Professional Documents
Culture Documents
0097-6156/82/0196-0003$06.00/0
1982 American Chemical Society
E x p e r i m e n t a l Set-Up and R e s u l t s
The r e s u l t s w e r e o b t a i n e d i n a c o n t i n u o u s l y o p e r a t e d p o l y t r o p i c p i l o t -
p l a n t r e a c t o r w i t h a f e e d o f a p p r o x i m a t e l y 2-5 m o l e s p r o p y l e n e p e r h o u r . The r e
a c t o r was a s i n g l e t u b e h a v i n g a c a t a l y t i c b e d l e n g t h o f 2.70 m a n d a n i n n e r
d i a m e t e r o f 0 . 0 2 0 5 m. T e m p e r a t u r e was c o n t r o l l e d b y a c i r c u l a t i n g m o l t e n s a l t
b a t h . T h e t e m p e r a t u r e p r o f i l e w i t h i n t h e r e a c t o r was m o n i t o r e d w i t h s i d e - e n t r y
t h e r m o c o u p l e s : e l e v e n i n t h e c e n t e r o f t h e t u b e , t w o i n a n 1/2 r a d i u s p o s i t i o n ,
and t h r e e a t t h e w a l l . F e e d s o f p r o p y l e n e , a i r , i n e r t g a s a n d w a t e r w e r e m o n i t o
red by r o t a m e t e r s and preheated t o s a l t bath temperature. O v e r a l l a c r o l e i n y i e l d s
a v e r a g e d o v e r 48 h o u r s p e r i o d s , were e v a l u a t e d by i s o l a t i n g c r u d e a c r o l e i n by
a b s o r p t i o n with water and subsequent d e s o r p t i o n . Unreacted p r o p y l e n e , c a r b o n o x i -
d e s a n d o x y g e n w e r e m e a s u r e d i n t h e e f f l u e n t g a s ( G . C . ) a n d a c r y l i c a c i d was
a n a l y s e d (G.C.) i n t h e a c r o l e i n - f r e e bottoms. To measure t h e a x i a l c o n c e n t r a t i o n
Downloaded by UNIV OF WATERLOO on May 6, 2016 | http://pubs.acs.org
Publication Date: September 16, 1982 | doi: 10.1021/bk-1982-0196.ch001
3
P = 1145 kg/m f o r t h e c a t a l y t i c b e d . The range o f v a r i a b l e s s t u d i e d i n t h e
g
Modeling
Run
No. w max C o m p o s i t i o n o f R e a c t o r F e e d ( M o l e F r a c t i o n ) O v e r a l l
propene
propene propane N 2 0 2 H 0
2
c o n v e r s i o n {%)
1 296 301 0.047i 0.0022 0.595 0.158 0.198 45
2 320 335 0.047 6 0 . 0 0 2 4 0 . 5 9 9 0.159 0.192 72
3 311 325 0.088 2 0.0041 0 . 5 7 0 0.151 0.187 42
4 334 358 0.089! 0 . 0 0 3 8 0.569 0.151 0.187 67
5 377 415 0.089 5 0 . 0 0 4 3 0.567 0.150 0.190 85
T =T(salt bath);
w G - 1.16 0.02 ( k g / m * . s ) ;
= 1.63 0.01 ( b a r ) a t r e a c t o r i n l e t ; p r e s s u r e d r o p : A P = 0 . 0 4 9 g - 0 . 0 0 2 ,
* = remains unreacted under a l l o p e r a t i n g c o n d i t i o n s . (bar/m)
bed l e n g t h temperatureQ) m o l e f r a c t i o n x\ ]
p r o p e n e I C 0 , CO a c r o l e i n a c r y l i c
2
acid;
() C
0 377 0.089 5 0 0 0 .
0.15 415
0.30 413 0.071 6 0.003J 0.0162 0.00054 :
0.45 387
0.60 407 0.056 3 0.005 4 0.030 2 0.0010 8 ]
0.80 406 ;
1.00 385 1
Downloaded by UNIV OF WATERLOO on May 6, 2016 | http://pubs.acs.org
Publication Date: September 16, 1982 | doi: 10.1021/bk-1982-0196.ch001
15 i n c e n t e r o f t u b e , (^ 2 i n 1/2 r p o s i t i o n G = 1.178 ( k g / m * . s )
= 0.051 ( b a r / m )
a r
= 1.633 ( )
3 y
M
j 1 3 , '
3j r~ 3" a ] : V
r ; j=l (1)
3z 1
r ( 2 i e f f
i=l
with t h e boundary conditions:
and f o r t h e e n e r g y b a l a n c e :
3 z=0:yj=yj ; 9=0 (r), 0 0 0*r*l
S-^f k (- H
i
r
) i,eff
3 y
1=1 i 3
O^z^l
3 y
i 3
0 ; B i ( e
0^z="l
^ = 3 T - V
The t r a n s p o r t p a r a m e t e r s i n a j , b j a n d B i a r e e f f e c t i v e p a r a m e t e r s w i t h w h i c h ,
j u s t a s w i t h t h e e f f e c t i v e r a t e r f f , s e v e r a l d i f f e r e n t p h y s i c a l phenomena a r e
e
lumped.
The t w o - d i m e n s i o n a l p s e u d o h o m o g e n o u s r e a c t o r m o d e l ( E q . l ) i s t h e b a s i s f o r
t h e s t a n d a r d i z e d c o m p u t e r p r o g r a m F I B S A S ( 9 ) , w h i c h was u s e d f o r t h e e v a l u a t i o n
and s i m u l a t i o n r e p o r t e d h e r e .
l e i n . Side r e a c t i o n s o f t h i s intermediate s p e c i e s as w e l l as d i -
r e c t p a r a l l e l r e a c t i o n s are p o s s i b l e . However, previous mechanistic
i n v e s t i g a t i o n s l e a d n e i t h e r to unequivocal c o n c l u s i o n s over the
r e a c t i o n scheme nor over the r e a c t i o n k i n e t i c s .
A l a r g e number o f i n v e s t i g a t i o n s do not even consider the
formation o f the i n d u s t r i a l l y important a c r y l i c a c i d (Models I -
I I I ) . The most d e t a i l e d Model V, on the other hand, i s too com-
plex f o r a p r a c t i c a l a p p l i c a t i o n . I n v e s t i g a t i o n s o f model s i m p l i -
f i c a t i o n s f o r i n d u s t r i a l l y r e l e v a n t c a t a l y s t s are e i t h e r nonexis-
tent or lead to d i f f e r i n g r e s u l t s (Models I-IV).
A p o i n t common to a l l the models i s that they are based upon
a redox-type mechanism, i n which the r e o x i d a t i o n o f the c a t a l y s t
i s not a l i m i t i n g f a c t o r . Corresponding, none o f them employ the
Downloaded by UNIV OF WATERLOO on May 6, 2016 | http://pubs.acs.org
Publication Date: September 16, 1982 | doi: 10.1021/bk-1982-0196.ch001
Fo,Ad
Ac acrolein
Ad acetaldehyde
V (32-36) Pe - M s C0,C0 2 As acrylic acid
9 Fo formaldehyde
\ y
Fo.Ad Pe propylene
Downloaded by UNIV OF WATERLOO on May 6, 2016 | http://pubs.acs.org
Publication Date: September 16, 1982 | doi: 10.1021/bk-1982-0196.ch001
(5)
mole nj
100 mole Pe
two a s s u m p t i o n s w e r e made: 1. t h e m o d e l e x p r e s s i o n g i v e n i n ( 7 ) ( w i t h o u t t h e l o n
g i t u d i n a l c o r r e c t i o n ( 9 ) i s c o r r e c t ) ; 2 . B i o t i s c o n s t a n t ( t h e same c o r r e c t i o n
f a c t o r f o r h and * f f )
w e
r. = A. exp(-Ei/RT)T Pj
ij
(6)
was chosen. An i n i t i a l s e t o f parameters ( , E l f n j ) was de
x
I t p r o v e d e f f e c t u a l t o s e t s m a l l v a l u e s f o r i{ ( 4 0 - 7 0 x l 0 J / k m o l e )
6
and n i j
( 0 . 3 - 0 . 5 ) a n d a c h i e v e t h e f i r s t f i t b y v a r y i n g A j . A b e t t e r f i t was a c h i e v e d b y
v a r i a t i o n o f E j a n d n j : , w h e r e b y A j was r e c a l c u l a t e d f o r e a c h s u b s e q u e n t com
putation according to ( 7 ) .
I n r . = I n A. - ( E . / R T ) . . I n p . ( 8 )
j 1J j
and p. i n ( 8 ) a r e experimental values; the other parameters
a r i s e from the former f i t t i n g s f o r Runs 1 - 5 . In each step o f
approximation the best f i t i s f i r s t achieved f o r i = l and then,
one a f t e r another, f o r i = 2 - 4 .
The r e s u l t o f t h i s e s t i m a t i o n o f k i n e t i c parameters i s
shown i n Table V and F i g u r e s 2 - 4 .
., . _ . _
/ r- / i l 2 3
r A e RT
i , e f f " i * *P<-V > P P e \ P c A
A. E.
1 1 .
i [Z n..) "il n
i2 i3 0
K m o l e / n r . s . P a s c a l J i j J/Kmole
1 16.7 -* 5
47.4 106 0.44 0.93 0
2 1.3 10~ 6
42.8 10 6
0.54 0.54 0
3 1.28x 10" 3
52.8 10 6
0.66 0 0
4 77.1 10~ 3
93.2 10 6
0 0 1
Downloaded by UNIV OF WATERLOO on May 6, 2016 | http://pubs.acs.org
Publication Date: September 16, 1982 | doi: 10.1021/bk-1982-0196.ch001
Discussion
1
G = 1.17 - 1.70 kg.m^s" ) as w e l l as f o r a c a t a l y s t d i f f e r e n t
from t h a t used i n Runs 1-5 . The new c a t a l y s t was based upon
the same chemical system but contained more a c t i v e m a t e r i a l ( 8 ) .
It was s u r p r i s i n g t h a t only the pre-exponential f a c t o r s A^
had to be newly estimated (Table VI) whereby the conversion
f a c t o r s f o r A f o r the three p a r a l l e l r e a c t i o n s s t a r t i n g from
x
i n . . A. (5 new r u n s )
1 A. 3
(Kmole/m s . P a s c a l J
) A* ( r u n 1 - 5 )
1 J
1 1
1 j 30.4 " 6
1.8 2
2 2.26 10~ 6
1.7 4
3! 2.03 10" 3
1.5g
4 272.5 10" 3
3.53
Figure 3. Experimental results from Run 4, Table I. Symbols are the same as in
Figure 2.
Figure 4. Experimental results from Run 5, Table I. Symbols are the same as in
Figure 2.
Figure 5. Data plotted of a predicted run. Symbols are the same as in Figure 2.
Legend of Symbols
Cp = mass s p e c i f i c h e a t a t c o n s t a n t time s
1
pressure K J k g " "* temperature
CJ = molar c o n c e n t r a t i o n kmole linear velocity ms - 1
dp,d|.= d i a m e t e r ( p a r t i c l e , t u b e ) mole f r a c t i o n
^r,eff effective radial dispersion pseudo-mole f r a c t i o n y j = n j / 5 n j 0
h
w = wall heat t r a n s f e r stoichiometric coefficient
1
coefficient KJ.nrV ^| Y i j
v o l u m e t r i c mass kg m - 3
reaction
L = lenght of reactor superscript:
M = mean m o l a r mass kg k m o l e - 1 i , (i+1) step o f i t e r a t i o n
= amount o f s u b s t a n c e mole
= reaction order
subscripts:
g = gasphase s = s o l i d phase
i = f o r t h e it h r e a c t i o n t = tube
j = f o r t h e jt h s p e c i e s w = wall
= particle 0 = conditions at reactor inlet
Literature Cited