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The Production of Butyl Acetate and Methanol via Reactive and

Extractive Distillation. I. Chemical Equilibrium, Kinetics, and


Mass-Transfer Issues
Laureano J imenez,*
,
Alfonso Garvn, and J ose Costa-Lopez
Department of Chemical Engineering and Metallurgy, University of Barcelona, c/ Mart i Franques 1,
08028 Barcelona, Spain
We studi ed the ki neti c and chemi cal equi l i bri um of the transesteri fi cati on of methyl acetate
wi th n-butanol i n a batch sti rred-tank reactor wi th a pol ymeri c aci d resi n as a catal yst. The
ai m of thi s work was to determi ne whether reacti ve and extracti ve di sti l l ati on i s a promi si ng
al ternati ve for managi ng a byproduct from the pol y(vi nyl al cohol ) process. The experi ments were
performed i n concentrati on and temperature ranges si mi l ar to those predi cted for operati on.
The entrai ner (o-xyl ene) was observed to have no i nfl uence on the ki neti cs. I nternal and external
mass-transfer resi stances were found to be negl i gi bl e under the operati ng condi ti ons consi dered.
The experi mental resul ts were best descri bed (average error of 2%) by a pseudohomogeneous
model wi th a fi rst-order dependency on the reactants. The i nfl uence of the temperature was
model ed wi th the Arrheni us equati on. The forward and reverse ki neti c constants were consi stent
wi th the chemi cal equi l i bri um val ues.
Introduction
The use of uni t operati ons separatel y and consecu-
ti vel y to achi eve cost-effecti ve conversi on requi res hi gh
refl ux rati os and prohi bi ti ve recycl e fl ow rates. Reacti ve
separati on processes such as reacti ve di sti l l ati on, reac-
ti ve absorpti on, and reacti ve crystal l i zati on have at-
tracted growi ng i nterest as promi si ng al ternati ves i n
both i ndustri al appl i cati ons and sci enti fi c research. Thi s
paper focuses on reacti ve di sti l l ati on, a technol ogy that
i s parti cul arl y sui ted for reversi bl e reacti ve systems i n
whi ch chemi cal equi l i bri um l i mi ts the conversi on. Other
advantages are that si de reacti ons can be bypassed, the
l i mi tati ons of azeotropi c mi xtures can be overcome, hot-
spot probl ems can be avoi ded, and the heat of reacti on
can be used for sel ecti ve product removal .
1
These
synergi sti c effects mean that reacti ve di sti l l ati on can
have si gni fi cant economi c advantages over a conven-
ti onal desi gn. Al though reacti ve di sti l l ati on i s not
advantageous i n every case (e.g., reacti on rates must
be si mi l ar to those i n a reactor at pressures sui tabl e
for di sti l l ati on), i t i s commonl y used for etheri fi cati on
and esteri fi cati on reacti ons, al though i t has been frui t-
ful l y appl i ed to al kyl ati on, ni trati on, and ami dati on
processes. Reacti ve di sti l l ati on has been proposed for
methyl acetate (MeAc) hydrol ysi s,
2,3
and i t i s used as a
model for research. A very useful desi gners checkl i st
has been publ i shed by Hoshang and Fai r.
4
I n addi ti on,
a compl ete l i st of references, cl assi fi ed as patents,
thermodynami c properti es, and case studi es can be
found i n the work by Hauan.
5
ProblemStatement
We devel oped a new process to recover MM20, a
byproduct from the pol y(vi nyl al cohol ) i ndustry. On one
hand, a byproduct processi ng pl ant i s more el aborate
and costl y today than ever before, because qual i ty
requi rements are severe. On the other hand, a recovery
system i s a busi ness opportuni ty.
MM20, a mi xture of MeOH and MeAc ri ch i n MeOH
(30 wt % MeAc), i s fi rst converted i nto MM80 (80
wt % MeAc, 0.05 wt % maxi mum water content, and
0.05%maxi mum aci di ty). The objecti ve i s to process the
MM80 by reacti ve di sti l l ati on wi th n-butanol (BuOH)
and obtai n hi gh-puri ty MeOH and butyl acetate (BuAc).
Despi te vol ati l e organi c carbon l egi sl ati on, BuAc con-
sumpti on i s expected to grow i n the near future.
6
The
overal l process can be represented by
The probl em i s that the system si mul taneousl y has a
l ow chemi cal equi l i bri um extent and several azeotropes.
To el i mi nate azeotropes, two techni ques are wi del y
used: pressure swi ng di sti l l ati on, whi ch changes the
system composi ti on and moves the di sti l l ati on bound-
ari es, or entrai ners, whi ch modi fy the rel ati ve vol ati l i ty.
I n our case, the sol vent goal ai ms to break the azeo-
tropes and i mprove contact between the reactants i n the
reacti ve secti on of the reacti ve and extracti ve di sti l l ati on
(RED) uni t.
No ki neti c or chemi cal equi l i bri um data were avai l -
abl e i n the l i terature, and al though they can be esti -
mated from group contri buti on methods,
7,8
experi mental
data are strongl y recommended, parti cul arl y when
product speci fi cati ons are based on maxi mum i mpuri -
ti es.
The l i terature
9,10
shows that heterogeneous catal ysts
such as sul fonated macroporous i on-exchange resi ns
accel erate esteri fi cati on. Resi ns provi de products of
constant qual i ty and mi ni mi ze wastewater and corro-
* To whom correspondence shoul d be addressed. Tel .: +34-
977-559617. Fax: +34-977-559667/21. E-mai l : l ji menez@
etseq.urv.es.

Present address: Department of Chemi cal Engi neeri ng,


ETSEQ, Uni versi ty Rovi ra i Vi rgi l i , Av. del s Pa sos Catal ans
26, 43007 Tarragona, Spai n.
MeAc + BuOH T BuAc + MeOH
6663 I nd. Eng. Chem. Res. 2002, 41, 6663-6669
10.1021/i e0107643 CCC: $22.00 2002 Ameri can Chemi cal Soci ety
Publ i shed on Web 11/16/2002
si on probl ems. The mai n drawbacks are the l ow thermal
stabi l i ty, the need for catal yst contai ners to i mprove
mechani cal properti es, and the possi bi l i ty of di ffusi on
probl ems. Resi ns are al so suscepti bl e to both short-term
poi soni ng and l ong-term deacti vati on.
The fi rst part of thi s paper focuses on chemi cal
equi l i bri um and ki neti c aspects, usi ng a si mi l ar ap-
proach to that of Popken et al .
11
The desi gn of reacti ve
di sti l l ati on i s currentl y based on expensi ve and ti me-
consumi ng sequences of l aboratory and pi l ot-pl ant
experi ments. The second part
12
presents the RED uni t
and the sol vent recovery system desi gn and dynami c
model i ng. Recentl y, Castor et al .
13
and Podrebarac et
al .
14
have used si mi l ar approaches for vari ous appl i ca-
ti ons.
Experimental Work
Chemicals. E. Merck (Darmstadt, Germany) sup-
pl i ed the chemi cal s. MeOH and BuOH were Uvasol
spectroscopy-grade (puri ty > 99.9 wt %), and MeAc and
BuAc were hi gh-puri ty (puri ty > 99.8 wt %). o-Xyl ene
(puri ty > 99.0 wt %) and N,N-di methyl formami de
(puri ty > 99.0 wt %) were di sti l l ed twi ce i n a packed
col umn, and thei r fi nal puri ti es were 99.6 and 99.8 wt
%, respecti vel y. The substances were dri ed wi th Uni on
Carbi de 3 mol ecul ar si eves, provi ded by Fl uka AG
(Buchs, Swi tzerl and). Al l puri ti es were checked by gas
chromatography.
Catalyst. Amberl yst 15,
13
a sul foni c i on-exchange
resi n (exchange capaci ty of 4.81 mol
H
+
kg
-1
), manufac-
tured by Rohm & Haas (Phi l adel phi a, PA), was used
as catal yst. Before the experi ments, the catal yst was
dri ed at 95 C for 24 h to remove the water from the
pores. Under these condi ti ons,
15
the equi l i bri um moi s-
ture i s l ess than 1 wt %, and therefore, no hydrol ysi s
reacti on occurs.
Apparatus. Fi gure 1 shows a schemati c di agram of
the setup. The experi ments were conducted i n a stai n-
l ess steel sti rred-tank reactor (FC-3 model , 300 mL)
manufactured by Pressure Products I ndustri es (Warm-
i ster, PA). The uni t was equi pped wi th a turbi ne motor
and a di gi tal tachometer speed control l er (Dyna/Mag
model MM-016-06). The temperature was measured
wi th PT-100 thermometers (accuracy of (0.1 K) and
control l ed by a PI D wi thi n (0.2 K wi th a potenti ometer.
The pressure i ndi cator was a di gi tal manometer ((0.1
kPa). A fi l ter (45-m) was used to prevent any of the
catal yst from bei ng dragged i nto the external recycl e.
The external pump was a Tuthi l l seri es D model (Al si p,
I L).
Analysis. The anal yses were carri ed out i n a Hewl ett-
Packard (Pal o Al to, CA) 5890 Seri es I I Pl us gas chro-
matograph, equi pped wi th an FI D and el ectroni c pres-
sure control . The capi l l ary col umn was a Supel co 2-4159
col umn wi th a 1-m PTE-5 fi l m (30 m, 0.0032-mm i .d.)
wi th hel i um as the carri er gas.
Procedure. The experi ments were conducted i n a
thermostated batch reactor that was overpressuri zed (10
atm) to mai ntai n al l of the chemi cal s i n the l i qui d phase.
To fi x the starti ng poi nt of the ki neti c experi ments
preci sel y, the fol l owi ng procedure was used. Fi rst, the
reactor (A) was fi l l ed wi th the sol vent, the nonreacti ve
mi xture, and the catal yst. Then, the system was heated
to the temperature set poi nt, and the pressure was fi xed
at around 3-4 atm under the worki ng condi ti ons wi th
ni trogen (B) by C1. When the requi red temperature was
reached, the three-way val ve (D) was swi tched, and the
pressure i ncreased; the ni trogen passed through C2 and
pushed the reactant (E) i nto the reactor. The external
recycl e stream was cool ed wi th a heat exchanger (F)
before i t entered the pump (G) to prevent any fl ashi ng
at the sampl e poi nt (H). The resi dence ti me i n the
external recycl e l oop (l i ne F-G-H) was l ess than 1.5
mi n, and thi s i nfl uence was negl ected compared wi th
the l ong ki neti c and chemi cal equi l i bri um experi ments.
The i ni ti al composi ti on was known from the fi rst
anal ysi s. Sampl es were taken every 5 mi n at the
begi nni ng of the experi ments and every 20-30 mi n
thereafter (8-12 sampl es per test) to moni tor the
progress of the reacti on. The amount of sampl e was
around 1-2 mL. TI C, PI , TI , and SI (I ) control l ed and
moni tored the systems operati ng vari abl es.
Experimental Plan. Vari ous experi ments were car-
ri ed out starti ng from di fferent composi ti ons: (a) al co-
hol , ester, and entrai ner mi xtures, because forward and
backward reacti ons occur si mul taneousl y; (b) mi xtures
wi th MM80 as the feed; and (c) mi xtures wi th di fferent
o-xyl ene concentrati ons, because of the possi bl e i nfl u-
ence of o-xyl ene on catal yst acti vi ty.
The thermal stabi l i ty of the catal yst restri cts the
operati ng temperature to 90-95 C. Prel i mi nary si mu-
l ati on resul ts predi cted that temperatures i n the RED
uni t shoul d be hi gher than 50 C to achi eve measurabl e
reacti on rates.
The ki neti c experi ments l asted for 5-6 h (1.5 wt %
catal yst), whereas the equi l i bri um experi ments l asted
for 9-12 h (6.5 wt % catal yst). Over 40 equi l i bri um
and 25 ki neti c experi mental runs were made to eval uate
the effects of catal yst concentrati on, sti rrer speed,
catal yst si ze, temperature, and chemi cal concentrati on.
Results
Duri ng the experi ments, no l oss of catal yti c acti vi ty
or damage by swel l i ng forces was observed. A set of fi ve
experi ments was performed wi th the same catal yst, and
no di fference i n acti vi ty was observed. Neverthel ess, the
catal yst was di scarded after each experi ment. The mol ar
yi el ds cal cul ated from the anal yti cal resul ts for repl i cate
experi ments al ways agreed to wi thi n a few percent
((3%). Equi l i bri um and ki neti c expressi ons were de-
ri ved separatel y, and thei r coi nci dence was used as a
gl obal consi stency test.
Figure 1. Schemati c di agram. A, batch sti rred-tank reactor; B,
ni trogen cyl i nder; C1 and C2, fl ow paths; D, three-way val ve; E,
contai ner; F, heat exchanger; G, pump; H, sampl e poi nt; I , control
moni tor.
6664 I nd. Eng. Chem. Res., Vol . 41, No. 26, 2002
Estimation of Physical Properties. The acti vi ty
coeffi ci ents were esti mated by NRTL,
16
wi th tempera-
ture-dependent i nteracti on parameters (eqs 1 and 2).
Vapor-phase noni deal i ti es were cal cul ated usi ng Hay-
den and OConnel l s method.
17
Any other parameter
used was retri eved from the Aspen PLUS Database.
18
No VLE data was found i n the l i terature for the key
systems (except MeAc + BuOH), and T-x-y measure-
ments were performed.
19,20
The parameters are shown
i n Tabl es 1 and 2.
where G
ij
, R
ij
,
ij
, a
ij
, and b
ij
are the i nteracti on param-
eters i n the NRTL model . We found experi mental
evi dence of pseudoazeotrope behavi or for the methanol
+ o-xyl ene system at hi gh methanol composi ti on (not
predi cted by UNI FAC). Thi s aspect i s addressed i n more
detai l i n part I I of thi s paper.
12
ResidueCurveMapAnalysis. Resi due curve maps
(RCMs) have been successful l y appl i ed to compl ex
noni deal separati on systems and provi de val uabl e i n-
si ghts and desi gn assi stance for a vari ety of separati on
processes. RCMs are based sol el y on the systems
physi cal properti es: vapor-l i qui d equi l i bri um, l i qui d-
l i qui d equi l i bri um, and sol ubi l i ty data. The number and
type of si ngul ar poi nts i s unknown a pri ori . The tem-
perature al ways i ncreases al ong a resi due curve l i ne,
and the si ngul ar poi nts are ei ther nodes (stabl e or
unstabl e) or saddl es. The rol e of the si ngul ar poi nts can
be assi gned usi ng Doherty and Perki ns rul es,
21
and the
topol ogy for the whol e composi ti on space can be stated.
Thi s makes RCM a promi si ng techni que i n the earl y
phase of devel opment of any project. Aspen SPLI T
22
was
used to compute the RCM.
An accurate anal ysi s of the quaternary nonreacti ve
RCM di agram (Fi gure 2) reveal s that there are two
di sti l l ati on regi ons. The MeOH + MeAc azeotrope acts
as an unstabl e node, and BuAc and BuOH are both
stabl e nodes, whereas MeOH and the BuOH + BuAc
azeotrope are both saddl es. Any of the four feasi bl e
di sti l l ati on sequences detected l ead to the desi red
separati on. These two aspects show that i t i s advi sabl e
to use ei ther a boundary-crossi ng strategy or an en-
trai ner to separate the products.
ExtractiveDistillation. Sol vent sel ecti on i s the key
factor i n RED, as the entrai ner objecti ve i s to break the
azeotropes and the sol vent recovery system has consi d-
erabl e i nfl uence on the process performance.
23
The huge
number of possi bl e sol vents has l ed to some previ ous
sel ecti ons bei ng made on the basi s of heuri sti cs.
2,24
The most commonl y accepted parameter for sol vent
sel ecti on i s sel ecti vi ty.
25
The hi gher the sel ecti vi ty, the
better the sol vent. Di fferent entrai ners are compared
by consi deri ng the si tuati on at i nfi ni te di l uti on, as
stated i n eq 3
Experi mental work usi ng headspace gas chromatogra-
phy was done for al cohol + acetate + entrai ner sys-
tems.
26
The S
m,S

cri teri on i s useful for cl usteri ng the


sol vents i nto di fferent groups, but a defi ni ti ve sel ecti on
cri teri on cannot be stated. The experi mental resul ts
show that the best entrai ners are al kyl benzenes and
al kanes. Al so, the i mportance of peri pheral properti es
(e.g., safety, cost, densi ty), that i s, properti es that are
of i nterest when sel ecti ng a sol vent but that often do
not di rectl y affect the separati on, was di scussed. When
al l of these consi derati ons and parameters had been
wei ghed, o-xyl ene was sel ected as the best al ternati ve.
Fi gure 3 shows the MeOH + MeAc + o-xyl ene pseudo-
bi nary di agram. Thi s di agram was used to compute the
mi ni mum entrai ner concentrati on requi red to break the
bi nary azeotrope. Moreover, an anal ysi s of the space
composi ti on of the fi ve-component system resi due curve
Table 1. Binary Parameters for the NRTL Activity
Coefficient Model
system b12 (K) b21 (K) R12
MeAc + BuOH -3897.4 1567.7 0.30
MeOH + o-xyl ene 447.17 516.01 0.30
BuOH + o-xyl ene 130.32 387.12 0.30
BuAc + o-xyl ene -18.438 63.604 0.30
Table 2. Solvation and Association Parameters for the
Hayden and OConnell Method
MeOH MeAc BuOH BuAc o-xyl ene
MeOH 1.63
MeAc 1.30 0.85
BuOH 1.55 1.30 2.20
BuAc 1.30 0.53 1.30 0.53
o-xyl ene 0.00 0.60 0.00 0.60 0.00
G
ij
) exp(-R
ij

ij
) (1)

ij
) a
ij
+
b
ij
T
(2)
Figure 2. Nonreacti ve RCM for the MeAc + BuOH + BuAc +
MeOH system at 101.3 kPa.
Figure3. I nfl uence of o-xyl ene on the vapor-l i qui d equi l i bri um
of the MeOH + MeAc system 101.3 kPa. x
i
/
) xi/jxj, i, j ) MeOH,
MeAc (jx
i
/
) 1).
S
ij,S

i,S

j,S

(3)
I nd. Eng. Chem. Res., Vol . 41, No. 26, 2002 6665
map reveal s that there i s just one di sti l l ati on regi on,
where o-xyl ene and the MeOH + MeAc azeotrope are
the stabl e and unstabl e nodes, respecti vel y.
Entrainer Influence. Amberl yst 15 was sel ected as
the catal yst because of i ts capaci ty to work i n anhydrous
and nonpol ar condi ti ons. The sul foni c groups gi ve the
resi n a strong affi ni ty for pol ar mol ecul es, whi ch are
preferenti al l y adsorbed, and i nhi bi t the adsorpti on of
o-xyl ene. Moreover, as MM80 i s water-free, the possi bl e
reducti on of the avai l abl e catal yst acti ve si tes i s mi ni -
mi zed. Nei ther the chemi cal equi l i bri um nor the ki neti c
resul ts shows di spersi on dependi ng on the i ni ti al com-
posi ti on.
External and Internal Mass Transfer Effects.
The reactants and products must be transported through-
out the catal yst pores and i nsi de the gel beads where
95%of the aci d si tes are l ocated.
27
Di ffusi on phenomena,
therefore, can have an enormous effect on the resul ts.
The reacti ons are sl i ghtl y endothermi c, and the catal yst
parti cl es can be consi dered to be essenti al l y i sothermal .
The heat of mi xi ng was al so not found to have any
i nfl uence.
Three ful l sets of experi ments were carri ed out wi th
di fferent amounts of catal yst (Fi gure 4), di fferent agi ta-
ti on vel oci ti es (Fi gure 5) and di fferent si eved fracti ons
of the catal yst (Fi gure 6). Al l experi ments were per-
formed at 80 C and 10 bar. Fi gure 5 shows a mi nor
i nfl uence of the sti rri ng speed, but the di screpancy i s
i n the range of the error of thi s techni que. Fi gure 6
shows that, for hi gh o-xyl ene concentrati ons (thus, l ow
conversi on), no di ffusi on probl ems were found. The mai n
concl usi on i s that the external and/or i nternal mass-
transfer di ffusi on exerts no i nfl uence. As a secondary
concl usi on, we can state that the reproduci bi l i ty i s very
hi gh. A qual i tati vel y theoreti cal veri fi cati on of mass-
transfer resi stance was made usi ng the di mensi onl ess
Bi ot number and the Thi el e modul us.
28
The resul ts
provi ded by the Bi ot number confi rm that the transport
across the l i qui d-sol i d i nterface i s over 1 order of
magni tude l arger than the transport i nsi de the pores
of the catal yst. Al so, the l ow Thi el e modul us val ues
(between 0.058 at 60 C and 0.363 at 90 C) had a
correspondi ng effecti veness factor that i s vi rtual l y 1
(>0.95). I n accordance wi th the resul ts from thi s secti on,
i n the subsequent experi mental work, we used unsi eved
catal yst parti cl es and a sti rri ng speed of 1000 rpm.
Side Reactions. The val ues of the equi l i bri um
constants were esti mated usi ng Aspen PLUS (Aspen
Technol ogy I nc., Cambri dge, MA), by mi ni mi zi ng the
Gi bbs free energy. As al l chemi cal s were water-free, the
conversi ons caused by hydrol ysi s were expected to be
i nsi gni fi cant. Gas chromatographi c anal ysi s confi rmed
that the formati on of such byproducts as di methyl ether
by dehydrati on of MeOH or aceti c aci d by hydrol ysi s was
negl i gi bl e (l ess than 0.01 wt %).
Chemical EquilibriumExperiments. For a homo-
geneous system wi th an equi l i bri um reacti on i n the
l i qui d phase, the equi l i bri um constant can be wri tten
as
28
Therefore, the equi l i bri um constant can be expressed
as the product of the acti vi ty coeffi ci ent constant (K

),
the l i qui d mol ar fracti on constant (K
x
), and the fugaci ty
constant (K
f
). Al though the entrai ner has a si gni fi cant
effect on the acti vi ty coeffi ci ents and equi l i bri um tem-
peratures, i ts i nfl uence on the acti vi ty coeffi ci ent con-
stant i s negl i gi bl e (Tabl e 3). As expected, the K
f
vari a-
ti on was i nsi gni fi cant, but i t was sti l l taken i nto
consi derati on i n the cal cul ati ons.
The chemi cal equi l i bri um constant under standard
condi ti ons can be deri ved from the Gi bbs free energy,
yi el di ng the equati on
Equati on 5 i s val i d assumi ng that the heat of reacti on
i s constant over the temperature range (experi ments
Figure 4. I nfl uence of the amount of catal yst on the BuAc rate
of formati on.
Figure 5. Effect of the sti rri ng speed on the BuAc rate of
formati on.
Figure 6. I mpact of the catal yst parti cl e si ze di ameter on the
BuAc rate of formati on.
K
a
)

x
i

[
f
i
f
i
o
]

i
) K

K
x
K
f
(4)
l n K
a
)
S
o
R
-
H
o
R
1
T
(5)
6666 I nd. Eng. Chem. Res., Vol . 41, No. 26, 2002
were performed every 5 C between 50 and 90 C).
Anal yses wi th l i qui d temperature-dependent heat ca-
paci ti es were performed (the parameters were retri eved
from the Aspen PLUS database). Usi ng temperature-
dependent heat capaci ti es or constant heat capaci ti es,
the model predi cti ons fi t the data very wel l (r
2
) 0.9968
and r
2
) 0.9993, respecti vel y), because the heat capaci -
ti es of the reactants and products are al most constant.
H
o
val ues (10 510 ( 141 and 11 570 ( 149 Jmol
-1
,
respecti vel y) and S
o
val ues (29.25 ( 0.49 and 31.22 (
0.51 Jmol
-1
, respecti vel y) were coi nci dent, and the
si mpl er expressi on was preferred. Fi gure 7 shows the
K
a
dependence on temperature. For exampl e, the theo-
reti cal standard heat of reacti on i s 4800 Jmol
-1
,
18
about
the same order of magni tude as the experi mental val ue,
al though the experi mental error associ ated wi th thi s
techni que can have val ues around 1 kJmol
-1
.
Equi l i bri um conversi on starti ng from di fferent feed
rati os was compl eted. An i terati ve method that com-
puted cal cul ati ons wi th Aspen PLUS i n the i nner l oop
(acti vi ty and fugaci ty coeffi ci ents) was used, whi l e
concentrati on cal cul ati ons were performed i n the outer
l oop. The equi l i bri um conversi on for the MeOH + MeAc
azeotrope and stoi chi ometri c BuOH ranged between 31
and 36% over the temperature range studi ed. These
resul ts confi rms that RED can be used to ci rcumvent
the chemi cal equi l i bri um constrai nt.
Kinetic Experiments. We eval uated the effects of
the temperature, the reagent concentrati on, and the
entrai ner on the reacti on rate (Tabl e 4). Fi gure 4 shows
that the reacti on rate i s proporti onal to the amount of
catal yst and that the reacti on rate can be affected by
usi ng thi s amount as the basi s. The SPSS software
package capabi l i ti es
29
were used to carry out the regres-
si ons.
The tool s and regressi on techni ques used (general i zed
reduced gradi ent) were not abl e to si mul taneousl y fi t
al l of the parameters of the Langmui r-Hi nsel wood-
Hougen-Watson (LHHW) equati on, no matter whi ch
adsorpti on mechani sm was sel ected.
28
Di fferent sets of
absorpti on k val ues wi th di fferent orders of magni tude
exhi bi t approxi matel y the same error. Thi s si tuati on can
be parti al l y justi fi ed for coupl i ng effects i n the di fferent
adsorpti on terms.
The pseudohomogeneous model wi th a second-order
expressi on (eq 6) was i n good agreement wi th the
experi mental data. The power-l aw model di d not si g-
ni fi cantl y i mprove the predi cti ve capabi l i ti es, as the
upgrade does not justi fy the need for four addi ti onal
parameters. Some authors
3,4,6,14,27
have al ready drawn
si mi l ar concl usi ons for the hydrol ysi s, esteri fi cati on, and
transesteri fi cati on of al cohol s and acetates. We assumed
an Arrheni us-type temperature dependence for both the
di rect and reverse constants.
Experi mental profi l es were obtai ned (Tabl e 4) for each
experi ment. For the sake of i l l ustrati on, Fi gure 8 shows
the runs at 80 C wi th experi ments i n whi ch both
forward and reverse reacti ons prevai l . At 50 C, because
of the smal l absol ute val ue of the reacti on rate, sl i ght
devi ati ons l ead to hi gh rel ati ve errors, and therefore,
these data sets were not used. Fi gure 9 shows the di rect
Table 3. Activity Coefficient EquilibriumConstant at
Different Temperatures at 10 atm
MeAc BuOH BuAc MeOH o-xyl ene
xeq (mol ) 0.1320 0.1976 0.0461 0.3698 0.2545
eq 1.3156 1.1641 1.2959 1.4387 1.9687
k 1.2174
Teq (K) 338.15
xeq (mol ) 0.1682 0.1428 0.0637 0.2049 0.4204
eq 1.1702 1.5234 1.0424 2.1177 1.3892
k 1.2382
Teq (K) 323.15
xeq (mol ) 0.0896 0.0884 0.0532 0.1096 0.6592
eq 1.2555 2.0367 1.0354 3.1378 1.1224
k 1.2705
Teq (K) 353.15
xeq (mol ) 0.2792 0.1716 0.1368 0.2954 0.1169
eq 1.1891 1.2191 1.2101 1.4614 1.9686
k 1.2198
Teq (K) 363.15
Figure 7. Dependence of the chemi cal equi l i bri um constant on
temperature for the transesteri fi cati on of MeAc wi th BuOH.
Table 4. Experimental Runs for the Kinetic
Experiments
a
set catal yst (g) T (C) i ni ti al mi xture
1
b
0.451 90 reagent-ri ch
2 1.428 90 product-ri ch
3
b
2.048 90 MM80
4 1.349 80 reagent-ri ch
5 2.003 80 product-ri ch
6
b
2.028 80 MM80
7
b
2.323 80 MM80
8
b
0.451 70 reagent-ri ch
9 2.136 70 product-ri ch
10
b
3.542 70 MM80
11
b
0.541 60 reagent-ri ch
12 1.555 60 product-ri ch
13
b
2.026 60 MM80
a
Condi ti ons: 10 bar, 1000 rpm, and commerci al catal yst.
b
Tri pl i cate experi ment.
Figure 8. BuAc concentrati on profi l e at 80 C for the trans-
esteri fi cati on of MeAc wi th BuOH.
r ) kc
MeAc
c
BuOH
- kc
BuAc
c
MeOH
(6)
I nd. Eng. Chem. Res., Vol . 41, No. 26, 2002 6667
and reverse ki neti c fi tti ng for the set of experi ments
conducted at 90 C.
The regressed ki neti c parameters for the pseudohomo-
geneous model (eq 6) and the dependence of thi s
parameter on temperature are shown i n Tabl e 5. These
val ues fol l ow the Arrheni us model , and the resul ts are
provi ded i n Tabl e 6. I t i s noteworthy that, al though the
forward and reverse reacti ons had si mi l ar coeffi ci ents
of determi nati on (over 0.99 i n both cases), the Fi sher
distribution values (F) were significantly different (13 517
and 45 331, respecti vel y). The F val ue i s an i ndi cator
that consi ders the vari ance taken i nto account by the
model and the number of parameters: hi gh F val ues
i ndi cate better model s.
29
Thi s factor and the i nherent
probl em of regressi ng l ogari thmi c val ues l ead to hi gh
rel ati ve errors i n some parameter esti mates (see Tabl e
7). The val ues for the equi l i bri um constant and the
ki neti c parameters are si mi l ar to those found for the
transesteri fi cati on of MeAc wi th ethanol .
30
Conclusions
Reacti on ki neti cs, chemi cal equi l i bri um, and mass-
transfer i ssues have been eval uated for the transesteri -
fi cati on of MeAc wi th BuOH, where the yi el d i s strongl y
l i mi ted by the equi l i bri um conversi on. The advantage
of usi ng an aci d resi n catal yst i s that very few byprod-
ucts are formed. o-Xyl ene was i denti fi ed as a sui tabl e
extracti ve agent, and i t was used as the reacti on sol vent.
The operati ng condi ti ons were such that the control step
was the reacti on at the catal yst surface, and therefore,
the ki neti c expressi on was consi dered to be essenti al l y
representati ve of the i ntri nsi c rate of reacti on and free
of mass-transfer effects. The pseudohomogeneous ki -
neti c model proved to have very good predi cti ve capa-
bi l i ti es (average errors around 2%). Equi l i bri um and
ki neti c resul ts were consi stent (K
a
k/k). The effects
of temperature and composi ti on were studi ed so that
an expressi on coul d be devel oped to model the RED uni t
i n part I I of thi s paper.
12
Acknowledgment
The authors thank DGI CYTand CI RI Tfor provi di ng
the necessary faci l i ti es and A. Destro (UTN, Panama)
and R. Pei s (UTM, Germany) for carryi ng out some of
the experi ments. Some of the authors (L.J. and A.G.)
grateful l y acknowl edge the fi nanci al support from Fun-
daci on Caja de Madri d.
Notation
a
ij
) i nteracti on parameter i n the NRTL model
A
i
) preexponenti al factor, Lmol mi ng
cat
-1
b
ij
) i nteracti on parameter i n the NRTL model , K
-1
c
i
) mol ar concentrati on, mol L
-1
E
a
) acti vati on energy, kJmol
-1
F ) Fi sher di stri buti on val ue (si gni fi cance ) 95%)
f
i
) fugaci ty, Pa
G
ij
) i nteracti on parameter i n the NRTL model
G ) Gi bbs free energy of formati on, Jmol
-1
H ) enthal py, Jmol
-1
K
a
) chemi cal equi l i bri um constant
MM20 ) byproduct from the pol y(vi nyl al cohol ) process
MM80 ) azeotropi c mi xture of MeOH + MeAc from the
pol y(vi nyl al cohol ) process
r ) reacti on rate, mol L
-1
mi n
-1
g
cat
-1
RCM ) resi due curve map
RED ) reacti ve and extracti ve di sti l l ati on
rpm ) revol uti ons per mi nute
S
i
) sel ecti vi ty
S ) entropy, Jmol
-1
K
-1
T ) temperature, K or C
x
i
, y
i
) l i qui d/vapor phase mol ar fracti ons
x
i
/
, y
i
/
) l i qui d/vapor phase pseudobi nary mol ar fracti ons
Greek Symbols
R
ij
) i nteracti on parameter i n the NRTL model

i
) l i qui d-phase acti vi ty coeffi ci ent

ij
) temperature-dependent i nteracti on parameter i n the
NRTL model

i
) stoi chi ometri c coeffi ci ent
Subscripts and Superscripts
i, j ) ith and jth components, respecti vel y
m ) mul ti component
o ) standard state/condi ti ons
S ) i n the presence of sol vent
) i nfi ni te di l uti on
s ) mean val ue
) reverse reacti on
* ) pseudobi nary basi s
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Revised manuscript received August 21, 2002
Accepted September 19, 2002
I E0107643
I nd. Eng. Chem. Res., Vol . 41, No. 26, 2002 6669

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