Beruflich Dokumente
Kultur Dokumente
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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Figure 9. Fi t of forward and reverse ki neti c constants at 90 C
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(C)
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(Lmol
-1
mi n
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gcat
-1
)
k
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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