for Unit 400

Tble B.3.2 Utility Summry for Unit 400
Tble B.3.3 Mjor Equipment Summry for Unit 400

* See Figure B.3.1 nd Tle B.3.1 for shell-nd-tue side pressures.

B.3.2 Rection Kinetics

The styrene rection my e equilirium limited, nd the equilirium constnt is given s Eqution
(B.3.4).

(B.3.4)
where T is in K nd P is in r.

The equilirium clcultion is given s:

totl = N + 1 + x includes N moles of inert stem

(B.3.5)

where P is in r.

Eqution (B.3.5) cn e used to generte dt for equilirium conversion, x, versus P, T, nd N.

The kinetic equtions re dpted from Snyder nd Surmnim [3]. Suscripts on r refer to rections in
Equtions (B.3.1) (B.3.3), nd the positive ctivtion energy cn rise from nonelementry kinetics; it is
thought tht perhps these kinetics re n elementry pproximtion to nonelementry kinetics.

(B.3.6)

(B.3.7)

(B.3.8)
(B.3.9)

where p is in kP, T is in K, R = 1.987 cl/mol K, nd ri is in mol/m3-rector s.

You should ssume tht the ctlyst hs ulk ctlyst of 1282 kg/m3, n effective dimeter of 25 mm, nd
void frction = 0.4.

B.3.3 Simultion (CHEMCAD) Hints

Results for the simultion given here were otined using SRK s the k-vlue nd enthlpy options in the
thermodynmics pckge.

B.3.4 References

1. Shiou-Shn Chen, Styrene, Kirk-Othmer Encyclopedia of Chemical Technology , on-

line version (ew York: John Wiley & Sons, 2006).

2. Styrene, Encyclopedia of Chemical Processing and Design, vol. 55, J. J. cKett, ed.
(ew York: rcel Dekker, Inc., 1984), 197 217.

3. Snyder, J. D., nd B. Surmnim, A ovel Reverse Flow Strtegy for Ethylenzene

Dehydrogention in Pcked-Bed Rector, Chem. Engr. Sci. 49 (1994): 5585 5601.

B.4 Drying Oil Production, Unit 500

Drying oils re used s dditives to pints nd vrnishes to id in the drying process when these products
re pplied to surfces. The fcility mnufctures drying oil (D) from cetylted cstor oil (AC). Both
of these compounds re mixtures. However, for simultion purposes, cetylted cstor oil is modeled s
plmitic (hexdecnoic) cid (C15H31COOH) nd drying oil is modeled s 1-tetrdecene (C14H28). In n
undesired side rection, gum cn e formed, which is modeled s 1-octcosene (C28H56).

B.4.1 Process Description

The process flow digrm is shown in Figure B.4.1. AC is fed from holding tnk where it is mixed
with recycled AC. The AC is heted to rection temperture in H-501. The rection does not require
ctlyst, since it is initited t high tempertures. The rector, R-501, is simply vessel with inert
pcking to promote rdil mixing. The rection is quenched in E-501. Any gum tht hs een formed is
removed y filtrtion. There re two holding vessels, V-502 A/B. ne of them is used to hold rection
products, while the other one feeds the filter (not shown). This llows continuous flow of mteril into
Strem 7. In T-501 the AC is

Figure B.4.1 Unit 500: Drying il Process Flow Digrm

seprted nd recycled, nd in T-502, the D is purified from the cetic cid. The contents of Strems 11
nd 12 re cooled (exchngers not shown) nd sent to storge.

Strem summry tles, utility summry tles, nd mjor equipment specifictions re shown in Tles
B.4.1 B.4.3.

Tble B.4.1 Strem Tbles for Unit 500

Tble B.4.2 Utility Flow Summry for Unit 500
Tble B.4.3 Mjor Equipment Summry for Unit 500
B.4.2 Rection Kinetics

The rections nd rection kinetics re dpted from Smith [1] nd re s follows.

(B.4.1)

(B.4.2)
where

(B.4.3)

(B.4.4)

nd

(B.4.5)

(B.4.6)

The units of rection rte, ri, re kmol/m3s, nd the ctivtion energy is in cl/mol (which is equivlent to
kcl/kmol).

B.4.3 Simultion (CHEMCAD) Hints

If you wnt to simulte this process nd 1-octcosene is not compound in your simultor s dtse, you
cn dd gum s compound to the simultor dtnk using the following physicl properties:
moleculr weight = 392
oiling point = 431.6C
For the group contriution method dd the following groups
1 CH3 group

25 > CH2 groups

1 = CH2 group
 1 = CH group

B.4.4 Reference

1. Smith, J. ., Chemical Engineering Kinetics, 3rd ed. (ew York: John Wiley & Sons,
1981), 224 228.

B.5 Production of Mleic Anhydride from Benzene, Unit 600

Currently, the preferred route to mleic nhydride in the United Sttes is vi isoutene in fluidized-ed
rectors. However, n lterntive route vi enzene my e crried out using shell-nd-tue rector,
with ctlyst in the tues nd cooling medium eing circulted through the shell.

B.5.1 Process Description

A process flow digrm for the rector section of the mleic nhydride process is shown in Figure B.5.1.
Benzene is vporized in E-601, mixed with compressed ir, nd then heted in fired heter, H-601,
prior to eing sent to pcked-ed ctlytic rector, R-601, where the following rections tke plce.

Figure B.5.1 Unit 600: leic Anhydride Process Flow Digrm

(B.5.1)

(B.5.2)

(B.5.3)

(B.5.4)

All the rections re highly exothermic. For this reson, the rtio of ir to enzene entering the rector is
kept very high. A typicl inlet concentrtion (Strem 6) of pproximtely 1.5 vol% of enzene in ir is
used. Cooling is chieved y circulting molten slt ( mixture of sodium nitrite nd sodium nitrte)
cocurrently through the shell of the rector nd cross the tues contining the ctlyst nd rectnt gses.
This molten slt is cooled in two externl exchngers E-602 nd E-607 prior to returning to the
rector.

The rector effluent, Strem 7 contining smll mounts of unrected enzene, mleic nhydride,
quinone, nd comustion products is cooled in E-603 nd then sent to n sorer column, T-601,
which hs oth reoiler nd condenser. In T-601, the vpor feed is contcted with recycled hevy
orgnic solvent (diutyl phthlte), Strem 9. This solvent sors the mleic nhydride, quinone, nd
smll mounts of wter. Any wter in the solvent leving the ottom of the sorer, T-601, rects with
the mleic nhydride to form mleic cid, which must e removed nd purified from the mleic
nhydride. The ottoms product from the sorer is sent to seprtion tower, T-602, where the diutyl
phthlte is recovered s the ottoms product, Strem 14, nd recycled ck to the sorer. A smll
mount of fresh solvent, Strem 10, is dded to ccount for losses. The overhed product from T-602,
Strem 13, is sent to the mleic cid column, T-603, where 95 mol% mleic cid is removed s the
ottoms product.

The overhed strem is tken to the quinone column, T-604, where 99 mol% quinone is tken s the top
product nd 99.9 mol% mleic nhydride is removed s the ottoms product. These lst two purifiction
columns re not shown in Figure B.5.1 nd re not included in the current nlysis.

Strem summries, utility summries, nd equipment summries re presented in Tles B.5.1 B.5.3.

Tble B.5.1 Flow Summry for Unit 600

Tble B.5.2 Utility Summries for Unit 600

Tble B.5.3 Equipment Summry for Unit 600

B.5.2 Rection Kinetics

The rections nd rection kinetics [3] given in Equtions (B.5.1) (B.5.4) re given y the expression

(B.5.5)
where

(B.5.6)

(B.5.7)

(B.5.8)

(B.5.9)

The units of rection rte, ri, re kmol/m3(rector)s, the ctivtion energy is given in cl/mol (which is
equivlent to kcl/kmol), the units of ki re m3(gs)/m3 (rector)s, nd the units of concentrtion re
kmol/m3(gs).

The ctlyst is mixture of vndium nd molydenum oxides on n inert support. Typicl inlet rection
tempertures re in the rnge of 350C to 400C. The ctlyst is plced in 25 mm dimeter tues tht re
3.2 m long. The ctlyst pellet dimeter is 5 mm. The mximum temperture tht the ctlyst cn e
exposed to without cusing irreversile dmge (sintering) is 650C. The pcked-ed rector should e
costed s shell-nd-tue exchnger. The het trnsfer re should e clculted sed on the totl
externl re of the ctlyst-filled tues required from the simultion. Becuse of the high tempertures
involved, oth the shell nd the tue mteril should e stinless steel. An overll het trnsfer coefficient
for the rector should e set s 100 W/m2C. (This is the vlue specified in the simultion.)

B.5.3 Simultion (CHEMCAD) Hints

The CHECAD simultion used to generte the PFD shown in Figure B.5.1 hs severl simplifictions
tht re vlid for this system. The removl of trce mounts of noncondensles is chieved fter the
sorer using component seprtor, which voids prolems with column convergence downstrem.
The formtion of mleic cid is simulted y using stoichiometric rector nd setting the conversion of
wter to 1.

Tower T-601, the mleic nhydride scruer, is simulted using the rigorous tower simultor. Tower T-
602, the diutyl phthlte tower, is simulted using the Shortcut column module. Currently, we do not
hve ny experimentl vpor pressure dt for the components in this simultion. It ppers tht the vpor
pressures of the components differ widely, nd no zeotropes re known t this time. For this reson, the
idel vpor pressure K-vlue option nd the ltent het enthlpy option re used.

In order to simulte the temperture spike in the rector, the rector is simulted s cocurrent, pcked-
ed kinetic rector, with molten slt strem s the utility. This configurtion provides greter
temperture differentil t the front end of the rector, where the rection rte is highest. Countercurrent
flow could e investigted s n lterntive. The kinetics given ove re used in the simultion.
Dimensions of the rector tues re given in Section B.5.2.

B.5.4 References

1. Felthouse, T. R., J. C. Burnett, B. Horrell, . J. ummey, nd Y-J Kuo, leic

Anhydride, leic Acid, nd Fumric Acid, Kirk-Othmer Encyclopedia of Chemical
Technology, on-line version (ew York: John Wiley & Sons, 2001).

2. leic Acid nd Anhydride, Encyclopedia of Chemical Processing and Design, vol.

29, J. J. cKett, ed. (ew York: rcel Dekker, Inc., 1984), 35 55.

3. Wohlfhrt, Emig G., Compre leic Anhydride Routes, Hydrocarbon Processing

(June 1980): 83 90.

B.6 Ethylene Oxide Production, Unit 700

Ethylene oxide is chemicl used to mke ethylene glycol (the primry ingredient in ntifreeze). It is lso
used to mke polyethylene-oxide, nd oth the low-moleculr-weight nd high-moleculr-weight
polymers hve mny pplictions including s detergent dditives. Becuse ethylene oxide is so rective,
it hs mny other uses s rectnt. However, ecuse of its rectivity, dnger of explosion, nd toxicity,
it is rrely shipped outside the mnufcturing fcility ut insted is often pumped directly to nery
consumer.

B.6.1 Process Description [1, 2]

The process flow digrm is shown in Figure B.6.1. Ethylene feed (vi pipeline from neighoring plnt)
is mixed with recycled ethylene nd mixed with compressed nd dried ir (drying step not shown),
heted, nd then fed to the first rector. The rection is exothermic, nd medium-pressure stem is mde
in the rector shell. Conversion in the rector is kept low to enhnce selectivity for the desired product.
The rector effluent is cooled, compressed, nd sent to scruer, where ethylene oxide is sored y
wter. The vpor from the scruer is heted, throttled, nd sent to second rector, followed y
second series of cooling, compression, nd scruing. A frction of the unrected vpor strem is purged,
with the reminder recycled to recover unrected ethylene. The comined queous product strems re
mixed, cooled, throttled, nd distilled to produce the desired product. The required purity specifiction is
99.5 wt% ethylene oxide.

Figure B.6.1 Unit 700: Ethylene xide Process Flow Digrm

Strem summry tles, utility summry tles, nd mjor equipment specifictions re shown in Tles
B.6.1 B.6.3.

Tble B.6.1 Strem Tble for Unit 700

Tble B.6.2 Utility Summry for Unit 700

Tble B.6.3 Mjor Equipment Summry for Unit 700

*ote tht ll compressors hve electric-explosion-proof drives with ckup. These units re
designted D-701 A/B through D-705 A/B ut re not shown on the PFD.
B.6.2 Rection Kinetics

The pertinent rections (dpted from Stoukides nd Pvlou [3]) re s follows.

(B.6.1)

(B.6.2)
(B.6.3)

The kinetic expressions re, respectively,

(B.6.4)

(B.6.5)

(B.6.6)

The units for the rection rtes re moles/m3 s. The pressure unit is r. The ctivtion energy numertor
is in cl/mol. The ctlyst used for this rection is silver on n inert support. The support consists of 7.5
mm dimeter spheres tht hve ulk density of 1250 kg/m3 nd void frction of 0.4.

B.6.3 Simultion (CHEMCAD) Hints

The following thermodynmics pckges re strongly recommended for simultion of this process.
K-vlues: Use glol model of PSRK ut use UIFAC s locl model for T-701 nd T-702.
Enthlpy: Use SRK.

B.6.4 References

1. Dever, J. P., K. F. George, W. C. Hoffmn, nd H. Soo, Ethylene xide, Kirk-Othmer

Encyclopedia of Chemical Technology , on-line version (ew York: John Wiley & Sons,
2004).
 2. Ethylene xide, Encyclopedia of Chemical Processing and Design, vol. 20, J. J.
cKett, ed. (ew York: rcel Dekker, Inc., 1984), 274 318.

3. Stoukides, ., nd S. Pvlou, Ethylene xidtion on Silver Ctlysts: Effect of Ethylene

xide nd of Externl Trnsfer Limittions, Chem. Eng. Commun. 44 (1986): 53 74.

B.7 Formlin Production, Unit 800

Formlin is 37 wt% solution of formldehyde in wter. Formldehyde nd ure re used to mke ure-
formldehyde resins tht susequently re used s dhesives nd inders for prticle ord nd plywood.

B.7.1 Process Description [1, 2]

Unit 800 produces formlin (37 wt% formldehyde in wter) from methnol using the silver ctlyst
process. Figure B.7.1 illustrtes the process.

Figure B.7.1 Unit 800: Formlin Process Flow Digrm

Air is compressed nd preheted, fresh nd recycled methnol is pumped nd preheted, nd these two
strems re mixed to provide rector feed. The feed mixture is out 39 mole % methnol in ir, which is
greter thn the upper flmmility limit for methnol. (For methnol, UFL = 36 mole %; LFL = 6 mole
%.) In the rector, the following two rections occur.

(B.7.1)
(B.7.2)

The rector is unique configurtion, in which the silver ctlyst is in the form of wire guze, suspended
ove het exchnger tue nk. Becuse the net rection is very exothermic, the het generted in the
ditic rector section must e removed quickly, hence the close proximity of the het exchnger tues.
The het exchnger resemles pool oiler, with pool of wter on the shell side. If the temperture of
the effluent is too high, the set point on the stem pressure line is lowered to increse the vporiztion of
oiler feed wter (BFW). In generl, the liquid-level controller on the BFW is djusted to keep the tue
undle fully immersed. The rector effluent enters n sorer in which most of the methnol nd
formldehyde re sored into wter, with most of the remining light gses purged into the off-gs
strem. The methnol, formldehyde, nd wter enter distilltion column, in which the methnol
overhed is recycled; the ottoms product is formldehyde/wter mixture tht contins 1 wt%
methnol s n inhiitor. This mixture is cooled nd sent to storge tnk, which is sized t four dys
cpcity. This storge tnk is essentil, ecuse some of the downstrem processes re tch. The
composition in the storge tnk exceeds 37 wt% formldehyde, so the pproprite mount of wter is
dded when the downstrem process drws from the storge tnk. This is not shown in the PFD (Figure
B.7.1).

Storge of formldehyde/wter mixtures is tricky. At high tempertures, undesirle polymeriztion of

formldehyde is inhiited, ut formic cid formtion is fvored. At low tempertures, cid formtion is
inhiited, ut polymeriztion is fvored. There re stilizers tht inhiit polymeriztion, ut they re
incomptile with resin formtion. ethnol, t concentrtions etween 5 wt% nd 15 wt%, cn lso
inhiit polymerizton, ut no seprtion equipment for methnol currently exists on site, nd methnol
greter thn 1 wt% lso cuses defective resin production. With 1 wt% methnol, the storge tnk
contents must e mintined etween 35C nd 45C.

Strem summry tles, utility summry tles, nd mjor equipment specifictions re shown in Tles
B.7.1 B.7.3.

Tble B.7.1 Strem Tbles for Unit 800

Tble B.7.2 Utility Strem Flow Summry for Unit 800
Tble B.7.3 Mjor Equipment Summry for Unit 800
B.7.2 Rection Kinetics

Due to the very high temperture nd lrge surfce re of the wire guze, the rection my e considered
to e instntneous.

B.7.3 Simultion (CHEMCAD) Hints

Solutions of formldehyde nd wter re very non-idel. Individully, the voltilities re, from most
voltile to lest voltile, formldehyde, methnol, nd wter. However, formldehyde ssocites with
wter so tht when this three-component mixture is distilled, methnol is the light key nd wter is the
hevy key. The formldehyde will follow the wter. The ESDK K-vlue pckge in CHECAD
simultes this ppropritely nd ws used for the simultion presented here. Ltent het should e used
for enthlpy clcultions. The expert system will recommend these choices. Alterntively, the dt
provided in Tle B.7.4 cn e used directly or to fit n pproprite non-idel VLE model.

Tble B.7.4 K-vlues for Formldehyde/Wter/Methnol System [2]

When simulting n entire process, we recommend first using the Shortcut distilltion column within the
process for the methnol-wter/formldehyde distilltion. A rigorous column solver should then e used
s seprte item to simulte the column sed on the results otined from the shortcut column.
However, due to the non-idelity of the thermodynmics, the ctul column simultion using the rigorous
column will proly require mny more stges thn predicted y the shortcut simultion, possily twice
the numer. nce the prmeters for the rigorous column hve een estlished, the Shortcut column cn
e replced y the rigorous column nd the simultion rerun to get converged simultion.

B.7.4 References

1. Gererich, H. R., nd G. C. Semn, Formldehyde, Kirk-Othmer Encyclopedia of

Chemical Technology, on-line version (ew York: John Wiley & Sons, 2004).

2. Formldehyde, Encyclopedia of Chemical Processing and Design, vol. 23, J. J.

cKett, ed. (ew York: rcel Dekker, Inc., 1984), 350 371.

3. Gmehling, J., U. nken, nd W. Arlt, Vapor-Liquid Equilibrium Data Collection ,

Chemistry Dt Series (Aqueous-rgnic Systems, Supplement 1), vol. 1, prt 1,
DECHEA, 1981, 474 475.

B.8 Btch Production of L-Phenyllnine nd L-Asprtic Acid, Unit 900

Phenlylnine nd L-sprtic cid re mino cids. When they ond together, the corresponding di-
peptide methyl ester is sprtme, known y the rnd nme utr-Sweet or Equl. Production of oth
mino cids cn e ccomplished vi fermenttion of geneticlly ltered cteri. Production rtes of
1,000 nd 1,250 tonnes/yr of L-sprtic cid nd L-phenyllnine re desired.

B.8.1 Process Description

To ccomplish fermenttion process, cteri must grow in the presence of pproprite nutrients tht
fcilitte the production of the desired product. In processing context, the fermenttion rector must first
e primed with the cteri nd the nutrients. The nutrient feed includes the rectnt tht the cteri
metolize to produce the desired mino cid. Air is lso sprged into the fermenter s source of
oxygen. All of these feeds re pssed through steriliztion filters prior to entering the rector. The
cteri re then llowed to multiply, nd the desired product, n mino cid in this cse, is produced. In
this process, oth products re extrcellulr. After the desired production level of the mino cid is
reched, the fermenttion roth pH is lowered y ddition of sulfuric cid, the cteri re removed from
the fermenttion roth y filtrtion, nd the product strem is sent to holding tnk. The ddition of cid
titrtes the mino cid, mking it positively chrged. The ddition of cid is done only for phenyllnine,
ecuse L-sprtic cid ypsses the ion exchnge column nd is crystllized directly vi precipittion
from solution.

In this process, oth mino cids re produced in the sme fcility. Becuse fermenttion is involved nd
production levels re low compred with typicl commodity chemicls, tch processes re involved. In
tch processes, the key vrile is the tch time, or the length of time tht the unit is llowed to run. For
exmple, in tch rector, the tch time is nlogous to the spce time in continuous rector.

The seprtion sequence is continuous process, which is ccomplished y continuous feed from the
holding tnk. This is not uncommon in tch fcilities, ecuse mny seprtion processes re more esily
ccomplished in the continuous mode. The seprtion sequence for the two mino cids differs slightly.
Phenyllnine is isolted using ion exchnge followed y crystlliztion; in contrst, L-sprtic cid is
crystllized directly from the filtered fermenttion roth. For phenyllnine, it is dsored on the ion
exchnge resin nd susequently eluted using sic solution. The ddition of se neutrlizes the
positive chrge to promote desorption from the ion exchnge resin. For oth mino cids, filtrtion
follows crystlliztion. The product is then sent to storge. The process is shown in Figure B.8.1.

Figure B.8.1 Unit 900: Amino Acid Process Flow Digrm

The use of tch processing requires tch scheduling of the type discussed in Chpter 3, which llows
use of the sme equipment to mnufcture oth mino cids in the sme fcility. In this description, only
the PFD, rector clcultions, nd generl descriptions of the seprtion units re presented. The design
of individul equipment, the utility consumption, nd the production schedule for the plnt re left s
exercises for the student. A description of process to produce four mino cids (including the two mino
cids in this process) in the sme fcility is ville t
http://www.che.cemr.wvu.edu/pulictions/projects/lrge_proj/tch-production_of_mino_cids.pdf.
This process description includes possile tch schedules for oth the rectors nd the seprtion
section.

B.8.2 Rection Kinetics

L-Asprtic Acid. The rection of fumric cid to form L-sprtic cid is n enzymtic conversion
crried out using the sprtse ctivity of cteri Escherichia Coli (E. Coli) cells ccording to the
following rection.

(B.8.1)

The cteri cells re suspended in mtrix polycrylmide gel, nd the recting species must diffuse in
nd out of the mtrix. The diffusivities of the sustrte (fumric cid) nd product (L-sprtic cid) in the
gel decrese s their concentrtions increse due to the tendency of the gel to shrink t low pH.

The kinetic model for this rection follows ichelis-enten form for reversile rection, which
rerrnges to

(B.8.2)

CFA is the concentrtion of fumric cid (kmol/m3).

CAA is the concentrtion of L-sprtic cid (kmol/m3).

is the concentrtion of mmonium ions (kmol/m3).

where K is rection equilirium constnt (m3/kmol).

Va is the pprent rte of production of L-sprtic cid (kmol/h/kg-gel).

Va,mx is the pprent mximum rte of production of L-sprtic cid (kmol/h/kg-gel).

Ka,M is the pprent ichelis constnt for the rection (kmol/m3).

Rection rte prmeters hve een modified from reference [1] nd re used for the current process
using 1.0 sustrte solution t rection temperture of 32C.
It should e noted tht the reltionship = 2.04CFA cn e chieved only in tch rector y
mesuring the concentrtion of fumric cid nd djusting the mmoni concentrtion with time. This
pproch is ssumed here; however, if fixed mount of mmoni is initilly dded to the rector, then
the reltionship etween nd CFA must e found from the mteril lnce nd sustituted in
Eqution (B.8.2).

Sustituting the ove vlues into Eqution (B.8.2) nd using the conversion, X, of fumric cid (CFA =
CFA,0(1 X) nd CAA = CFA,0X), we get

(B.8.3)

V is the volume of the recting mss in the rector (m3).

W is the weight of the gel (kg) = V(1- ) bead .

where
is the void frction of eds in the recting mss.

bead is the ed density (kg/m3).

Sustituting into Eqution (B.8.3) we hve

(B.8.4)

For the specified initil concentrtion of fumric cid of 1.0 = 1 kmol/m3 nd with bead 1,000 kg/m3
nd ssuming voidge of 0.5, Eqution (B.8.4) simplifies to

(B.8.5)
Seprting vriles nd integrting Eqution (B.8.5) yield the conversion s function of tch rection
time. This reltionship is shown in Figure B.8.2.

Figure B.8.2 Conversion of Fumric Acid to L-Asprtic Acid s Function of Rection Time

Preliminry Sizing of Rector R-901. For conversion of 45% (90% of equilirium), rection time
of pproximtely 30 hours is required. Assuming tht n dditionl 5 hours is required for filling,
clening, nd heting, the totl rector step time is 35 hours.

Using rector size of 37.9 m3 (10,000 gl) nd ssuming 90% fill volume nd voidge of 0.5, the
mount of fumric cid fed to the tch is (37.9)(0.9)(0.5) = 17.04 m3, or 17.04 kmol (17.04 116 =
1977 kg). The mount of L-sprtic cid produced = (17.04)(0.45) = 7.67 kmol = (7.67)(133) = 1020 kg.

Production rte of L-sprtic cid from 10,000 gllon rector is 1020 kg/tch using tch time of 35
hr.

L-Phenyllnine. L-phenyllnine is produced vi fermenttion using mutnt Brevibacterium

lactofermentum 2256 (ATCC o. 13869) known s o. 123 [ 2]. The rte equtions for iomss
(cteri, X), sustrte (minly glucose, S), nd product (L-phenyllnine, P) re descried y onod
kinetics.

(B.8.6)
(B.8.7)

(B.8.8)

where
X is the concentrtion of cteri (kg/m3).

S is the concentrtion of sustrte (glucose) (kg/m3).

P is the concentrtion of product (L-phenyllnine) (kg/m3).

m is the mximum specific growth rte (hr 1).

Ks is the onod constnt (kg/m3).

YXS is iomss yield.

YPS is product yield.

According to Tsuchid et l. [2], for culture medium contining 13% glucose, 1% mmonium sulfte,
nd 1.2% fumric cid (plus other trce nutrients etc.) the yield of L-phenyllnine ws 21.7 mg/ml fter
72 hr of cultivtion t temperture of 31.5C. This represents yield of pproximtely 16.7% from
glucose y weight. ther mino cids re lso produced in smll quntities (<5 kg/m3), with Lysine
mking up pproximtely 50%.

To otin kinetic model of the growth of cteri nd susequent production of L-phenyllnine nd

depletion of glucose, the prmeters in Equtions (B.8.6) (B.8.8) were ck clculted to give est-fit
profiles of X, S, nd P compred to pulished vlues ([2], Figure 4). The prmeter vlues re shown in
Tle B.8.1, nd the profiles re plotted in Figure B.8.3.

Tble B.8.1 Best-Fit Prmeters for Monod Kinetics Using Brevibacterium lactofermentum
2256 (ATCC No. 13869) Strin No. 123
Figure B.8.3 Concentrtion Profiles s Function of Rector Time

Preliminry Sizing of Rector R-901. For rection time of pproximtely 60 hours, the finl
concentrtion of L-phenyllnine is 21.0 kg/m3. Assuming n dditionl 5 hours for filling, clening, nd
heting gives totl rector step time of 65 hours.

Using 37.9 m3 (10,000 gl) rector for the fermenttion nd ssuming tht 90% fill volume is used, the
volume of rectnts is (37.9)(0.9) = 34.11 m3.

The mount of L-phenyllnine produced in 60 h tch rection is (34.11)(21.0) = 716 kg.

Production rte of L-sprtic cid from 10,000 gllon rector is 716 kg/tch, with rector step time
of 65 hr.

Preliminry Informtion on Other Equipment. As mentioned in the process description, the

production of oth L-sprtic cid nd L-phenyllnine follows similr pths. A rief discussion of the
unit opertions involved with the seprtion nd purifiction of the finl products is in order, ecuse
these opertions re not typicl of the unit opertions covered in this text. Size informtion is not included
for the equipment descried next; however, estimtes of processing times, where pplicle, re given.

Filtrtion of Bcteri. After rection, the cteri must e filtered from the mother liquor prior to
storge. The cteri tend to give rise to slimy filter ckes, nd the filtrtion of such mteril is est
ccomplished using rotry drum filter utilizing precot. Typicl precoting mterils re dolomite,
perlite, nd cellulose, nd these re pplied to the drum in two-stge process prior to filtrtion. The
precoting process involves depositing lyer of the precot mteril (5 15 cm thick) on the drum prior
to the filtrtion opertion. nce the precot hs een pplied, the filtrtion strts, nd the iomss forms
thin lyer on the precot. This lyer of iomss is continuously removed, long with thin lyer of the
precot mteril, using shrp-edged Doctor lde. Additionl informtion is given t
http://www.solidliquid-seprtion.com [3]. Without doing detiled clcultions, it is difficult to
determine the time required for the precot stge nd filtrtion stges. For this project you my ssume
tht these steps tke 25 h nd 5 h, respectively.

Intermedite Storge. The fermenttion roth (free of solids, or iomss) leving the filters is stored in
n intermedite storge tnk prior to eing sent to the ion exchnge column (for L-phenyllnine) nd on
to the crystllizer. The use of n intermedite storge vessel llows the reminder of the process to
operte s continuous process.

Ion Exchnge Column. The ion exchnge columns operte s semitch processes. Hydrochloric cid
is dded to the L-phenyllnine-contining solution nd is pssed through freshly regenerted ion
exchnge resin such s DW s Dowex rthon C [4]. The resin cptures the positively chrged mino
cid. nce the ed is full, it is ckwshed with sic solution of mmonium or sodium hydroxide,
which reks the resin mino cid ond. The resin is susequently wshed free of the hydroxide, nd the
cycle strts gin.

Continuous Crystllizer nd Filtrtion. Drft tue ffle crystllizers cn e used for the
crystlliztion of L-sprtic cid nd L-phenyllnine. These crystllizers offer the dvntges of high
circultion rtes for efficient mixing. Fines removl is fcilitted through the use of ffles, nd certin
mount of product clssifiction (crystl size control) is otined through the elutriting leg. Btch
crystllizers could lso e used, ut product qulity nd efficiency suffer. The sturted liquid from the
crystllizer, contining mino cid crystls, is sent to filter (such s rotry drum filter), where the
crystls re removed nd sent for wshing, drying, nd pckging. The sturted liquid is returned to the
crystllizer for further product recovery, therey incresing the efficiency of the opertion. Both mino
cids cn e crystllized t tempertures greter thn 100C. Therefore, the crystlliztion my tke plce
t mient pressure y removing the excess wter through evportion. The soluilities of L-sprtic cid
nd L-phenyllnine t 100C re 67 g/liter nd 100 g/liter, respectively.

B.8.3 References

1. Tkmtch, T., K. Ymshit, nd A. Sumi, Kinetics of Production of L-sprtic Acid y

Asprtse of Immoilized E. Coli Cells, Japanese Journal of Fermentation Technology
58, no. 2 (1980): 129 133.

2. Tsuchid, T., K. Kuot, Y. oring, H. tsui, H. Enei, nd F. Yoshing, Production

of L-phenyllnine y utnt of Brevibacterium lactofermentum 2256, Agric. Bio.
Chem. 51, no. 8 (1987): 2095 2101.

3. http://www.solidliquid-seprtion.com.

4. DWEX rthon C dt sheet,

 4. DWEX rthon C dt sheet,
http://www.dow.com/PulishedLiterture/dh_0082/090180380082f5.pdf?
filepth=liquidseps/pdfs/noreg/177-01593.pdf&fromPge=GetDoc.

B.9 Acrylic Acid Production vi the Ctlytic Prtil Oxidtion of Propylene [ 1, 2, 3,

4, 5]

Acrylic cid (AA) is used s precursor for wide vriety of chemicls in the polymer nd textile
industries. There re severl chemicl pthwys to produce AA, ut the most common one is vi the
prtil oxidtion of propylene. The usul mechnism for producing AA utilizes two-step process in
which propylene is first oxidized to crolein nd then further oxidized to AA. Ech rection step usully
tkes plce over seprte ctlyst nd t different operting conditions. The rection stoichiometry is
given elow:

Severl side rections my occur, most resulting in the oxidtion of rectnts nd products. Some typicl
side rections re given elow:

Therefore, the typicl process setup consists of two-rector system, with ech rector contining
seprte ctlyst nd operting t conditions so s to mximize the production of AA. The first rector
typiclly opertes t higher temperture thn the second.

As with ny rection involving the prtil oxidtion of fuel-like feed mteril (propylene), considerle
ttention must e pid to the composition of hydrocrons nd oxygen in the feed strem. In the current
design, fluidized-ed rector is used, which provides essentilly isotherml conditions in the rector
nd, with the ddition of lrge mounts of stem, llows sfe nd stle opertion. The second sfety
concern is ssocited with the highly exothermic polymeriztion of AA, which occurs in two wys. First,
if this mteril is stored without pproprite dditives, then free rdicl initition of the polymeriztion
cn occur. This potentilly disstrous sitution is discussed y Kurlnd nd Brynt [1]. Second, AA
dimerizes when in high concentrtions t tempertures greter thn 90C, nd thus much of the seprtion
sequence must e operted under high vcuum in order to keep the ottom tempertures in the columns
elow this temperture.

B.9.1 Process Description

The process shown in Figure B.9.1 produces 50,000 metric tons per yer of 99.9% y mole AA product.
The numer of operting hours is tken to e 8000/yr, nd the process is somewht simplified ecuse
there is only one rector [5]. It is ssumed tht oth rections tke plce on single ctlyst to yield AA
nd y-products. It is impertive to cool the products of rection quickly to void further oxidtion
rections, nd this is chieved y rpidly quenching the rector effluent with cool recycle, Strem 8, of
dilute queous AA in T-1001. Additionl recovery of AA nd cetic cid ( y-product) is chieved in
the sorer, T-1002. The strem leving the sorption section is dilute queous cid, Strem 9. This
is sent to liquid-liquid extrctor, T-1003, to remove preferentilly the cid frction from the wter prior
to purifiction. There re mny possile solvents tht cn e used s the orgnic phse in the seprtion;
high soluility for AA nd low soluility for wter re desirle. Some exmples include ethyl crylte,
ethyl cette, xylene, diisoutyl ketone, methyl isoutyl ketone, nd diisopropyl ether (DIPE), which is
used here. The orgnic phse from T-1003 is sent to solvent recovery column, T-1004, where the
diisopropyl ether (nd some wter) is recovered overhed nd returned to the extrctor. The ottom
strem from this column, Strem 14, contins virtully ll the AA nd cetic cid in Strem 9. This is sent
to the cid purifiction column, T-1005, where 95% y mole cetic cid y-product is produced
overhed, nd 99.9 % y mole AA is produced s ottoms product nd cooled prior to eing sent to
storge.

Figure B.9.1 Unit 1000: Production of Acrylic Acid from Propylene PFD (The point where Strems 1
nd 2 re mixed with Strem 3 to form Strem 4 ctully occurs within Recor R-1001.)

The queous phse from the extrctor, Strem 12, is sent to wstewter column, T-1006, where smll
mount of DIPE is recovered overhed nd returned to the extrctor. The ottoms product, contining
wter nd trce quntities of solvent nd cid, is sent to wstewter tretment. Process strem informtion
nd preliminry equipment summries re given in Tles B.9.1 nd B.9.2, respectively. A utility
summry is lso provided in Tle B.9.3.

Tble B.9.1 Flow Summry Tble for Acrylic Acid Process in Figure B.9.1
Tble B.9.2 Preliminry Equipment Summry Tble for Acrylic Acid Process
 Tble B.9.3 Utility Summry for Unit 1000

B.9.2 Rection Kinetics nd Rector Configurtion

The rections tking plce re kineticlly controlled t the conditions used in the process; tht is,
equilirium lies fr to the right. The rection kinetics for the ctlyst used in this process re given
elow:
Prtil pressures re in kP, nd the ctivtion energies nd preexponentil terms for rections 1 3 re s
follows.

The rector configurtion used for this process is fluidized ed, nd it is ssumed tht the ed of ctlyst
ehves s well-mixed tnk tht is, it is isotherml t the temperture of the rection (310C). The gs
flow is ssumed to e plug flow through the ed, with 10% of the gs ypssing the ctlyst. This ltter
ssumption is mde in order to simulte the gs chnneling tht occurs in rel fluid-ed rectors.

B.9.3 Simultion (CHEMCAD) Hints

The use of liquid-liquid extrctor requires the use of thermodynmic pckge (or physicl property
dt) tht reflects the fct tht two phses re formed nd tht significnt prtitioning of the AA nd cetic
cid occurs, with the mjority going to the orgnic phse (in this cse DIPE). Distriution coefficients for
the orgnic cids in wter nd DIPE s well s mutul soluility dt for wter/DIPE re desirle. The
process given in Figure B.2 ws simulted using UIFAC thermodynmics pckge nd the ltent het
enthlpy option on CHECAD nd should give resonle results for preliminry process design. uch
of the process ckground mteril nd process configurtion ws tken from the 1986 AIChE student
contest prolem in Reference [5]. The kinetics presented ove re fictitious ut should give resonle
preliminry estimtes of rector size.

B.9.4 References

1. Kurlnd, J. J., nd D. B. Brynt, Shipord Polymeriztion of Acrylic Acid, Plant

Operations Progress 6, no. 4 (1987): 203 207.

2 . Kirk-Othmer Encyclopedia of Chemical Technology , 3rd ed., vol. 1 (ew York: John
 2 . Kirk-Othmer Encyclopedia of Chemical Technology , 3rd ed., vol. 1 (ew York: John
Wiley nd Son, 1978), 330 354.

3 . Encyclopedia of Chemical Processing and Design, ed. J. J. cKett nd W. A.

Cunninghm, vol. 1 (ew York: rcel Dekker, 1976), 402 428.

4. Skuym, S., T. hr, . Shimizu, nd K. Kuot, A ew xidtion Process for

Acrylic Acid from Propylene, Chemical Technology (June 1973): 350.

5. 1986 Student Contest Prolem, The AIChE Student Annual 1986, ed. B. Vn Wie, nd
R. A. Wills (AIChE, 1986), 52 82.

B.10 Production of Acetone vi the Dehydrogention of Isopropyl Alcohol (IPA) [ 1,

2, 3, 4], Unit 1100

The prevlent process for the production of cetone is s y-product of the mnufcture of phenol.
Benzene is lkylted to cumene, which is further oxidized to cumene hydroperoxide nd finlly cleved to
yield phenol nd cetone. However, the process shown in Figure B.10.1 nd discussed here uses
isopropyl lcohol (IPA) s the rw mteril. This is vile commercil lterntive, nd few plnts
continue to operte using this process. The primry dvntge of this process is tht the cetone produced
is free from trce romtic compounds, prticulrly enzene. For this reson, cetone produced from IPA
my e fvored y the phrmceuticl industry due to the very tight restrictions plced on solvents y the
Food nd Drug Administrtion (FDA). The rection to produce cetone from IPA is s follows.

Figure B.10.1 Unit 1100: Production of Acetone from Isopropyl Alcohol PFD

The rection conditions re typiclly 2 r nd 350C, giving single-pss conversions of 85% 92%.

B.10.1 Process Description

Referring to Figure B.10.1, n zeotropic mixture of isopropyl lcohol nd wter (88 wt% IPA) is fed
into surge vessel (V-1101), where it is mixed with the recycled unrected IPA/wter mixture, Strem
14. This mteril is then pumped nd vporized prior to entering the rector. Het is provided for the
endothermic rection using circulting strem of molten slt, Strem 4. The rector effluent, contining
cetone, hydrogen, wter, nd unrected IPA, is cooled in two exchngers prior to entering the phse
seprtor (V-1102). The vpor leving the seprtor is scrued with wter to recover dditionl
cetone, nd then this liquid is comined with the liquid from the seprtor nd sent to the seprtions
section. Two towers re used to seprte the cetone product (99.9 mole %) nd to remove the excess
wter from the unused IPA, which is then recycled ck to the front end of the process s n zeotropic
mixture. Strem summries, preliminry equipment nd utility summries re given in Tles B.10.1,
B.10.2 nd B.10.3, respectively.

Tble B.10.1 Flow Tble for Acetone Process in Figure B.10.1

Tble B.10.2 Preliminry Equipment Summry Tble for Acetone Process

Tble B.10.3 Summry Tble Unit 1100
B.10.2 Rection Kinetics

The rection to form cetone from isopropyl lcohol (isopropnol) is endothermic, with stndrd het
of rection of 62.9 kJ/mol. The rection is kineticlly controlled nd occurs in the vpor phse over
ctlyst. The rection kinetics for this rection re first order with respect to the concentrtion of lcohol
nd cn e estimted from the following eqution [3,4]:

In prctice, severl side rections cn occur to smll extent. Thus, trce quntities of propylene,
diisopropyl ether, cetldehyde, nd other hydrocrons nd oxides of cron cn e formed [1]. The
noncondensles re removed with the hydrogen, nd the ldehydes nd ethers my e removed with cid
wshing or dsorption. These side rections re not ccounted for in this preliminry design.

For the design presented in Figure B.10.1, the rector ws simulted with ctlyst in 2-in (50.4 mm)
dimeter tues, ech 20 feet (6.096 m) long, nd with cocurrent flow of het trnsfer medium on the
shell side of the shell-nd-tue rector. The resulting rrngement gives 90% conversion of IPA per
pss.

B.10.3 Simultion (CHEMCAD) Hints

Isopropyl lcohol nd wter form minimum oiling point zeotrope t 88 wt% isopropyl lcohol nd 12
wt% wter. Vpor-liquid equilirium (VLE) dt re ville from severl sources nd cn e used to
ck-clculte inry interction prmeters or liquid-phse ctivity coefficients. The process presented
in Figure B.3 nd Tle B.6 ws simulted using the UIQUAC VLE thermodynmics pckge nd the
ltent het enthlpy option in the CHECAD simultor. This pckge correctly predicts the formtion of
the zeotrope t 88 wt% lcohol.

B.10.4 References

1 . Kirk-Othmer Encyclopedia of Chemical Technology , 3d ed., vol. 1 (ew York: John

Wiley & Sons, 1976), 179 191.

2. Shreves Chemical Process Industries , 5th ed., ed. G. T. Austin (ew York: cGrw-
Hill, 1984), 764.

3 . Encyclopedia of Chemical Processing and Design, ed. J. J. cKett nd W. A.

 3 . Encyclopedia of Chemical Processing and Design, ed. J. J. cKett nd W. A.
Cunninghm, vol. 1 (ew York: rcel Dekker, 1976), 314 362.

4. Sheely, C. Q., Kinetics of Catalytic Dehydrogenation of Isopropanol , Ph.D. Thesis,

University of Illinois, 1963.

B.11 Production of Heptenes from Propylene nd Butenes [1], Unit 1200

This ckground informtion for this process is tken from Chuvel et l. [1]. This exmple is n
illustrtion of preliminry estimte of process to convert mixture of C3 nd C4 unsturted
hydrocrons to 1-heptene nd other unsturted products. The mrket for the 1-heptene product would e
s highoctne lending gent for gsoline or in the production of plsticizers. Bsed on preliminry
mrket estimtes, production cpcity of 20,000 metric tons per yer of 1-heptene using 8000 operting
hours/yr ws set. This process differs from the other exmples in Appendix B in severl wys. First, the
rw mterils to the process contin wide vriety of chemicls. This is typicl for oil refinery nd some
petrochemicl opertions. Second, no specific kinetic equtions re given for the rections. Insted, the
results of lortory tests using the desired ctlyst t different conditions nd using different feed
mterils re used to guide the process engineer to n optimum, or close to n optimum, rector
configurtion. The flowsheet in Figure B.11.1 nd strem, equipment summry, nd utility summry
tles, Tles B.11.1 B.11.3, hve een developed using such informtion. It should e noted tht
preliminry economic nlysis, nd hence the fesiility of the process, cn e determined without this
informtion, s long s yield nd conversion dt re ville nd the rector configurtion cn e
estimted.

Figure B.11.1 Unit 1200: Production of Heptenes from Propylene nd Butenes PFD

Tble B.11.1 Flow Summry Tble for Heptene Process in Figure B.11.1
Tble B.11.2 Preliminry Equipment Summry Tble for Heptene Process Unit 1200
*Are nd duty given for one exchnger; five identicl exchngers re needed.
 Tble B.11.3 Utility Summry for Unit 1200

*Flow of cooling wter shown for one exchnger only.

B.11.1 Process Description

Two liquid feed strems contining propylene nd utene nd strem of ctlyst slurried with 1-hexene
re mixed t pressure of pproximtely 8 r prior to eing sent to the rector. The rector consists of
five essentilly well-mixed sections, with similr concentrtions in ech section. Het removl is
chieved y using pump-rounds from ech stge through externl het exchngers. The rector effluent is
prtilly vporized efore eing fed to the first of three distilltion columns. The first column (T-1201)
removes the unrected C3 nd C4 components, which re used susequently s fuel (Strem 7) or sent to
LPG storge (Strem 6). The next column (T-1202) seprtes the 1-hexene product overhed (Strem 10)
nd sends the ottoms strem to the finl column (T-1203). In T-1203, the min 1-heptene product
(Strem 13) is tken overhed, nd the C8 nd hevier compounds re tken s the ottoms product
(Strem 14). The ottoms product is processed off-site to remove the hevy mteril nd to recover spent
ctlyst.

B.11.2 Rection Kinetics

The process given in Figure B.11.1 is sed on the liquid-phse ctlytic codimeriztion of C3 nd C4
olefins using n orgnometllic ctlyst. This ctlyst is slurried with smll volume of the hexenes
product nd fed to the rector with the feed strems. The volume of the ctlyst strem is smll compred
with the other strems nd is not included in the mteril lnce given in Tle B.11.1. In 1976 (CEPCI
= 183), consumption of ctlyst mounted to $9.5/1000 kg of 1-heptene product [1].

The primry rections tht tke plce re s follows:

C3H6 + C3H6 C6H12

1-Hexene

C3H6 + C4H8 C7H14

1-Heptene

C4H8 + C4H8 C8H16

1-Octene

C3H6 + 2C4H8 C11H22

1-Undecene

In order to mximize the selectivity of the heptene rection, severl rector configurtions were
considered [1]. The rector configurtion tht mximized the heptene production, in minimum volume,
ws found to e plug flow rector in which the utene feed ws introduced t one end nd the propylene
strem ws injected long the side of the rector. However, due to other considertions such s rector
complexity, it ws finlly decided to use rector with five equl stges in which the concentrtion in
ech stge is mintined pproximtely the sme. Het removl nd mixing in ech stge re
ccomplished y withdrwing strem of mteril nd pumping it through n externl het exchnger nd
ck into the sme stge of the rector. The liquid cscdes downwrd from stge to stge y mens of
liquid downcomers. The inside of the rector cn thus e considered similr to five-plte distilltion
column (without vpor flow). The distriution of the feeds into the different stges is not shown in Figure
B.4, nd the dimensions of the rector re tken directly from Chuvel et l. [1].

B.11.3 Simultion (CHEMCAD) Hints

All the hydrocron components used in the simultion cn e considered to e well ehved, i.e., no
zeotrope formtion. The simultions were crried out using the SRK VLE nd enthlpy pckges using
the CHECAD simultor.

B.11.4 Reference

1. Chuvel, A., P. Leprince, Y. Brthel, C. Rimult, nd J-P Arlie, Manual of Economic

Analysis of Chemical Processes, trns. R. iller nd E. B. iller (ew York: cGrw-