KI NETI CS, CATALYSI S, AND REACTI ON ENGI NEERI NG

Heterogeneous Models of Tubular Reactors Packed with

Ion-Exchange Resins: Simulation of the MTBE Synthesis
Rosa M. Quinta Ferreira* and Cristina A. Almeida-Costa
Department of Chemical Engineering, University of Coimbra, Largo Marques dePombal,
3000 Coimbra, Portugal
Alrio E. Rodrigues
Department of Chemical Engineering, University of Porto, Rua dos Bragas, 4099 Porto Codex, Portugal
The study of the behavi or of fi xed-bed reactors usi ng i on-exchange resi ns as catal ysts was carri ed
out by maki ng use of a compl ete bi di mensi onal heterogeneous model for the reactor, whi ch
i ncl uded the resi stances i nsi de the i on-exchange resi n parti cl es, consi dered wi th a macroreti cul ar
structure. The acti ve si tes were l ocated i nsi de the gel phase of the resi n, represented by
mi crospheres, and on the macropores wal l s. The overal l effi ci ency of such heterogeneous catal yst
parti cl es was defi ned by the macroeffecti veness and mi croeffecti veness factors accounti ng for
the process behavi or on the macropores and i nsi de the mi crospheres. The synthesi s of methyl
tert-butyl ether, MTBE, a l i qui d-phase reversi bl e exothermi c reacti on between methanol and
i sobutene, was consi dered as a reference case. Thi s system was studi ed i n the temperature
range of 313-338 K, and the effect of the thermodynami c equi l i bri um condi ti ons was exami ned.
The resul ts predi cted by the compl ete heterogeneous model were compared wi th those obtai ned
wi th the si mpl e pseudohomogeneous model , whi ch reveal ed hi gher hot spots. Moreover, a
compari son between bi di mensi onal and uni di mensi onal model s was al so performed. The
orthogonal col l ocati on method was used for the di screti zati on of the di fferenti al equati ons i nsi de
the catal yst parti cl es, whi ch were reduced from three (correspondi ng to the three mass bal ances
for the three compounds, i sobutene, methanol , and MTBE) to onl y one di fferenti al equati on, by
usi ng the concept of the general i zed vari abl e.
Introduction
I on-exchange syntheti c resi ns are produced through
a copol ymeri zati on procedure wi th styrene and di vi nyl -
benzene used as a cross-l i nki ng agent. The acti ve
groups, contai ni ng hydrogen i ons i n the form of sul foni c
aci d groups, are attached to the pol ymeri c matri x
devel oped i n the gel phase by l ong pol ystyrene chai ns
fi xed by bri dges of di vi nyl benzene, l eadi ng to a stabl e
and ri gi d structure al so cal l ed a sol i d aci d. Thi s paper
deal s wi th the anal ysi s of the performance of a reactor
packed wi th such a strongl y aci di c resi n, Amberl yst 15.
The behavi or of the catal yst parti cl es was studi ed by
usi ng a model presented by I hm et al. (1982), whi ch
accounts for the macroreti cul ar structure of the resi n.
The gel phase of the pol ymeri c matri x was assumed to
be represented by mi crospheres of uni form si ze and the
free space between them accounted for the macropores,
Fi gure 1. Therefore, two types of reacti ve si tes were
consi dered: a fracti on, , l ocated on the wal l s of the
macropores and the remai ni ng fracti on, 1 - , l ocated
i nsi de the mi crospheres. We have al ready used thi s
model i n a previ ous work (Qui nta Ferrei ra and Rod-
ri gues, 1993) where the behavi or of such a macroreti cu-
l ar resi n wi th a zero-order reacti on was anal yzed, onl y
at the parti cl e l evel .
I t i s our objecti ve to i l l ustrate the strategy proposed
by Ari s (1975) at the catal yst l evel , for reacti ve systems
wi th Langmui r-Hi nshel wood ki neti cs. Thi s method
poi nts out the use of onl y one mass bal ance i nvol vi ng a
general i zed vari abl e i nstead of the vari ous parti al mass
bal ance equati ons correspondi ng to the di fferent reac-
ti ve compounds usual l y requi red for cal cul ati ng thei r
concentrati on i n each spati al posi ti on of the catal yst.
The i ndi vi dual composi ti on of each speci es wi l l be
rel ated to that general i zed vari abl e through si mpl e
al gebrai c expressi ons. Usi ng thi s methodol ogy i n both
types of acti ve si tes of the macroreti cul ar resi n, i t i s
possi bl e to si gni fi cantl y reduce the number of second-
order ODEs to be sol ved si mul taneousl y. I n fact, one
needs to deal wi th onl y one di fferenti al equati on on the
macropore wal l s and another i nsi de the mi crospheres,
no matter the number of reacti ve compounds present
i n the fl ui d mi xture.
The other i ssue we woul d l i ke to strengthen i n thi s
work i s the effect of the reactor operati on under
thermodynami c equi l i bri um condi ti ons on the behavi or
of such heterogeneous systems runni ng wi th reversi bl e
* To whom correspondence shoul d be addressed. Tel e-
phone: 351-39-28392. Fax: 351-39-27425.
Figure 1. Sketch of a resi n parti cl e.
3827 I nd. Eng. Chem. Res. 1996, 35, 3827
S0888-5885(96)00242-4 CCC: $12.00 1996 Ameri can Chemi cal Soci ety
reacti ons. I n order to ful fi l l these objecti ves, we have
chosen the MTBE synthesi s as a reference case due to
i ts i ndustri al i mportance. Thi s anal ysi s was carri ed out
consi deri ng that the heterogeneous model of the catal yst
parti cl es was i ncl uded i n a fi xed-bed reactor whi ch was
si mul ated through one- and two-di mensi onal heteroge-
neous model s (Qui nta Ferrei ra et al., 1994). The
i mportance of taki ng i nto account the catal yst gradi ents
was establ i shed by compari ng those predi cti ons wi th the
resul ts obtai ned wi th the pseudohomogeneous model ,
where al l the i nternal and external resi stances are
negl ected. The effect of the thermodynami c equi l i bri um
condi ti ons was emphasi zed i n the feed range tempera-
ture of 313-338 K.
The restri cti ve l aws about envi ronmental pol l uti on
requi re the use of unl eaded gasol i nes i n automobi l es.
Among the avai l abl e processes to reduce the l ead
content, the addi ti on of methyl tert-butyl ether (MTBE)
was reveal ed to be one of the most i nteresti ng tech-
ni ques; because of i ts hi gh octane i ndex, onl y a l ower
amount of the dangerous octane enhancer tetraethyl l ead
must be used, wi thout changi ng the performance of the
engi ne. Therefore, hi gher i nterest has been put i n the
producti on of that compound, whi ch i s obtai ned through
the reversi bl e reacti on between methanol and i sobutene
i n the l i qui d phase:
Thi s moderate exothermi c reacti on can be catal yzed by
mi neral aci ds i n the homogeneous phase, whi ch has
been associ ated, however, wi th qui te severe corrosi on
probl ems and di ffi cul ti es i n the separati on of the aci ds.
Thus, a heterogeneous process i s usual l y used i n
i ndustry, the reacti on bei ng performed i n mul ti tubul ar
fi xed-bed reactors where aci di c i on-exchange resi ns are
used as sol i d catal ysts. I sobutene conversi ons hi gher
than 98% are usual l y obtai ned i n i ndustri al pl ants,
where the reacti on temperatures range between 303 and
373 K and the pressure between 7 and 14 atm. A
comprehensi ve revi ew of the studi es concerni ng the
ki neti cs of MTBE synthesi s was presented by Hutchi ngs
et al. (1992).
The experi mental studi es concerni ng the ki neti cs of
the MTBE synthesi s wi th Amberl yst 15 performed by
Gi cquel and Torck (1983) i n the temperature range of
323-368 K reveal ed that the reacti on takes pl ace
between the i sobutene i n the sol uti on and the adsorbed
methanol at the catal yst surface; the MTBE produced
i s then desorbed to the sol uti on. Accordi ng to these
authors and fol l owi ng the mechani sm of Langmui r-
Hi nshel wood, the expressi on for the reacti on rate refer-
Table 1. Operating Conditions and Reaction, Reactor,
and Catalyst Characteristics
operati ng condi ti ons reacti on
P ) 9 atm -H ) 37.3 kJ/mol
u0 ) 4.4 10
-3
m/s EB ) 82 kJ/mol
C
C
4
) 3840 mol /m
3
E* ) 122 kJ/mol
C
MeOH
/C
C
4
) 1.10 E ) -22 kJ/mol
C
i nerts
/C
C
4
) 1.348 KB0 ) 2.74 10
7
m
3
/(K gcat s)
T0 ) 313-338 K KA0R 0 ) 9.99 10
15
mol /(K gcat s)
R 0 ) 7.41 10
-5
reactor catal yst
L ) 7.5 m da ) 8 10
-4
m
Dt ) 0.027 m di ) 3 10
-8
m
Fb ) 760 kg/m
3
p ) 0.36
) 0.4 c ) 1.69
Fc ) 1980 kg/msol
3
) 0.05
CH
3
OH + (CH
3
)
2
CdCH
2
h (CH
3
)
3
CH
3
Table 2. Dimensionless Equations for the
Bidimensional, Heterogeneous Model (HT)
Fl ui d Phase
mass bal ance
Y
k,b
z*
) R
k
j
ov
DaR
b
+
L
2
R
0
2
1
Pe
rm
[

2
Y
k,b
r*
2
+
1
r*
Y
k,b
r*
]
(k )
C
4
, MeOH, MTBE) (1)
thermal bal ance

b
z*
) j
ov
DaBR
b
+
L
2
R
0
2
1
Pe
rh
[

2

b
(r*)
2
+
1
r*

b
r*]
(2)
boundary condi ti ons
z* ) 0; r* g 0: Y
C
4
) 1; Y
MeOH
)
C
MeOH
C
C
4
; Y
MTBE
) 0

b
) 1 (3)
z* g 0; r* ) 0:
Y
k,b
r*
|
r*)0
)

b
r*
|
r*)0
) 0
r* ) 1:
Y
k,b
r*
|
r*)1
) 0 (k ) C
4
, MeOH, MTBE)
-

b
r*
|
r*)1
) Bi

(
b
-

) (4)
Fl ui d/Parti cl e I nterface
thermal bal ance

s
)
b
+ B
N
f,C
4
N
fh
(Y
C
4
,b
- Y
C
4
,s
) (5)
Catal yst Parti cl e
macropores

2
Y
k,a
x
a
2
+
2
x
a
Y
k,a
x
a
) -R
k

k,a
2
R
a
+ 3

k,a
2

k,i
2
Y
k,i
x
i
|
x
a
;x
i
)1
(k )
C
4
, MeOH, MTBE) (6)
boundary condi ti ons
z* g 0, r* g 0: x
a
) 0
Y
k,a
x
a
) 0
x
a
) 1 Y
C
4
,s
) Y
C
4
,b
-
Da
N
f,C
4

ov
R
s
Y
MeOH,s
) Y
MeOH,b
-
K
f,C
4
K
f,MeOH
(Y
C
4
,b
- Y
C
4
,s
)
Y
MTBE,s
) Y
MTBE,b
-
K
f,C
4
K
f,MTBE
(Y
C
4
,b
- Y
C
4
,s
) (7)
mi crospheres

2
Y
k,1
x
i
2
+
2
x
i
Y
k,i
x
i
) -R
k
(1 - )
k,i
2
R
i
(k )
C
4
, MeOH, MTBE) (8)
boundary condi ti ons
z* g 0, r* g 0, x
a
g 0: x
i
) 0
Y
k,i
x
i
) 0 (9)
x
i
) 1 Y
k,i
) Y
k,a
(x
a
)
3828 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996
ri ng to the mass of catal yst (mol /(K g
cat
s)) i s gi ven by
where KB (m
f
3
/(K g
cat
s)) and KA (mol /(K g
cat
s)) are the
forward and backward rate constants. The surface
fracti ons covered by methanol and MTBE are gi ven by
where b
MeOH
and b
MTBE
are the adsorpti on coeffi ci ents
for methanol and MTBE, respecti vel y. The reacti on rate
wi l l then become
wi th the rate constants defi ned by
where EB and EA are the acti vati on energi es of the
synthesi s and the decomposi ti on of MTBE, respecti vel y;
E

)
MTBE
-
MeOH
represents the di fference between
the heats of adsorpti on of MTBE and methanol , and the
thermal i ncrement E* i s gi ven by E* ) EA - E

.
I n the present study, we have used thi s ki neti c model ,
whi ch was al so poi nted out to be the most adequate for
the MTBE synthesi s wi th Amberl yst 15 by the work of
Al i and Bhati a (1990). Caetano et al. (1994) presented
a ki neti c model very si mi l ar to the one of Gi cquel and
Torck (1983) for the producti on of MTBE catal yzed by
Amberl yst 18. More recentl y, rate expressi ons of the
Langmui r-Hi nshel wood type have been reported as a
functi on of UNI FAC l i qui d-phase acti vi ti es i nstead of
concentrati ons (Rehfi nger and Hoffman, 1990a; Parra
et al., 1994), due to the hi gh noni deal i ty of the al cohol -
ether-hydrocarbons mi xture. For processes i n whi ch
i sobutene i s present i n l arge excess, Rehfi nger and
Hoffman (1990b) anal yzed the effect of macropore
di ffusi on of methanol , represented by a pseudobi nary
di ffusi on model , on the acti vi ty and sel ecti vi ty of the
macroporous resi n catal yst and concl uded that the
observed reacti on coul d be si gni fi cantl y affected by the
di ffusi onal resi stances i n the macropores. Berg and
Harri s (1993) poi nt out that for commerci al processes,
where the rati o of methanol to i sobutene i s stoi chi o-
metri c, i t i s necessary to i ncl ude mul ti component di f-
fusi on effects.
The operati ng condi ti ons, reacti on parameters, and
reactor and catal yst characteri sti cs used i n thi s work
are shown i n Tabl e 1.
Model Equations for Steady-State Operation of
Fixed-Bed Reactors with Ion-Exchange Resins
The model equati ons of the system representi ng the
steady-state regi me were used i n the di mensi onl ess
form. The concentrati ons of i sobutene (C
4
), methanol
(MeOH), and methyl tert-butyl ether (MTBE) were
Table 3. Model Parameters for the Heterogeneous Model
(HT)
Arrheni us no.
b )
EB
RT
0
29
* )
E*
RT
0
43

)
E

RT
0
8
Damkhol er no.
Da ) F
b
KB(T
0
)
5.6
di mensi onl ess adi abati c
temp ri se
B )
(-H)C
C
4
T
0
F
f
c
p
f
0.3
no. of fi l m mass-transfer
uni ts
N
f,C
4
)
1 -

K
f,C
4
a
p

2.26 10
5
no. of fi l m heat-transfer
uni ts
N
fh
)
1 -

ha
p

F
f
c
p
f
3.98 10
3
radi al mass Pecl et no.
Pe
rm
)
Lu
0
D
er
85812*
radi al heat Pecl et no.
Pe
rh
)
Lu
0
F
f
c
p
f

er
49122*
wal l heat Bi ot no.
Bi
w
)
h
w
R
0

er
11.2
pore Thi el e modul us

k,a
) R
a

F
c
(1 -
p
)KB(T
0
)
D
k,a
0.5
mi crospheres Thi el e
modul us
k,i
) R
i

F
c
KB(T
0
)
D
k,i
0.1
radi cal Pecl et nos. based
on the parti cl e di am
Pe
rm
(d
p
) )
d
p
u
0
D
er
9.2
Pe
rh
(d
p
) )
d
p
u
0
F
f
c
p
f

er
7.5
Table 4. Generalized Equations for the Catalyst
Particle
Catal yst Parti cl e
macropores

2
U
a
x
a
2
+
2
x
a
U
a
x
a
)
a
2
R
a
(U
a
) + 3

a
2

i
2
R
i
(U
i
) 1)
R
a
(U
a
) 1)
U
i
x
i
|
x
a
,x
i
)1
(10)
boundary condi ti ons
z* g 0, r* g 0: x
a
) 0
U
a
x
a
) 0
x
a
) 1 U
a
) 1 (11)
mi crospheres

2
U
i
x
i
2
+
2
x
i
U
i
x
i
) (1 - )
i
2
R
i
(U
i
) (12)
Boundary condi ti ons
z* g 0, r* g 0, x
a
g 0: x
i
) 0
U
i
x
i
) 0
x
i
) 1 U
i
) 1 (13)
where

a
) R
a

F
c
(1 -
p
)KB(T
0
)
C
a
R
a
(U
a
) 1)

i
) R
i

F
c
KB(T
0
)
C
i
R
i
(U
i
) 1)
R ) KBC
C
4

MeOH
- KA
MTBE
(14)

MeOH
)
b
MeOH
C
MeOH
b
MeOH
C
MeOH
+ b
MTBE
C
MTBE

MTBE
)
b
MTBE
C
MTBE
b
MeOH
C
MeOH
+ b
MTBE
C
MTBE
(15)
R )
KBC
C
4
C
MeOH
- KAR C
MTBE
C
MeOH
+ R C
MTBE
(16)
KB ) KB
0
e
-EB/ (RT)
KA ) KA
0
e
-EA/ (RT)
R )
b
MTBE
b
MeOH
) R
0
e
E

/ (RT)
KAR ) KA
0
R
0
e
-E*/ (RT)
(17)
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3829
normal i zed by the i sobutene concentrati on at the reactor
i nl et, C
C
4
: Y
k
) C
k
/C
C
4
, wi th k ) C
4
, MeOH, MTBE; the
reduced temperatures i nsi de the reactor were referred
to as the feed temperature, T
0
: ) T/T
0
. We have al so
used di mensi onl ess rate equati ons, R, by di vi di ng the
actual val ues, R, by the rate val ues cal cul ated at the
condi ti ons of the reactor entrance, R
0
(R ) R/R
0
,
where, R
0
) KB(T
0
)C
C
4
). Usi ng the normal i zed vari -
abl es for the concentrati ons and temperatures, the rate
equati on defi ned by eq 16 wi l l then become
I n order to refer to the val ues of the reacti on rates,
concentrati ons, and temperatures occurri ng i n the di f-
ferent phases of the system, we have used di fferent
subscri pts: b for the bul k phase, s for the resi n surface,
a for the macropores, and i for the mi crospheres.
The di mensi onl ess equati ons for the bi di mensi onal
heterogeneous model (HT) whi ch accounted for the
macroreti cul ar structure of the sol i d parti cl es are wri t-
ten i n Tabl e 2. For the fl ui d phase, eq 1 represents the
three mass bal ances for the three compounds: i sobutene,
k ) C
4
and R
k
) -1; methanol , k ) MeOH and R
k
)
-1; and methyl tert-butyl ether, k ) MTBE and R
k
) 1.
The thermal bal ance i s represented by eq 2, the bound-
ary condi ti ons of these equati ons bei ng defi ned by eqs
3 and 4.
The catal yst parti cl es were consi dered wi th an i so-
thermal behavi or, and the sol i d temperature,
s
, i n each
radi al and axi al posi ti on of the reactor was cal cul ated
through a thermal bal ance i n the fl ui d-parti cl e i nter-
face, eq 5 i n Tabl e 2. I nsi de the sol i d parti cl es, the
process whi ch takes pl ace on the pore wal l s depends on
the di ffusi onal fl ux and chemi cal reacti on occurri ng
there and al so on the di ffusi onal fl ux goi ng on i nsi de
the mi crospheres, eqs 6 and 7. The mass bal ances for
the mi crospheres consi der thei r i nternal di ffusi onal
fl uxes and chemi cal reacti on, eqs 8 and 9. The reacti on
rates at the resi n surface, R
s
, at the pore wal l s, R
a
,
and i nsi de the mi crospheres, R
i
, were cal cul ated
through eq 18 by usi ng the respecti ve normal i zed
concentrati ons Y
k,s
, Y
k,a
, and Y
k,i
for each of the three
compounds (k ) C
4
, MeOH, MTBE) and consi deri ng the
normal i zed sol i d temperature (
s
) i n al l the cases. The
model parameters cal cul ated at 329 K are shown i n
Tabl e 3.
For the macropores and for the mi crospheres, the
three second-order di fferenti al equati ons, correspondi ng
to the three mass bal ances of the three compounds, can
be reduced to onl y one, by taki ng i nto account an
adequate vari abl e change (Ari s, 1975). A general i zed
concentrati on i n the pores, U
a
, and i nsi de the mi cro-
spheres, U
i
, can now repl ace the di mensi onl ess concen-
trati ons, Y
k,a
and Y
k,i
, through the fol l owi ng equati ons:
Substi tuti ng these expressi ons i n eq 18, the di mensi on-
l ess reacti on rates for the catal yst parti cl es were al so
defi ned i n terms of the general i zed concentrati ons, U
a
and U
i
, as fol l ows:
Moreover, normal i zed reacti on rates for the macropores,
R
a
, and for the mi crospheres, R
i
, were used whi ch
were obtai ned by di vi di ng the actual val ues, R
a
and
R
i
, by the rates whi ch woul d take pl ace at the condi -
ti ons of the resi n surface (Y
k,a
) Y
k,s
) for the reacti on
on the macropores and at the condi ti ons of the mi cro-
spheres surface (Y
k,i
) Y
k,a
) for the reacti on rates i nsi de
the mi crospheres. I n these condi ti ons, U
a
and U
i
are
equal to one (eq 19), and therefore,
Substi tuti ng eq 20 i n these expressi ons, one fi nal l y gets
The vari abl es i nvol ved i n the above expressi ons are
defi ned as fol l ows:
E
1
) e
-( b/
s
)-1
E
2
)
KA
0
R
0
K(TB
0
)C
C
4
e
-*/
s
(22)
E
3
) R
0
e

/
s
C
a
)
(
1
D
MeOH,a
-
E
3
D
MTBE,a
)
-1
C
i
)
(
1
D
MeOH,i
-
E
3
D
MTBE,i
)
-1
(23)

a
) Y
MeOH,s
+ E
3
Y
MTBE,s
- 1

i
) Y
MeOH,a
+ E
3
Y
MTBE,a
- 1 (24)

a
) E
1
Y
C
4
,s
Y
MeOH,s
+
E
1
(
-Y
C
4
,s
C
a
D
MeOH,a
- Y
MeOH,s
C
a
D
C
4
,a
+
C
a
2
D
C
4
,a
2
D
MeOH,a
)
+
E
2
(
-Y
MTBE,s
-
C
a
D
MTBE,a
)
R )
e
- b((1/)-1)
Y
C
4
Y
MeOH
-
KA
0
R
0
KB(T
0
)C
C
4
e
(-*/)
Y
MTBE
Y
MeOH
+ R
0
e

/
Y
MTBE
(18)
macropores Y
k,a
) Y
k,s
+
R
k
D
k,a
(1 - U
a
)C
a
mi crospheres Y
k,i
) Y
k,a
+
R
k
D
k,i
(1 - U
i
)C
i
(19)
macropores R
a
(U
a
) )

a
+
a
U
a
+
a
U
a
2

a
+ U
a
mi crospheres R
i
(U
i
) )

i
+
i
U
i
+
i
U
i
2

i
+ U
i
(20)
R
a
(U
a
) )
R
a
(U
a
)
R
a
(U
a
) 1)
R
i
(U
i
) )
R
i
(U
i
)
R
i
(U
i
) 1)
macropores R
a
(U
a
) )

a
+
a
U
a
+
a
U
a
2

a
+
a
+
a

a
+ 1

a
+ U
a
mi crospheres R
i
(U
i
) )

i
+
i
U
i
+
i
U
i
2

i
+
i
+
i

i
+ 1

i
+ U
i
(21)
3830 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996

i
) E
1
Y
C
4
,a
Y
MeOH,a
+
E
1
(
-Y
C
4
,a
C
i
D
MeOH,i
- Y
MeOH,a
C
a
D
C
4
,i
+
C
i
2
D
C
4
,i
D
MeOH,i
)
+
E
2
(
-Y
MTBE,a
-
C
i
D
MTBE,i
)
(25)

a
) E
1
(
Y
C
4
,s
C
a
D
MeOH,a
+ Y
MeOH,s
C
a
D
C
4
,a
-
2
C
a
2
D
C
4
,a
D
MeOH,a
)
+ E
2
C
a
D
MTBE,a

i
) E
1
(
Y
C
4
,a
C
i
D
MeOH,i
+ Y
MeOH,a
C
i
D
C
4
,i
- 2
C
i
2
D
C
4
,i
D
MeOH,i
)
+
E
2
C
i
D
MTBE,i
(26)

a
) E
1
C
a
2
D
C
4
,a
D
MeOH,a

i
) E
1
C
i
2
D
C
4
,i
D
MeOH,i
(27)
Taki ng i nto account the general i zed vari abl es defi ned
above, the mass bal ances for the macropores and
mi crospheres represented by eqs 6-9 i n Tabl e 2 were
reduced to general i zed expressi ons presented i n Tabl e
4, eqs 10-13. I n thi s way, the three i ntraparti cl e mass
bal ance equati ons for the three compounds were re-
placed by only one generalized balance for the macropores
and one for the mi crospheres.
EffectivenessFactors. The overal l effi ci ency of the
sol i d resi ns has to account for the effecti veness factors
associated with the microspheres, j
i
, and the macropores,

a
, as defi ned by I hm et al. (1982) and al so used i n our
previ ous paper (Qui nta Ferrei ra and Rodri gues, 1993).
For the mi crospheres, j
i
represents the average of the
i ndi vi dual effecti veness factors,
i
, al so cal l ed mi croef-
fecti veness factors, whi ch are gi ven by
or
I ntroduci ng the di mensi onl ess vari abl es, one gets
Thus, the average mi croeffecti veness factor, j
i
, wi l l be
or
Repl aci ng eq 28, i t wi l l become Usi ng the di mensi onl ess
vari abl es, one gets
For the process taki ng pl ace i n the macropores (reacti on
and mass transfer), the macroeffecti veness factor,
a
,
i s defi ned as
Then,
or

i
) observed reacti on rate i n the
mi crosphere/i ntri nsi c reacti on rate i n
the mi crosphere at the surface condi ti ons

i
)

V
i
R
i
dV
i
R
a
V
i
(28)

i
) 3

0
1
R
i
(U
i
)x
i
2
dx
i
(29)
j
i
) observed reacti on rate i n al l the
mi crospheres/i ntri nsi c reacti on rate i n
al l the mi crospheres at thei r surface condi ti ons
Figure2. HTmodel . Radi al mean temperatures (a) and i sobutene
concentrati on profi l es (b) i n the bul k phase for di fferent reactor
feed temperatures.
j
i
)

V
a
[

V
i
R
i
dV
i
] dV
a

V
a
R
a
V
i
dV
a
(30)
j
i
)

V
a

i
R
a
dV
a

V
a
R
a
dV
a
(31)
j
i
)

0
1

i
R
a
(U
a
)x
a
2
dx
a

0
1
R
a
(U
a
)x
a
2
dx
a
(32)

a
) (observed reacti on rate i n the pores +
observed reacti on rate i n the mi crospheres)/
(i ntri nsi c reacti on rate i n the pores at
concentrati on C
s
+ reacti on rate i n al l the
mi crospheres i f thei r surface concentrati on was C
s
)

a
)

V
a
R
a
dV
a
+ (1 - )j
i

V
a
R
a
dV
a
R
s
V
a
+ (1 - )j
i
R
s
V
a
(33)
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3831
Figure 3. HT model . I sobutene conversi on i n the bul k phase at the operati ng condi ti ons, X, and i sobutene conversi on at equi l i bri um
condi ti ons, Xeq, al ong the reactor axi s for four i nl et temperatures: (a) T0 ) 313 K; (b) T0 ) 323 K; (c) T0 ) 329 K; (d) T0 ) 338 K.
Figure 4. HT model . Reactor rates i n the bul k phase al ong the reactor axi s: gl obal reacti on rate, Rb, di rect reacti on rate, RB, and
i nverse reacti on rate, RA, for four i nl et temperatures: (a) T0 ) 313 K; (b) T0 ) 323 K; (c) T0 ) 329 K; (d) T0 ) 338 K.
3832 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996
The use of the general i zed vari abl es, U
a
, al l ows us to
wri te
a
i n the fol l owi ng form: The overal l effecti veness
factor,
ov
, i s defi ned as
or
Compari ng thi s expressi on wi th eq 34, one can see that

ov
can al so be cal cul ated after knowi ng
a
and j
i
through the fol l owi ng expressi on:
Thi s overal l effecti veness factor referri ng to the condi -
ti ons at the surface parti cl es,
ov
, i s rel ated to the overal l
effecti veness factor referri ng to the bul k condi ti ons, j
ov
,
by the reacti on rates cal cul ated wi th the concentrati ons
and temperatures occurri ng i n the fl ui d phase, R
b
, and
at the surface of the resi n, R
s
:
Figure5. HT model . Radi al mean val ues of the three effecti ve-
ness factors: (a) overal l effecti veness factor, ov; (b) macroeffec-
ti veness factor, a; (c) average mi croeffecti veness factor, ji .
Figure 6. HT model . Radi al profi l es of (a) temperatures, (b)
i sobutene concentrati on, and (c) i sobutene concentrati on at l ocal
and equi l i bri um condi ti ons, i n the hot spots of the bul k phase for
four di fferent reactor feed temperatures: T0 ) 313 K (z* ) 0.17);
T0 ) 323 K (z* ) 0.14); T0 ) 329 K (z* ) 0.08); T0 ) 338 K (z* )
0.04).

a
)
1
R
s
V
a

V
a
R
a
dV
a
(34)

a
) 3

0
1
R
a
(U
a
)x
a
2
dx
a
(35)

ov
) (observed reacti on rate i n the pores +
observed reacti on rate i n the mi crospheres)/
i ntri nsi c reacti on rate i n al l the resi n parti cl e
(pores + mi crospheres) i f the concentrati on
was the one at the surface

ov
)

V
a
R
a
dV
a
+ (1 - )j
i

V
a
R
a
dV
a
R
s
V
a
(36)

ov
)
+ (1 - )j
i
R
s
V
a

V
a
R
a
dV
a
(37)

ov
)
a
[ + (1 - )j
i
] (38)
j
ov
)
R
s
R
b

ov
(39)
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3833
The catal yst model defi ned here to descri be the behavi or
of the resi n parti cl es wi th heterogeneous structure (0
< <1) can al so be used i n the case of uni forml y porous
catal ysts, by consi deri ng ) 1, whi ch wi l l l ead to the
known rel ati on
ov
)
a
. That model can sti l l be
extended to bi di sperse porous catal ysts by maki ng )
0, whi ch means
ov
)
a
j
i
. I n the fi rst case, the chemi cal
reacti on takes pl ace onl y on the pore wal l s where the
acti ve si tes are concentrated, and i n the second case,
al l the catal yti c si tes are l ocated i nsi de the mi cro-
spheres.
When i nternal and external sol i d resi stances are
negl ected, i .e., when the catal yst effi ci ency i s assumed
to be equal to one, one gets the pseudohomogeneous
model (PH model ), whi ch i s onl y descri bed by the mass
and thermal bal ances to the fl ui d phase. For thi s model ,
eqs 1-4 from Tabl e 2 can be used by putti ng j
ov
) 1.
The numeri cal sol uti on of the system of the parti al
di fferenti al equati ons of those bi di mensi onal model s was
achi eved through the method of l i nes. The mass and
thermal bal ances for the fl ui d phase, eqs 1-4 (Tabl e
2), were sol ved by usi ng the package PDECOL (Madsen
and Si ncovec, 1975), whi ch di screti zed automati cal l y the
vari abl es on the reactor radi al posi ti on, r*, through the
orthogonal col l ocati on method on fi ni te el ements usi ng
cubi c B-Spl i nes as tri al functi ons. We have used onl y
one fi ni te el ement, wi th two i nteri or col l ocati on poi nts,
si nce the use of two subi nterval s di d not l ead to
si gni fi cati ve changes on the si mul ated profi l es, requi r-
i ng, however, hi gher computi ng ti mes. The resul ti ng
ODEs were sol ved by the i mpl i ci t i ntegrator GEARI B
(Hi ndmarsh, 1976) i ncl uded i n PDECOL. For the
uni di mensi onal model s, the i ni ti al val ue probl em as-
soci ated wi th the ordi nary di fferenti al equati ons of the
bul k phase was sol ved by usi ng the GEAR code (Hi nd-
marsh, 1974). For the heterogeneous model s, the i n-
traparti cl e cal cul ati ons were performed, i n each radi al
and/or axi al posi ti on of the reactor, by usi ng the
general i zed equati ons for the macropores, eqs 10 and
11, and for the mi crospheres, eqs 12 and 13, Tabl e 4
(i nstead of the di mensi onl ess equati ons 6-9, Tabl e 2).
Thei r numeri cal sol uti on was carri ed out by usi ng the
orthogonal col l ocati on method descri bed i n Appendi x A.
The effecti veness factors of the resi n parti cl es were
cal cul ated through numeri cal quadrature fol l owi ng the
methodol ogy al so referred to i n Appendi x A.
Computer Results
For vari ous feed temperatures, Fi gure 2 shows the
radi al mean val ues of the bul k temperature i n a and
i sobutene concentrati on i n b al ong the reactor when the
compl ete bi di mensi onal heterogeneous model was used.
I ncreasi ng T
0
, the hot-spot magni tude al so i ncreases
and i ts l ocati on approaches the reactor entrance. These
resul ts al so show that the opti mal operati ng i nl et
temperature, for whi ch a maxi mum outl et i sobutene
conversi on i s obtai ned, i s approxi matel y T
0
) 329 K.
Compari ng the radi al mean val ues of the i sobutene
conversi on obtai ned al ong the reactor bed, X, wi th those
whi ch woul d be achi eved i f the chemi cal reacti on was
at equi l i bri um i n each reactor posi ti on, X
eq
, Fi gure 3
shows that the i ncrease of the feed temperature al l ows
the reactor operati on to be performed cl oser to those
equi l i bri um condi ti ons. Whi l e for T
0
) 329 K (Fi gure
3c) the equi l i bri um condi ti ons are reached just at the
reactor exi t, for hi gher feed temperatures, as for T
0
)
388 K (Fi gure 3d), those condi ti ons are achi eved some-
where i nsi de the reactor; after that poi nt, the i sobutene
conversi on was l i mi ted by the equi l i bri um val ue cal cu-
l ated at the same temperature. Si nce, for exothermi c
processes, the equi l i bri um conversi on decreases wi th
temperature, the operati ng temperatures above 329 K
wi l l l ead to a decrease of the fi nal reactant conversi on.
Thi s thermodynami c effect can al so be observed i n
Fi gure 4, where the gl obal reacti on rates (mean radi al
val ues) cal cul ated at the bul k condi ti ons, R
b
, are
compared wi th the val ues of the di rect, RB, and i nverse,
RA, reacti on rates (R
b
) RB - RA). The overal l reacti on
rate, R
b
, tends to zero for the hi gher operati ng temper-
atures when the equi l i bri um condi ti ons are approached,
as shown i n Fi gure 4d for T
0
) 338 K.
The effi ci ency of the catal yst can be observed i n
Fi gure 5, where the mean radi al val ues of the three
effecti veness factors associ ated wi th the macroreti cul ar
resi ns (
ov
,
a
, and j
i
) are represented al ong the catal yti c
bed. The gl obal effi ci ency of the catal yst i s mai nl y due
to the process occurri ng on the macropores, si nce the
effi ci ency i n the mi crospheres, j
i
, i s uni ty, as shown i n
Fi gure 5c. Therefore,
ov
fol l ows
a
very cl osel y, as
depi cted i n Fi gure 5a and b.
For the i nl et temperatures anal yzed before (T
0
) 313,
323, 329, and 338 K), Fi gure 6 presents, i n a, the
thermal radi al profi l es observed i n the hot spots and,
i n b, the correspondi ng mass radi al profi l es for the
i sobutene. One can see that for hi gh temperatures, the
thermal radi al gradi ents can be i mportant (40 K for
T
0
) 338 K). The mass radi al gradi ents for the hi ghest
temperature (curve D) are l ess pronounced than the
ones for l ower temperatures (curves B and C), due to
thermodynami c equi l i bri um effects. Compari ng i n sepa-
rate pl ots (Fi gure 6c) these radi al i sobutene concentra-
ti on profi l es, Y
C4,b
, to the correspondi ng profi l es i f
Figure7. HTmodel . Concentrati on profi l es for i sobutene i nsi de
the mi crospheres l ocated at the parti cl e surface (xa ) 1) i n the
hot spot, (a) at the reactor center, r* ) 0; and (b) at the reactor
wal l , r* ) 1, for four i nl et temperatures: T0 ) 313 K (z* ) 0.17);
T0 ) 323 K (z* ) 0.14); T0 ) 329 K (z* ) 0.08); T0 ) 338 K (z* )
0.04).
3834 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996
equi l i bri um condi ti ons were reached, Y
eq
, i t can be
observed that such condi ti ons are approached when the
feed temperatures i ncrease. The reverse reacti on i s
then favored, l eadi ng to hi gher i sobutene concentra-
ti ons, whi ch happens predomi nantl y at the reactor
center, where the l ocal temperatures are hi gher. Thi s
i s the case reported for T
0
) 338 K (curve D i n Fi gure
6b), where the i sobutene concentrati on i n the center
regi on of the reactor i s hi gher than the one observed
for T
0
) 329 K (curve C).
Our resul ts poi nt that mass and heat external resi s-
tances are not very si gni fi cant i n the reacti on system;
therefore, the catal yst temperature i s very cl ose to the
one of the bul k phase (i sothermal behavi or for the resi n
was consi dered). Al so the mass gradi ents i n the fi l m
are not very i mportant. The i sobutene concentrati on
i nsi de the mi crospheres (Y
C4,i
) and on the pore wal l s
(Y
C4,a
) of the resi n parti cl es l ocated at the hot spot can
be observed i n Fi gures 7 and 8, respecti vel y, for two
reactor radi al posi ti ons: (a) r* )0 and (b) r* )1. I nsi de
the mi crospheres, the mass gradi ents are al most absent
i n al l cases as observed before, through the uni t val ues
of
i
(Fi gure 5c), al so reported by I hm et al. (1988).
I n what concer ns the pr ocess occur r i ng on the
macropore wal l s, these resul ts show that the mass
gradi ents on the macropores can be l ower at the reactor
center (r* ) 0) than at the reactor wal l (r* ) 1), as
depi cted i n Fi gure 8a and b. The concentrati on profi l e
i s practi cal l y fl at i n the reactor center, i n parti cul ar for
T
0
) 338 K (curve D i n Fi gure 8a), where equi l i bri um
condi ti ons were cl osel y approached. Thi s i s shown i n
Fi gure 8c, where the actual profi l es for the same T
0
are
compared to the correspondi ng equi l i bri um concentra-
ti ons i n both radi al l ocati ons (r* ) 0 and r* ) 1). At
the reactor wal l , where the l ocal sol i d temperature (347
K) i s l ower than at the reactor center (387 K), the
system i s far from equi l i bri um, so the mass gradi ents
are hi gher. I n spi te of that, the catal yst effi ci ency at
the center (
ov
) 0.39) i s l ower than at the wal l (
ov
)
0.92). I n order to cl ari fy these resul ts, we represented
i n Fi gure 8d the profi l es of the overal l reacti on rate (R
a
)
on the macropore wal l s of the resi n parti cl es l ocated at
r* ) 0 and r* ) 1. I t can be observed that for r* ) 0,
the equi l i bri um i s reached toward the center of the
catal yst parti cl e (Fi gure 8c), so the reacti on rate wi l l
approach zero i n the i nner posi ti ons of the macropore
wal l s (Fi gure 8d). However, i t has a comparati vel y hi gh
val ue at the surface, whi ch resul ts from the effect of
the hi gh resi n temperature (387 K) on the rate constants
and the sl i ght devi ati on of concentrati on from equi l i b-
ri um condi ti ons. I n fact, when the reacti on rates are
cal cul ated, those di fferences are augmented due to the
hi gh val ues of the ki neti c constants. The steep gradi ent
of the overal l reacti on rate so obtai ned expl ai ns the l ow
val ue of
ov
, si nce thi s parameter i s defi ned as the rati o
between the average reacti on rate i nsi de the catal yst
and i ts surface val ue. For r* ) 1, the overal l reacti on
rate profi l e i nsi de the catal yst parti cl e i s more uni form
Figure 8. HT model . Concentrati on profi l es for i sobutene on the pore wal l s of the resi n parti cl es l ocated at the hotspot, (a) at the
reactor center, r* ) 0; and (b) at the reactor wal l , r* ) 1, for four i nl et temperatures: T0 ) 313 K (z* ) 0.17); T0 ) 323 K (z* ) 0.14); T0
) 329 K (z* ) 0.08); T0 ) 338 K (z* ) 0.04). (c) I sobutene concentrati on and correspondi ng equi l i bri um val ues for T0 ) 338 K; (d) gl obal
reacti on rates for T0 ) 338 K.
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3835
(Fi gure 8d), i n spi te of the l ess uni form concentrati on
profi l e (whi ch i s sti l l very far from equi l i bri um, Fi gure
8c), l eadi ng then to a hi gher effi ci ency.
The radi al average val ue of
ov
at thi s parti cul ar
poi nt, where the hot spot occurs, i s 0.63, as shown i n
Fi gure 5a for T
0
) 338 K. Thi s corresponds to the
mi ni mum val ue of the catal yst effi ci ency al ong the
reactor, si nce, i n thi s regi on of hi gher temperatures, the
gradi ents of the reacti on rate on the macropores are
more pronounced. The same expl anati on stands for the
si tuati ons where the process runs near equi l i bri um
condi ti ons (curves C and D i n Fi gure 5a). I n the cases
where equi l i bri um i s far from bei ng reached (curves A
and B), the effecti veness factors are determi ned by the
competi ti on between reacti on rate and di ffusi onal re-
si stances i nsi de the resi n parti cl es. I n the hot-spot
regi on, the hi ghest temperature of the catal yti c bed i s
attai ned. Therefore, the reacti on rate suffers the maxi -
mum i ncrease i n rel ati on to the rate of di ffusi onal
transport, whi ch i mposes the most pronounced concen-
trati on gradi ents. Consequentl y, the hi ghest overal l
rate profi l es are obtai ned at thi s poi nt, l eadi ng then to
the mi ni mum effi ci enci es.
The compari son of the resul ts predi cted by the
heterogeneous and pseudohomogeneous model s i s shown
i n Fi gure 9. For l ow feed temperatures, T
0
) 313 K,
the temperature ri se i n the catal yti c bed i s not si gni fi -
cant and the catal yst effi ci ency i s near one (Fi gure 5a),
the sol i d gradi ents than bei ng negl i gi bl e; therefore, the
system performance can be adequatel y represented by
the si mpl e PH model as shown i n Fi gure 9a. I ncreasi ng
the feed temperature to T
0
) 323 K, there i s an i ncrease
of the concentrati on gradi ents i nsi de the sol i d parti cl es.
Thus, the effi ci ency of the resi n parti cl es wi l l decrease
(Fi gure 5b) and the predi cti ons of the compl ete hetero-
geneous model wi l l be di fferent from the ones obtai ned
when those i nternal gradi ents are not accounted for, as
depi cted i n Fi gure 9b. These two cases refer to non-
equi l i bri um si tuati ons, as previ ousl y seen. I f total
equi l i bri um coul d be achi eved al l over the reactor, the
concentrati on profi l es i nsi de the resi n woul d certai nl y
be fl at (the equi l i bri um concentrati on i s onl y tempera-
ture dependent and the parti cl es are taken as i sother-
mal ). I n thi s l i mi ti ng case, the pseudohomogeneous
model woul d total l y match the heterogeneous model
predi cti ons (effi ci enci es woul d be uni ty). As anal yzed
before, i ncreasi ng the feed temperature above T
0
) 329
K, the process runs cl oser to thi s l i mi ti ng case; i .e., we
woul d expect a better representati on of the system
behavior through the simpler pseudohomogeneous model.
I ndeed, thi s i s what happens i n most of the catal yti c
bed (Fi gure 9c and d). However, i n the hot-spot zone,
the predi cti ons of both model s sti l l present some di ffer-
ences, whi ch i s due to the l ow effi ci enci es observed i n
thi s regi on, as expl ai ned above.
Representi ng the fi nal i sobutene conversi on, at the
reactor exi t, when predi cted by the heterogeneous
model , X
HT
, and by the pseudohomogeneous model , X
PH
,
for di fferent i nl et temperatures, Fi gure 10 shows once
more that after 329 K, the fi nal reactant conversi on
approaches assymptoti cal l y the equi l i bri um conversi on,
X
eq
. I n these condi ti ons, the pseudohomogeneous model
can predi ct qui te wel l the fi nal i sobutene conversi on at
the reactor exi t. However, and as can be seen i n Fi gure
9, the maxi mum temperatures i nsi de the reactor cal -
cul ated by thi s model are hi gher than for the hetero-
Figure9. Radi al mean temperature profi l es i n the bul k phase for the heterogeneous model , HT, and pseudohomogeneous model , PH, for
four i nl et temperatures: (a) T0 ) 313 K; (b) T0 ) 323 K; (c) T0 ) 329 K; (d) T0 ) 338 K.
3836 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996
geneous model . Thus, a detai l ed anal ysi s of the system
wi l l requi re the more real i sti c heterogeneous model .
Fi nal l y, we present i n Fi gure 11 a compari son between
the resul ts obtai ned wi th the heterogeneous model when
the radi al gradi ents are taken i nto account, HT
2D
, and
when they are negl ected, HT
1D
. The predi cti ons ob-
served i n both cases refl ect that the temperatures
obtai ned wi th the uni di mensi onal model are not very
far from the radi al average temperature predi cted by
the bi di mensi onal model . However, the use of the fi rst
si mpl er model wi l l not al l ow the knowl edge of the
temperature profi l es al ong the radi al coordi nate. I n
some cases, these gradi ents can be si gni fi cant, l eadi ng
to qui te hi gher temperatures i n the center of the reactor,
as we have observed before, i n Fi gure 6a. Thi s can be
i mpor tant when the ther mal stabi l i ty of the i on-
exchange resi ns has to be accounted for.
Conclusions
An anal ysi s of the behavi or of a catal yti c tubul ar
reactor packed wi th i on-exchange resi ns for a reversi bl e
process was performed by usi ng a mathemati cal model
accounti ng for the gradi ents i nsi de the sol i d. The
macroreti cul ar catal yst parti cl es were envi saged as an
aggl omerati on of mi crospheres, representi ng the gel
phase of the resi ns, whi ch formed between them the so-
cal l ed macropores. The acti ve si tes were l ocated i nsi de
of these mi crospheres and al so at thei r surface, i .e., on
the macropores wal l s. An i sothermal behavi or for the
sol i d parti cl es was assumed. However, separate con-
centrati on gradi ents were establ i shed on the macropores
and i nsi de the mi crospheres, l eadi ng al so to di fferent
effecti veness factors, the macroeffecti veness factors, and
mi croeffecti veness factors, further used on the deter-
mi nati on of the overal l effecti veness factor of these
catal ysts wi th heterogeneous structure. The synthesi s
of MTBE was used as a reference process i n thi s paper
to i l l ustrate the behavi or of such reversi bl e systems
catal yzed by macroreti cul ar i on-exchange resi ns. The
use of general i zed vari abl es for the mass bal ances on
the macropores wal l s and i nsi de the mi crospheres of the
catal yst parti cl es al l owed, i n each case, the reducti on
of the three di fferenti al equati ons of the three com-
pounds, i sobutene, methanol , and MTBE, to onl y one
di fferenti al equati on for the macropores and one for the
mi crospheres. The di screti zati on of these second-order
di fferenti al equati ons was achi eved by maki ng use of
the orthogonal col l ocati on method.
The performance of the system was studi ed i n the feed
temperature range 313-338 K, and our resul ts showed
that the process approaches thermodynami c equi l i bri um
condi ti ons after 329 K. I n these si tuati ons, the concen-
Figure 10. I nfl uence of the i nl et temperature on the fi nel
i sobutene conversi on for the heterogeneous model , XHT, and
pseudohomogeneous model , XPH, and on the i sobutene equi l i bri um
conversi on, Xeq.
Figure 11. Radi al mean temperature profi l es i n the bul k phase for the heterogeneous bi di mensi onal model , HT2D, and for the
heterogeneous uni di mensi onal model , HT1D, for four i nl et temperatures: (a) T0 ) 313 K; (b) T0 ) 323 K; (c) T0 ) 329 K; (d) T0 ) 338 K.
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3837
trati on gradi ents i nsi de the sol i d parti cl es are reduced
and the resul ts predi cted by the heterogeneous model s
become cl oser to those obtai ned wi th the pseudohomo-
geneous model s. However, and even i f the fi nal reactant
conversi on can be wel l cal cul ated through the PH model ,
the maxi mum temperatures i nsi de the reactor wi l l
devi ate from the ones predi cted by the more real i sti c
heterogeneous model . A compari son of the bi di men-
si onal model s and the uni di mensi onal model s was al so
achi eved. Our resul ts showed that the radi al thermal
profi l es can be i mportant, despi te the si mi l ar mean
radi al temperature val ues to those cal cul ated when the
radi al gradi ents are negl ected. Therefore, i t i s our bel i ef
that a more careful study of the process i n order to
i denti fy the l ocal maxi mum temperatures that are
possi bl e to occur i nsi de the system wi l l requi re the use
of the compl ete two-di mensi onal model .
Thi s study poi nts out the effect of thermodynami cs
on the control of the behavi or of heterogeneous revers-
i bl e systems. When the l ocal condi ti ons are far from
equi l i bri um, the process i s control l ed by the competi ti on
between chemi cal reacti on and di ffusi onal transport.
When equi l i bri um i s approached, the thermodynami c
effects are predomi nant over those phenomena.
Nomenclature
a
p
) speci fi c parti cl e area, m
-1
B ) di mensi onl ess adi abati c temperature ri se (B )
(-H)C
C
4
/T
0
F
f
c
pf
)
Bi
w
) wal l heat Bi ot number (Bi
w
) h
w
R
0
/
er
)
b
MeOH
) adsorpti on coeffi ci ents for methanol
b
MTBE
) adsorpti on coeffi ci ents for MTBE
C
k
) concentrati on of compound k, mol /m
3
C
C
4
) i nl et i sobutene concentrati on, mol /m
3
C
MeOH
) i nl et methanol concentrati on, mol /m
3
c
pf
) heat capaci ty of the fl ui d, cal /(kg K)
C
a
, C
i
) parameters defi ned by eq 10
Da ) Damkhol er number (Da ) F
b
KB(T
0
))
D
er
) effecti ve di ffusi vi ty i n the reactor radi al coordi nate,
m
2
/s
D
k
) effecti ve di ffusi vi ty of compound k, m
2
/s
D
t
) reactor di ameter, m
d
a
) di ameter of the resi n parti cl e, m
d
i
) di ameter of the mi crospheres, m
EB, EA ) acti vati on energi es of the forward and backward
reacti ons, cal /mol
E* ) thermal i ncrement (E* ) EA - E

)
E

) di fference between the adsorpti on heats of MTBE and

methanol (E

)
MTBE
-
MeOH
)
E
1
, E
2
, E
3
) parameters defi ned by eq 9
-H ) heat of reacti on, cal /mol
h ) fi l m heat transfer coeffi ci ent, cal /(m
2
s K)
h
w
) wal l heat transfer coeffi ci ent, cal /(m
2
s K)
KB ) forward reacti on ki neti c constant, m
f
3
/(K g
cat
s)
KA ) backward reacti on ki neti c constant, mol /(K g
cat
s)
K
f
) fi l m mass-transfer coeffi ci ent of the compound k, m/s
k
a
, k
i
) parameters defi ned by eq 11
L ) reactor l ength, m
N
f,k
) number of fi l m mass-transfer uni ts for compound k
(N
f,k
) [(1 - )/]K
f
,
k
a
p
)
N
fh
) number of fi l m heat-transfer uni ts (N
fh
) (1 - )-
ha
p
/F
f
c
pf
)
P ) total pressure, atm
Pe
rh
) radi al heat Pecl et number (Pe
rh
) Lu
0
F
f
c
pf
/
er
)
Pe
rh
(d
p
) ) radi al heat Pecl et number based on parti cl e
di ameter (Pe
rh
(d
p
) ) d
p
u
0
F
f
c
pf
/
er
)
Pe
rm
) radi al mass Pecl et number (Pe
rm
) Lu
0
/D
er
)
Pe
rm
(d
p
) ) radi al mass Pecl et number based on the parti cl e
di ameter (Pe
rm
(d
p
) ) d
p
u
0
/D
er
)
R ) i deal gas constant
R
0
) reactor radi us, m
R
a
) radi us of the resi n parti cl e, m
R
i
) radi us of a mi crosphere, m
R ) rati o of the adsorpti on coeffi ci ents of methanol and
MTBE (R ) b
MTBE
/b
MeOH
)
R ) chemi cal reacti on rate, mol /(K g
cat
s)
R
o
) reacti on rate at the reactor entrance, mol /(K g
cat
s)
R ) di mensi onl ess reacti on rate (R ) R/R
o
)
R
a
) normal i zed reacti on rate for the macropores (R
a
)
R
a
(U
a
)/R
a
(U
a
) 1))
R
i
) normal i zed reacti on rate for the mi crospheres (R
i
)
R
i
(U
i
)/R
i
(U
i
) 1))
r ) reactor radi al coordi nate, m
r* ) di mensi onl ess reactor radi al coordi nate (r* ) r/R
0
)
r
a
)spati al posi ti on on the macropores of the resi n parti cl e,
m
r
i
) spati al posi ti on i n the mi crospheres of the resi n
parti cl e, m
T ) absol ute temperature, K
T
0
) feed temperature, K
U
a
, U
i
) general i zed concentrati ons on the macropores and
i n the mi crospheres defi ned by eq 6
U
a
, U
i
) approxi mated general i zed concentrati on of U
a
and
U
i
u
0
) superfi ci al vel oci ty, m/s
X ) i sobutene conversi on
X
eq
) i sobutene conversi on at equi l i bri um condi ti ons
X
HT
) fi nal i sobutene conversi on predi cted by the hetero-
geneous model
X
PH
) fi nal i sobutene conversi on predi cted by the pseudo-
homogeneous model
x
a
) di mensi onl ess spati al posi ti on on the macropores of
the resi n parti cl e (x
a
) r
a
/R
a
)
x
i
) di mensi onl ess spati al posi ti on i n the mi crospheres (x
i
) r
i
/R
i
)
Y
k
) di mensi onl ess concentrati on for compound k (Y
k
)
C
k
/C
C
4
)
z ) reactor axi al coordi nate, m
z* ) di mensi onl ess reactor axi al coordi nate, (z* ) z/L)
Greek Symbols
R
k
) stoi chi ometri c coeffi ci ent of compound k
) fracti on of the acti ve si tes on the macropores wal l s of
the resi n parti cl e
b, *,

) Arrheni us numbers ( b ) EB/RT

0
) (* ) E*/RT
0
)
(

) E

/RT
0
)

a
,
i
) parameters defi ned by eq 12

a
,
i
) parameters defi ned by eq 13

a
,
i
) parameters defi ned by eq 14
) bul k porosi ty

p
) catal yst porosi ty

a
) effecti veness factor of the macropores

i
) effecti veness factor of a mi crosphere
j
i
) average effecti veness factor of the mi crospheres of the
resi n parti cl e

ov
) overal l effecti veness factor of the resi n parti cl e
referri ng to the resi n surface condi ti ons
j
ov
) overal l effecti veness factor of the resi n parti cl e
referri ng to the bul k condi ti ons
) di mensi onl ess temperature ( ) T/T
0
)

er
) radi al effecti ve thermal conducti vi ty, cal /(m s K)

MeOH
) adsorpti on heats of methanol

MTBE
) adsorpti on heats of MTBE
F
b
) bul k densi ty, kg/m
3
F
f
) fl ui d densi ty, kg/m
3
F
c
) catal yst densi ty, kg/m
3

MeOH
) catal yti c surface fracti ons covered by methanol

MTBE
) catal yti c surface fracti ons covered by MTBE
) space ti me for the fl ui d ( ) L/u
0
)

c
) catal yst tortuosi ty

k,a
) Thi el e modul us of compound k for the pores (
k,a
)
R
a
F
c
(1 -
p
)KB(T
0
)/D
k,a
)
3838 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996

k,i
) Thi el e modul us of compound k for the mi crospheres
(
k,i
) R
a
F
c
KB(T
0
)/D
k,i
)

a
) general i zed Thi el e modul us for the macropores (
a
) R
a
F
c
(1 -
p
)KB(T
0
)R
a
(U
a
) 1)/C
a
)

i
) general i zed Thi el e modul us for the mi crospheres (
i
) R
i
F
c
KB(T
0
)R
i
(U
i
) 1)/C
i
)
Subscripts
a ) macropores
b ) bul k condi ti ons
i ) mi crospheres
k ) compound: i sobutene, k ) C
4
; methanol , k ) MeOH;
MTBE, k ) MTBE
s ) resi n surface
w ) reactor wal l
Appendix A
I n the present study, the method of orthogonal
col l ocati on (Fi nl ayson, 1972; Vi l l adsen and Mi chel sen,
1978) was used to sol ve the general i zed di fferenti al
equati ons of the catal yst parti cl e, eqs 10-13, Tabl e 4.
Taki ng i nto account the symmetry of the concentrati on
profi l es, a change of the space coordi nates x
a
and x
i
was
i ntroduced:
Those mass bal ances may now be rewri tten as fol l ows:
For each catal yst parti cl e, the exact profi l e of the
general i zed vari abl e on the pore wal l s, U
a
(h), was
approxi mated by a tri al functi on, U
a
(h), through
where a
j
are unknown coeffi ci ents to be cal cul ated and
l
j
(h) are speci fi ed functi ons whi ch must sati sfy the
boundary condi ti ons.
The gradi ents i nsi de the mi crospheres, U
i
(v), l ocated
on each spati al posi ti on of the macroreti cul ar resi n
(i ncl udi ng the ones l ocated at the surface) were al so
approxi mated by the functi ons U
i
(v):
Sel ecti ng for the tri al functi ons l
j
(h) (j ) 1, 2, ..., N + 1)
and l
j
(v) (j ) 1, 2, ..., M + 1), the Lagrange pol ynomi al s
whi ch sati sfy the rel ati ons
and
the unknown parameters for the macropores and for the
mi crospheres are i denti fi ed wi th the correspondi ng
approxi mated sol uti ons cal cul ated at the same poi nts;
i .e., U
a
(h
j
) ) a
j
(j ) 1, 2, ..., N + 1) and U
i
(v
j
) ) b
j
(j )
1, 2, ..., M + 1). The Lagrange i nterpol l ati on pol ynomi -
al s l
j
(h) and l
j
(v) are defi ned by
where P
N+1
(R,)
(h) ) (h - h
1
)...(h - h
N+1
) and P
M+1
(R,)
(v) ) (v
-v
1
)...(v-v
M+1
) are the nodal pol ynomi al s wi th degrees
N + 1 and M + 1, respecti vel y; P
N+1
(R,)
(h
j
)
(1)
and P
M+1
(R,)
(v
j
)
(1)
are the fi rst deri vati ves of those pol ynomi al s, i n
order of the spati al posi ti ons h and v when cal cul ated
at the posi ti ons h ) h
j
and v ) v
j
, respecti vel y.
The approxi mated sol uti ons (A.5) and (A.6) are then
cal cul ated by
The profi l es on the pore wal l s were obtai ned wi th N
i nteri or col l ocati on poi nts wi th N unknown vari abl es U
a
) h
j
(j ) 1, 2, ..., N) and one boundary poi nt at the resi n
surface where the sol uti on i s known: h
N+1
) 1, U
a
) 1,
eq A.2. I nsi de the mi crospheres, l ocated on each posi -
ti on h
j
of the macropores (i ncl udi ng the resi n surface, j
) 1, 2, ..., N + 1), M i nteri or col l ocati on poi nts were
used al so wi th M unknown vari abl es; as seen before, at
the surface of the mi crospheres, the general i zed vari -
abl es are known: v
M+1
) 1, U
i
(1) ) 1, eq A.4. Thus, i t
i s necessary to cal cul ate N vari abl es for the macropores
and M unknowns for the mi crospheres l ocated on each
one of the N + 1 col l ocati on poi nts of the macropores i n
order to get the sol uti on of the system. Fol l owi ng the
methodol ogy of the orthogonal col l ocati on method, these
unknowns are determi ned by setti ng the resi dual s of
the approxi mated di fferenti al equati ons equal to zero
on each i nteri or col l ocati on poi nt. Substi tuti ng the tri al
U
i
(v) = U
i
(v) )

j)1
M+1
b
j
l
j
(v) (A.6)
l
j
(h
n
) )
{
0 j * n
1 j ) n
(A.7)
l
j
(v
n
) )
{
0 j * n
1 j ) n
(A.8)
l
j
(h) )
P
N+1
(R,)
(h)
(h - h
j
)P
N+1
(R,)
(h
j
)
(1)
(A.9)
l
j
(v) )
P
M+1
(R,)
(v)
(v - v
j
)P
M+1
(R,)
(v
j
)
(1)
(A.10)
U
a
(h) )

j)1
N+1
U
a
(h
j
)l
j
(h) (A.11)
U
i
(v) )

j)1
N+1
U
i
(v
j
)l
j
(v) (A.12)
h ) x
a
2
; v ) x
i
2
macropores
4h

2
U
a
h
2
+ 6
U
a
h
)
a
2
R
a
(U
a
) +
6

a
2

i
2
R
i
(U
i
) 1)
R
a
(U
a
) 1)
U
i
x
i
|
h,v)1
(A.1)
boundary condi ti ons
z* g 0, r* g 0: h ) 0
U
a
h
fi ni te (A.2)
h ) 1 U
a
) 1
mi crospheres
4v

2
U
i
v
2
+ 6
U
i
v
) (1 - )
i
2
R
i
(U
i
) (A.3)
boundary condi ti ons
z* g 0, r* g 0, h g 0: v ) 0
U
i
v
fi ni te (A.4)
v ) 1 U
i
) 1
U
a
(h) = U
a
(h) )

j)1
N+1
a
j
l
j
(h) (A.5)
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3839
functi on (A.11) i nto eqs (A.1) and (A.2), one gets N
di fferenti al equati ons defi ned for the pore wal l s:
For the mi crospheres, l ocated at each of the N + 1
col l ocati on poi nts, the substi tuti on of the tri al functi ons
defi ned by eq A.12 i nto eqs A.3 and A.4 generates M
di fferenti al equati ons wi th nul l resi dual s at the M
col l ocati on poi nts:
The fi rst and second deri vati ves of the tri al functi on on
each col l ocati on poi nt are gi ven by
where
These wei ghts of the approxi mated deri vati ves were
cal cul ated by maki ng use of the subroute DFOPR
(Vi l l adsen and Mi chel sen, 1978).
Substi tuti ng rel ati ons A.15 and A.16 i nto di fferenti al
equati ons (A.13) and (A.14), one gets the col l ocated
equati ons for the macropores and mi crospheres:
mi crospheres (l ocated on the N+1 col l ocati on poi nts of
the macropores)
Thi s system of N + (N + 1)M nonl i near al gebrai c
equati ons (N equati ons on the macropores and (N + 1)-
M i n the mi crospheres) was sol ved by the Newton-
Raphson method. After the cal cul ati on of the approxi -
mated sol uti ons of the general i zed vari abl es on the pore
wal l s and i n the mi crospheres, the concentrati on profi l es
of the di fferent compounds were achi eved through eq
19. The reacti on rates were then cal cul ated by maki ng
use of eq 18.
EffectivenessFactors. The effecti veness factors i n
the mi crospheres,
i
, are gi ven by eq 29:
I ntroduci ng the change of the spati al vari abl e whi ch
takes i nto account the symmetry condi ti on, v ) x
i
2
, one
gets
where (v) ) v

(1 - v)
R
) v
1/2
( )
1
/
2
; R ) 0) i s the
wei ght functi on. Usi ng the M + 1 col l ocati on poi nts i n
the mi crospheres, the Radau quadrature al l ows the
cal cul ati on of the approxi mated val ue of
i
on each
col l ocati on poi nt of the macropores (m ) 1, 2, ..., N +
1):
where
j
are the quadrature wei ghts cal cul ated by the
subrouti ne Radau (Vi l l adsen and Mi chel sen, 1978).
Si nce the boundary poi nt i ni ti al l y fi xed v
M+1
was al so
used, we wi l l have an exact Radau quadrature for a
pol ynomi al wi th a degree e 2M, i f the M quadrature
poi nts are the zeros of a pol ynomi al , whi ch must be
orthogonal wi th respect to the wei ght functi on (v)(1
- v) ) v
1/2
(1 - v) for any pol ynomi al P
j
(v), j e M - 1.
Thus, the concentrati ons of the compounds must be
cal cul ated at those poi nts, so the i nteri or col l ocati on
poi nts used i n the mi crosphere for the orthogonal
col l ocati on method were the zeros of the Jacobi pol yno-
mi al of degree M, P
m
(1,1/2)
(v), sati sfyi ng the orthogonal -
i ty rel ati on
Vi l l adsen and Mi chel sen (1978) devel oped the JCOBI
subrouti ne, whi ch was used to cal cul ate the roots of that
pol ynomi al .
The average mi croeffecti veness factor, j
i
, i s defi ned
through eq 32:
and can be repl aced by
4h

2
U
a
h
2
|
h)h
m
+ 6
U
a
h
|
h)h
m
-
a
2
R
a
(U
a
) -
6

a
2

i
2
R
i
(U
i
) 1)
R
a
(U
a
) 1)
U
i
v
|
h
m
,v
M+1
)1
) 0 (m)
1, 2, ..., N) (A.13)
4v

2
U
i
v
2
|
v
k
+ 6
U
i
v
|
v
k
- (1 - )
i
2
R
i
(U
i
)|
v
k
) 0
(k ) 1, 2, ..., M) (A.14)
dU
a
dh
|
h
m
)

j)1
N+1
A
mj
U
a
(h
j
)
d
2
U
a
dh
2
|
h
m
)

j)1
N+1
B
mj
U
a
(h
j
) (m) 1, 2, ..., N) (A.15)
dU
i
dv
|
v
k
)

j)1
M+1
AI
kj
U
i
(v
j
)
d
2
U
i
dv
2
|
v
k
)

j)1
M+1
BI
kj
U
i
(v
j
) (k ) 1, 2, ..., M) (A.16)
A
mj
)
dl
j
(h)
dh
|
h
m
B
mj
)
d
2
l
j
(h)
dh
2
|
h
m
AI
kj
)
dl
j
(v)
dv
|
v
k
BI
kj
)
d
2
l
j
(v)
dv
2
|
v
k
macropores
4h
m
j)1
N+1
B
mj
U
a
(h
j
) + 6

j)1
N+1
A
mj
U
a
(h
j
) -
a
2
R
a
(U
a
)|
h
m
-
6

a
2

i
2
R
i
(U
i
) 1)
R
a
(U
a
) 1)

j)1
M+1
AI
M+1,j
U
i
(v
j
)|
h
m
) 0 (m)
1, 2, ..., N) (A.17)
4v
k
j)1
M+1
BI
kj
U
i
(v
j
) + 6

j)1
M+1
AI
kj
U
i
(v
j
) -
(1 - )
i
2
R
i
(U
i
)|
v
k
) 0 (k ) 1, 2, ..., M) (A.18)

i
) 3

0
1
R
i
(U
i
)x
i
2
dx
i
(A.19)

i
)
3
2

0
1
v
1/2
R
i
(U
i
) dv (A.20)

i
=
3
2

j)1
M+1

j
R
i
(U
i
)|v
j
(m) 1, 2, ..., N + 1) (A.21)

0
1
v
1/2
(1 - v) P
j
(v) P
M
(1,1/2)
(v) dv ) 0 (j )
1, 2, ..., M - 1) (A.22)
j
i
)

0
1

i
R
a
(U
a
)x
a
2
dx
a

0
1
R
a
(U
a
)x
a
2
dx
a
(A.23)
3840 I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996
after substi tuti ng the resi n radi al coordi nate by h ) x
a
2
.
The Radau quadrature was used agai n for the cal cul a-
ti on of both i ntegral s whi ch i ncl ude the wei ght functi on
(h) ) h

(1 - h)
R
) h
1/2
( ) 1/2; R ) 0):
I n order to sati sfy the preci si on requi rements of the
Radau quadrature when a fi xed node i s used (u
N+1
)
1), the N i nteri or quadrature poi nts must be the roots
of the Nth degree Jacobi pol ynomi al , P
N
(1,1/2)
(h), defi ned
by the orthogonal rel ati on
The same spati al posi ti ons were al so used for the
i nteri or col l ocati on poi nts on the macropores of the sol i d
resi ns. The quadrature wei ghts,
j
, and the zeros of
the pol ynomi al were al so cal cul ated through the sub-
routi nes RADAU and JCOBI , respecti vel y (Vi l l adsen
and Mi chel sen, 1978). The macroeffecti veness factor,

a
, i s gi ven by eq 35
or, i ntroduci ng the vari abl e change h ) x
a
2
,
Usi ng the Radau quadrature for the same reasons as
referred to above, the numeri cal cal cul ati ons of
a
wi l l
be performed by
The quadrature poi nts and the wei ghti ng functi ons
j
are the ones referred to before for the determi nati on of
j
i
.
Literature Cited
Al i , B.; Bhati a, S. Methyl Terti ary Butyl Ether Formati on i n a
Catal yti c Bed ReactorsKi neti c and Model l i ng Study. Chem.
Eng. J . 1990, 44, 97.
Ari s, R. TheMathematical Theoryof Diffusion Theoryof Diffusion
and Reaction in PermeableCatalysts; Cl arendon: Oxford, 1975.
Berg, D. A.; Harri s, T. Characteri zati on of Mul ti component
Di ffusi on Effects i n MTBE Synthesi s. I nd. Eng. Chem. Res.
1993, 32, 2147.
Caetano, N. S.; Lourei ro, J. M.; Rodri gues, A. E. MTBE synthesi s
catal yzed by i on exchange resi ns: ki neti c studi es and model i ng
of mul ti phase batch reactors. Chem. Eng. Sci. 1994, 49, 4589.
Fi nl ayson, B. A. The Method of Weighted Residuals and Varia-
tional Principles; Academi c: New York, 1972.
Gi cquel , A.; Torck, B. Synthesi s of Methyl Terti ary Butyl Ether
Catal yzed by I on-Exchange Resi n. I nfl uence of Methanol
Concentrati on and Temperature. J . Catal. 1983, 83, 9.
Hi ndmarsh, A. C. Report UCI D-30001; Lawrence Li vermore
Laboratory, 1974.
Hi ndmarsh, A. Prel i mi nary documentati on of GEARI BsReport
UCI D-30130; Lawrence Li vermore Laboratory, 1976.
Hutchi ngs, G. J.; Ni col ai des, C. P.; Scurrel l , M. S. Devel opments
i n the producti on of methyl tert-butyl ether. Catal. Today1992,
15, 23.
I hm, S. K.; Suh, S. S.; Oh, I . H. Reacti on and Mass Transfer i n a
Macroreti cul ar Resi n Catal yst. J . Chem. Eng. J pn. 1982, 15,
206.
I hm, S. K.; Chung, M. J.; Park, K. Y. Acti vi ty di fference between
the i nternal and external sul phoni c groups of macroreti cul ar
i on-exchange resi n catal ysts i n i sobutyl ene hydrati on. I nd. Eng.
Chem. Res. 1988, 27, 41.
Parra, D.; Tejero, X.; Cuni l l , F.; I borra, M.; I zqui erdo, J. Ki neti c
study of MTBE l i qui d-phase synthesi s usi ng C4 ol efi ni c cut.
Chem. Eng. Sci. 1994, 49, 4563.
Qui nta Ferrei ra, R. M.; Rodri gues, A. E. Di ffusi on and Catal yti c
Zero-Order Reacti on i n a Macroreti cul ar I on Exchange Resi n.
Chem. Eng. Sci. 1993, 48, 2927.
Qui nta-Ferrei ra, R. M.; Al mei da-Costa, C.; Sp nol a, A. D. C.;
Rodri gues, A. E. Model i ng of MTBE Synthesi s Reactor Wi th
Macroreti cul ar I on Exchange Resi ns. Proc. 44th Can. Chem.
Eng. Conf., Cal gary, Canada, 1994.
Madsen, N.; Si ncovec, R., PDECOL: General Col l ocati on on Fi ni te
El ements. Chem. Eng. Sci. 1975, 30, 587.
Rehfi nger, A.; Hoffman, U. Ki neti cs of methyl terti ary butyl ether
l i qui d phase synthesi s catal yzed by i on exchange resi nsI .
I ntri nsi c rate expressi on i n l i qui d phase acti vi ti es. Chem. Eng.
Sci. 1990a, 45, 1605.
Rehfi nger, A.; Hoffman, U. Ki neti cs of methyl terti ary butyl ether
l i qui d phase synthesi s catal yzed by i on exchange resi nsI I .
Methanol as rate-control l i ng step. Chem. Eng. Sci. 1990b, 45,
1619.
Vi l l adsen, J.; Mi chel sen, M. L. Solution of Differential Equation
Models by Polynomial Approximation; Prenti ce-Hal l : Engl e-
wood Cl i ffs, NJ, 1978.
Received for review Apri l 22, 1996
Accepted May 28, 1996
X
I E9602421
X
Abstract publ i shed i n AdvanceACS Abstracts, September
15, 1996.
j
i
)

0
1
h
1/2

i
R
a
(U
a
) dh

0
1
h
1/2
R
a
(U
a
) dh
(A.24)
j
i
=

j)1
N+1

j
R
a
(U
a
)
i
|
h
j

j)1
N+1

j
R
a
(U
a
)|
h
j
(A.25)

0
1
h
1/2
(1 - h) P
j
(h) P
N
(1,1/2)
(j ) 1, 2, ..., N - 1)
(A.26)

a
) 3

0
1
R
a
(U
a
)x
a
2
dx
a
(A.27)

a
)
3
2

0
1
h
1/2
R
a
(U
a
) dh (A.28)

a
=
3
2

j)1
N+1

j
R
a
(U
a
)|
h
j
(A.29)
I nd. Eng. Chem. Res., Vol . 35, No. 11, 1996 3841