Beruflich Dokumente
Kultur Dokumente
Chemical Reaction
EngineeringPlenary Lectures
Chemical Reaction
EngineeringPlenary Lectures
James Wei, EDITOR
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226
660.2'99
83-11876
Copyright 1983
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA
Advisory Board
David L . Allara
Robert Ory
Robert Baker
Geoffrey D . Parfitt
Donald D . Dollberg
Theodore Provder
Brian M. Harney
Charles N . Satterfield
W. Jeffrey Howe
Dennis Schuetzle
Herbert D . Kaesz
Marvin Margoshes
Charles S. Tuesday
Donald E . Moreland
C. Grant Willson
FOREWORD
The A C S S Y M P O S I U M
PREFACE
IN
T H E NARROW SENSE,
CHEMICAL
REACTION ENGINEERING
(CRE)
is
concerned with the design, operation, optimization, and control of processing equipment called chemical reactors. C R E is the counterpart
to unit
Except
(the tail)
usually wags the chemical reactors (the dog). A good design engineer
chooses the dog that has the smallest tail.
ix
In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
Function
Chemical Reactors
Unit Operations
Chemical reactions
Physical operations
needed to service the reactors
Individually tailored
Cost
Performance
Nearly linear
Design
kinetic dependence on
temperature and concen
trations
Intellectual
Collaborators
engineers
Mechanical engineers
other
hand, paper-making
In this volume, we print the six plenary speeches given at the 7th International Symposium on Chemical Reaction Engineering at Boston. First,
the intellectual foundation of chemical reaction engineering is described by
Aris, and second, the study of alternative reactors for the methanol-togasoline process is described by Penick. These two chapters form a powerful
contrast between the academic intellectual approach and the industrial
pragmatic approach. Fluidized beds are reviewed by Rowe, and fluidizedbed combustors are reviewed by Sarofim. These two chapters are concerned
with one of the most powerful reactors, in which scale up by design engiDownloaded by ILLINOIS STATE UNIV on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.pr001
neers is still done with great trepidation, and one of its most important
future applications. If fluidized-bed combustors for coal are well engineered, there will be little demand for clean synthetic fuels, except for
liquid fuels for transportation. Combustion should have been one of the
most central problems in reaction engineering. Only historical events decree
that it should be a meeting ground of chemical engineers, mechanical engineers, and chemists with their own Combustion Institute and highly successful International Symposium series. It is overdue for us to build bridges
to these outstanding people. Micromixing is reviewed by Villermaux, and
polymerization reactors are reviewed by Ray. These two chapters are concerned with homogeneous phase and nearly homogeneous phase reactors
that are of growing importance. Most textbooks of reaction engineering have
rather short sections on polymerization, a subject found more often in
polymer textbooks. These reviews will go a long way toward remedying
this defect.
The plenaries serve as a powerful centralizing force among reaction
engineers, who are always in danger of moving off in their own individual
rivulets and drying out. These plenaries should be read by all students of
chemical reaction engineering, whatever their subspecialty. They augment
the basic textbooks as part of "what every educated reaction engineer
should know."
JAMES
WEI
1982
xi
In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
1
Chemical Reaction Engineering as an Intellectual
Discipline
R. ARIS
University of Minnesota, Department of Chemical Engineering and Materials
Science, Minneapolis, MN 55455
C H E M I C A L REACTION ENGINEERING
G i l d e r s l e e v e does r e f e r to S y l v e s t e r s m e t r i c a l theory of
"phonetic syzygy" i n one of the B r i e f Mentions of the American
J o u r n a l of P h i l o l o g y , which he founded i n 1880 e a r l y i n h i s time at
Hopkins and published from there f o r many y e a r s a pleasant f o i l to
S y l v e s t e r ' s American J o u r n a l of Mathematics. G i l d e r s l e e v e was, of
course, a much younger man45 to S y l v e s t e r ' s 62when he came to
Hopkins b u t , i n c o n t r a s t to S y l v e s t e r ' s b r i e f tenure of 8 y e a r s ,
he presided over the d e s t i n y of the c l a s s i c s there f o r the next
39. During that time he e s t a b l i s h e d graduate s t u d i e s i n the
c l a s s i c a l d i s c i p l i n e s , d i r e c t i n g no l e s s than 67 d o c t o r a l d i s s e r t a t i o n s thus having a profound i n f l u e n c e on c l a s s i c a l s t u d i e s
throughout the country. I n 1901 some f o r t y - f i v e of h i s o l d p u p i l s
put together a volume of l a r g e l y p h i l o l o g i c a l s t u d i e s i n h i s
1.
ARis
C H E M I C A L REACTION
ENGINEERING
1.
ARis
C H E M I C A L REACTION ENGINEERING
1.
ARis
C H E M I C A L REACTION ENGINEERING
ee
a n d
11
1.
ARis
10
C H E M I C A L REACTION
ENGINEERING
1.
ARIS
11
12
C H E M I C A L R E A C T I O N ENGINEERING
1.
ARis
13
14
C H E M I C A L REACTION ENGINEERING
expiyw/(+w)}
1 - u{l+aE(w)}
=
=
auE(w) - v { l + a a E ( w ) }
-(1+K)W + a3uE(w) + $ vE (w)
1.
ARIS
15
2.
3.
4.
5.
6.
7.
16
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
C H E M I C A L REACTION ENGINEERING
1.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
ARIS
17
C H E M I C A L REACTION
18
61.
62.
63.
64.
65.
66.
67.
68.
69.
ENGINEERING
2
Development of the Methanol-to-Gasoline
Process
1
10017
Correspondence should be sent to W. Lee, Mobil Research and Development Corporation, Paulsboro, NJ 08066
0097-6156/83/0226-0019$08.50/0
1983 American Chemical Society
Ash
Coal
Gasifier
Stearn
MTG
Process
GASOLINE
Water
Raw
Methanol
Water
MTG
r-*-GASOLINE
Process
F i g u r e 1.
Methanol
Process
Methanol
Process
Raw
Methanol
Synthesis
Gas
(CO + hh)
(CO + H2)
Synthesis
Gas
Steam
Reforming
Process
NATURAL G A S
Steam
Oxygen
COAL
2.
PENICK E T A L .
Methanol-to-Gasoline Process
21
D i s t i l l a t e dewaxing
Xylene i s o m e r i z a t i o n
Toluene d i s p r o p o r t i o n a t i o n
Ethylbenzene
synthesis
L u b r i c a t i n g o i l dewaxing
22
C H E M I C A L REACTION
ENGINEERING
2.
PENICK E T A L .
23
Methanol-to-Gasoline Process
-H 0
2CH OH
3
CH3OCH3
> C -C
Olefins
2
Paraffins
> Aromatics
Cycloparaffins
The i n i t i a l dehydration r e a c t i o n i s s u f f i c i e n t l y f a s t t o
form an e q u i l i b r i u m mixture of methanol, dimethyl e t h e r , and
water. These oxygenates dehydrate f u r t h e r t o g i v e l i g h t
o l e f i n s . They i n t u r n polymerize and c y c l i z e t o form a v a r i e t y
of p a r a f f i n s , aromatics, and c y c l o p a r a f f i n s . The above
r e a c t i o n path i s i l l u s t r a t e d f u r t h e r by Figure 3 i n terms o f
product s e l e c t i v i t y measured i n an isothermal l a b o r a t o r y
r e a c t o r over a wide range of space v e l o c i t i e s . ( 3 )
The r a t e
l i m i t i n g step i s the conversion of oxygenates t o o l e f i n s , a
r e a c t i o n step that appears t o be a u t o c a t a l y t i c . I n the absence
of o l e f i n s , t h i s rate i s slow; but i t i s a c c e l e r a t e d as the
c o n c e n t r a t i o n of o l e f i n s i n c r e a s e s .
Under MTG c o n d i t i o n s , almost no hydrocarbons are found
higher than C ^ Q due to the shape s e l e c t i v i t y o f ZSM-5. While
higher molecular weight compounds may be formed w i t h i n the
c a t a l y s t channels, they do not escape due t o the s p a t i a l
hindrance of the c a t a l y s t s t r u c t u r e .
Reactor Design
Although the design of a r e a c t o r system f o r the MTG process
i n v o l v e s c l a s s i c a l chemical engineering p r i n c i p l e s , the unique
c a t a l y s t and r e a c t i o n mechanisms impose important design
c o n s t r a i n t s . These i n c l u d e the h i g h l y exothermic nature of the
r e a c t i o n , the need f o r e s s e n t i a l l y complete methanol conversion,
steam d e a c t i v a t i o n of the c a t a l y s t , the "band-aging" phenomena,
and durene formation.
Wt. %
Products,
( ^ )
i l 111
1I
Olefins)
1 1 ifrQ-o-i
Olefins
1
Aromatics
PD-D-
Paraffins
(and C $ +
10
M i l l
o-o o- W a t e r
111
C2-C5
S p a c e Time
w
w
S
m
>
to
-
2.
PENiCK E T A L .
Methanol-to-Gasoline Process
25
C a t a l y s t D e a c t i v a t i o n - Under MTG r e a c t i o n
c o n d i t i o n s , ZSM-5 c a t a l y s t undergoes two types of
aging which c o n t r i b u t e to a gradual l o s s of
c a t a l y s t a c t i v i t y . A r e v e r s i b l e l o s s r e s u l t s from
"coke" formed on the c a t a l y s t as a r e a c t i o n
byproduct.
This d e a c t i v a t i o n i s a t y p i c a l
c a t a l y t i c process design problem. What i s unusual
about the MTG process i s that a r e a c t i o n product,
steam, i s a l s o r e s p o n s i b l e f o r a gradual l o s s o f
a c t i v i t y . However, low r e a c t o r temperatures and
low p a r t i a l pressure of water w i l l minimize t h i s
aging and favor a long c a t a l y s t l i f e .
Band-Aging - E s p e c i a l l y w i t h f r e s h c a t a l y s t s , the
r e a c t i o n occurs over a r e l a t i v e l y s m a l l zone i n a
f i x e d bed. This r e a c t i o n f r o n t marches down the
c a t a l y s t bed as the coke d e p o s i t s f i r s t d e a c t i v a t e
the f r o n t part of the bed (Figure 4 ) . Use o f a
s u f f i c i e n t c a t a l y s t volume permits a fixed-bed
design i n which on-stream periods are long enough
to avoid o v e r l y frequent regeneration c y c l e s .
26
CHEMICAL
II
frft^frofr;ii^
0.1
0.2
0.3
ENGINEERING
0.4
0.5
0.6
0.7
0.8
0.9
Fractional Bed
Figure k.
bed.
REACTION
Length
2.
PENICK E T A L .
Methanol-to-Gasoline Process
27
Systems
28
C H E M I C A L REACTION ENGINEERING
Standard
Feed
Quench
Radial Flow
Recycle
Feed
^ ^Recycle
Feed
Recycle
Figure 5a. A d i a b a t i c r e a c t o r s .
Tubular
Isothermal
Feed
Heat
Exchange
Medium
Fluid-Bed Systems
Recycle
Heat
Exchange
Medium
Heat
Exchange
Medium
Feed
PENICK E T A L .
Methanol-to-Gasoline Process
MeOH
Feed ^ ^Recycle
X
r Steam
H 0'
2
Gas
Recycle
%
-C
Gas
Make
Raw
Gasoline
H0
2
MeOH
Feed
I n t e r s t a g e heat removal.
Recycle^
Gasoline
I n t e r s t a g e feed quenching.
C H E M I C A L REACTION ENGINEERING
30
PENICK E T A L .
Methanol-to-Gasoline Process
Figure T.
C H E M I C A L R E A C T I O N ENGINEERING
32
Tubular, Heat-Exchange
Reactor Systems
2.
PENICK E T A L .
Methanol-to-Gasoline Process
33
34
C H E M I C A L REACTION ENGINEERING
2.
PENICK E T A L .
Methanol-to-Gasoline Process
Table I .
35
4 B/D Unit
Conditions
Methanol/Water Chg. (W/W)
Conversion Reactor I n l e t
Temperature (C)
Conversion Reactor O u t l e t
Temperature (C)
Methanol Space V e l o c i t y (WHSV)
Separator Temperature (C)
Recycle R a t i o (mol/mol chg)
Pressure (kPa)
83/17
83/17
358
360
404
1.
49
9
2,163
407
1.6
52
9.2
2,156
Average F i r s t Cycle Y i e l d
(Wt%)
Hydrocarbon Products
Methane
Ethane
Ethylene
Propane
Propylene
Isobutane
n-Butane
Butnes
C 5 + Hydrocarbons
Gasoline (Wt%)
Octane, R+0
1.33
0.82
0.02
8.54
0.15
8.45
4.06
0.71
75.92
100.00
1.25
0.86
0.03
8.60
0.15
8.39
4.20
0.74
75.78
100.00
80.2
95
80.2
95
CHEMICAL REACTION
ENGINEERING
36
2.
PENICK E T A L .
Methanol-to-Gasoline Process
37
38
C H E M I C A L REACTION ENGINEERING
Recycle Gas
Gas
Make
Gasoline
Stabilizer
Steam
Product
Separator
^^Steam
-Stabilized
Gasoline
Raw
Gasoline
Waste Water,
Cooled
Reactor
Effluent
Figure 9.
MeOH
Superheater
DME
Reactor
r
MeOH
Vaporizer
Crude
MeOH
Hot Excess
Effluent
From ZSM-5
Reactors
To Duplicate
Reactor/Effluent
Exchanger Trains
ZSM-5 Reactors
MeOH
JrlPreheater
Cooling
Water
To Separator
/ t [ \ Effluent/Recycle
\[ y
Exchanger
Cooled Effluent
From ZSM-5 Reactor
,1 1,1
Cooler
Compressed
Recycle Gas
From Separator
J-UJ
2.
PENICK E T A L .
Methanol-to-Gasoline Process
39
C H E M I C A L REACTION ENGINEERING
40
Fluid-Bed Development
c a t a l y s t a t t r i t i o n and u l t i m a t e l i f e .
(
y
OO
"I
Catalyst
Recirculation
Line
Catalyst
Storage
Vessel
Air
Regenerator
Flue G a s
Water
H2O
Tank
h B/D f l u i d - b e d p i l o t p l a n t .
Reactor10.2 c m
7.6 m
F i g u r e 11.
Vapor Feed
Liquid F e e d
Water
Tank Car
l eF ecT
Preparation
oo
Methanol
Disengager
Filter -
Gas
Liquid
Hydrocarbons
HC Prod
Tank
Separator
Off
Condenser
42
C H E M I C A L REACTION
ENGINEERING
F l u i d Bed
83/17
83/17
Conditions
Methanol/Water Chg. (W/W)
Dehydration Reactor I n l e t
Temperature (C)
Dehydration Reactor O u t l e t
Temperature (C)
Conversion Reactor I n l e t
Temperature (C)
Conversion Reactor O u t l e t
Temperature (C)
Pressure (kPa)
Recycle R a t i o (mol/mol chg.)
Space V e l o c i t y (WHSV)
316
404
360
413
415
413
2,170
9.0
2.0
275
1.0
0.0
43.4
56.0
0.4
0.2
100.0
0.2
43.5
56.0
0.1
0.2
100.0
1.4
5.5
0.2
8.6
3.3
1.1
79.9
100.0
5.6
5.9
5.0
14.5
1.7
7.3
60.0
100.0
85.0
13.6
1.4
100.0
88.0
6.4
5.6
100.0
93
97
Gasoline ( i n c l u d i n g A l k y l a t e )
[RVP-62 kPa ( 9 p s i ) ]
LPG
Fuel Gas
2.
PENICK E T A L .
Methanol-to-Gasoline Process
43
6h
Reactor
Elevation,
Meters Above
Feed Inlet
100
Figure 12.
Figure 13.
300
500
Temperature, C
700
F l u i d - b e d r e a c t o r temperature p r o f i l e .
C H E M I C A L R E A C T I O N ENGINEERING
44
c i r c u l a t i o n of c a t a l y s t through an e x t e r n a l c a t a l y s t
c o o l e r , and
To m a i n t a i n a constant c a t a l y s t a c t i v i t y i n the r e a c t o r , a
small f r a c t i o n of "coked" c a t a l y s t w i l l be c o n t i n u o u s l y
regenerated and returned to the r e a c t o r .
The mechanical design b a s i s of the 100 B/D u n i t has been
v e r i f i e d on a f u l l - s c a l e Cold Flow Model (CFM). This
non-reacting model proved very u s e f u l f o r o p t i m i z i n g b a f f l e
design and c a t a l y s t c i r c u l a t i o n s t r a t e g i e s . S e v e r a l d i f f e r e n t
b a f f l e designs h o r i z o n t a l and v e r t i c a l arrangements
(Figure 14) have been t e s t e d i n the CFM using s e v e r a l
experimental techniques: gas t r a c e r , capacitance probes, bed
expansion a n a l y s i s , and v i s u a l o b s e r v a t i o n . Integrated
residence time behavior of the bed and q u a n t i t a t i v e , l o c a l
g a s / s o l i d s d i s t r i b u t i o n and bubble s i z e d i s t r i b u t i o n were
measured.
Experimental r e s u l t s i n d i c a t e that h o r i z o n t a l b a f f l e s are
e f f e c t i v e i n breaking bubbles. In the t u r b u l e n t f l u i d i z a t i o n
regime, h o r i z o n t a l b a f f l i n g provides a l s o the e f f e c t of s t a g i n g
the f l u i d bed and l i m i t i n g the formation of gross c i r c u l a t i o n
p a t t e r n s w i t h i n the bed. Thus, h o r i z o n t a l b a f f l e s were
s e l e c t e d f o r i n s t a l l a t i o n i n the p i l o t p l a n t . The b a f f l e
design was optimized to ensure s u f f i c i e n t c a t a l y s t f l u x through
the b a f f l e d s e c t i o n . An o v e r l y r e s t r i c t i v e design can cause a
marked d e n s i t y gradient i n the bed, w i t h most of the c a t a l y s t
accumulating above the top b a f f l e s e c t i o n . The f i n a l b a f f l e
design chosen f o r the 100 B/D p i l o t p l a n t d i d not e x h i b i t t h i s
c a t a l y s t segregation phenomenon.
We b e l i e v e that the 100 B/D p l a n t represents the f i n a l
development step before a commercial-size r e a c t o r can be
designed w i t h confidence.
Future Development
The fixed-bed MTG process designed f o r New Zealand
represents a simple but h i g h l y r e l i a b l e design concept.
The
development of the HGT, which r e l a x e s the durene c o n s t r a i n t ,
opens the process v a r i a b l e window c o n s i d e r a b l y . For example,
i f the r e c y c l e r a t i o i s reduced from 9:1 to 7:1, the s i z e of
the r e c y c l e c i r c u i t i s reduced and i t becomes more e f f i c i e n t ,
l e a d i n g to reductions of about 30% i n heat t r a n s f e r area and
compressor horsepower. However, the octane of the g a s o l i n e
product i s reduced by about one number. S e v e r a l more advanced
fixed-bed process arrangements which reduce processing c o s t s
without reducing octane are being considered and subjected to
p r e l i m i n a r y screening t e s t s .
PENiCK E T A L .
Figure Ik.
Methanol-to-Gasoline Process
Examples o f f l u i d - b e d r e a c t o r i n t e r n a l b a f f l e s .
46
CHEMICAL
REACTION
ENGINEERING
2.
PENICK E T A L .
Methanol-to-Gasoline Process
47
Methanol
Methanol
To
Olefins
r,Pr,c =
Olefins
4
MTG
371-427C
172-2068 kPa
Gasoline
MOGD
Distillate
204-316C
3447-5516 kPa
F i g u r e 15.
P r o d u c t i o n o f e t h y l e n e , g a s o l i n e , and d i s t i l l a t e
methanol.
American Chemical
Society Library
1155 16th St., N.W.
In Chemical Reaction
EngineeringPlenary
Lectures; Wei, J., et al.;
Washington,
D.C. 20036
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
from
C H E M I C A L REACTION
48
Literature Cited
1. Meisel, S. L., McCullough, J. P., Lechthaler, C. ., and
Weisz, P. B., CHEMTECH, 1976, 6, 86-9.
2. Kokotailo, G. T., Lawton, S. L., Olson, D. ., and Meier,
W. ., Nature, 1978, 272, 437-8.
3. Chang, C. D., and Silvestri,
A. J., J. Catal., 1977, 47,
249-59.
4. Fitch, F. B., and Lee, W., "Methanol-to-Gasoline, An
Alternative Route to High Quality Gasoline," presented at
the International Pacific Conference on Automotive
Engineering, Honolulu, Hawaii, Nov., 1981.
5. Garwood, W. E., "Conversion of C -C
Olefins to Higher
Olefins Over Synthetic Zeolite ZSM-5," presented at Am.
Chem. Soc. Mtg., Las Vegas, Nevada, March, 1982.
6. Meisel, S. L. and Weisz, P. B., "Hydrocarbon Conversion and
Synthesis Over ZSM-5 Catalysts", presented at Advances in
Catalytic Chemistry II Symposium, Salt Lake City, Utah,
May, 1982.
2
ENGINEERING
10
1983
3
Fluidized-Bed Reactors
P. N . ROWE
0097-6156/83/0226-0049$06.00/0
1983 American Chemical Society
C H E M I C A L REACTION ENGINEERING
50
would never get away w i t h that l e n g t h today) and gives an imp r e s s i o n of being r a t h e r tedious and t a k i n g a long time to come
to the p o i n t . This i s a poignant reminder of how deeply we have
accepted h i s ideas and now take f o r granted t h i s imaginative and
f r u i t f u l approach. The heart of h i s i d e a i s the b e a u t i f u l l y
l o g i c a l combination of b a s i c laws of chemistry w i t h simple
models of how the r e a c t a n t s come i n t o contact w i t h each other.
The PFR and CSTR are r e a d i l y imagined and widely a p p l i c a b l e
d e s c r i p t i o n s of how r e a l l a r g e s c a l e r e a c t o r s a c t u a l l y behave.
These models of the patterns of r e a c t a n t c o n t a c t i n g form the
b a s i s f o r much of present day chemical r e a c t i o n engineering.
The reason f o r me reminding you of these foundations i s to
draw a t t e n t i o n to the s c a r c i t y of f u r t h e r models beyond these two
b a s i c types. The bubbling gas f l u i d i s e d bed i s one of the very
few a d d i t i o n a l models a l b e i t a much more complicated one and
n e c e s s a r i l y more l i m i t e d i n a p p l i c a t i o n . This i s why i t i s such
a f a s c i n a t i n g subject to chemical r e a c t i o n engineers.
To r e t u r n f o r a moment to the t r a d i t i o n a l models, they have
been expanded, elaborated upon and mixed i n a l l p o s s i b l e (and
some impossible) proportions and, w i t h the w i l l i n g a i d of modern
computational methods, developed to a l e v e l of complexity that i s
i n some cases out of touch w i t h r e a l i t y and c e r t a i n l y no longer
p h y s i c a l l y imaginable but t h i s process of p a r a l y s i s by a n a l y s i s
i s the f a t e of many o r i g i n a l l y simple i d e a s . F o r t u n a t e l y f l u i d i s e d bed r e a c t o r models are s t i l l reasonably c l o s e l y r e l a t e d to
what a c t u a l l y happens and by and l a r g e the models can s t i l l be
imagined as p h y s i c a l r e a l i t i e s .
At t h i s stage I should f o r the b e n e f i t of those l e s s f a m i l i a r
w i t h f l u i d i s e d beds spend a few minutes d e s c r i b i n g the p r i n c i p a l
features that govern t h e i r behaviour as r e a c t o r s ( 9 ) . A l l
powders bubble when f l u i d i s e d by gas at v e l o c i t i e s i n excess of a
minimum value and look r a t h e r as i n F i g u r e 1 which i s a photograph of a two-dimensional bed sandwiched between glass p l a t e s .
I t i s the bubbles that cause p a r t i c l e mixing and b r i n g about the
h i g h heat t r a n s f e r r a t e s that can occur between the bed and w a l l s
or immersed s u r f a c e s . They are r e s p o n s i b l e f o r the high degree of
u n i f o r m i t y , e s p e c i a l l y of temperature and p a r t i c l e composition,
w i t h i n the bed and without them the system would behave more or
l e s s as a packed bed.
Bubbling leads immediately to the concept of two phases w i t h
p a r t of the gas f l o w i n g i n t e r s t i t i a l l y amongst c l o s e l y spaced
p a r t i c l e s and the r e s t f l o w i n g i n the form of bubbles. The i n t e r s t i t i a l f l o w remains constant at the minimum f l u i d i s a t i o n value
although f i n e powders may expand a l i t t l e and permit a r a t h e r
l a r g e r flow. The bubble flow i s t h e r e f o r e e a s i l y evaluated from
Q
Qi
=
Qmf.
Fluidized-Bed Reactors
ROWE
52
C H E M I C A L REACTION
ENGINEERING
3.
ROWE
Fluidized-Bed Reactors
53
g'4
<=> |
tut
54
C H E M I C A L REACTION
interstitial
"
exchange
phase
Figure h.
ENGINEERING
bubble
phase
particle
flow
induced
Figure 5
clouds.
gas circulation
3.
ROWE
Fluidized-Bed Reactors
55
56
C H E M I C A L REACTION
ENGINEERING
ROWE
Fluidized-Bed Reactors
3.
57
58
C H E M I C A L REACTION ENGINEERING
3.
ROWE
Fluidized-Bed Reactors
59
60
CHEMICAL REACTION
ENGINEERING
ski
1
|
3.
ROWE
61
Fluidized-Bed Reactors
mental work has been reported on the former (21, 22) but there i s
i n c r e a s i n g i n t e r e s t i n the l a t t e r (23-29). I t i s becoming f a i r l y
c l e a r that when compared a t the same s u p e r f i c i a l gas v e l o c i t y ,
bubble s i z e decreases as pressure i n c r e a s e s . The reason f o r t h i s
seems t o be that p r o p o r t i o n a t e l y more gas flows i n t e r s t i t i a l l y as
pressure increases and bubbles are smaller because the reduced
f l o w gives l e s s opportunity f o r growth by coalescence. Powders
that normally behave as Geldart type ( i . e . U f = U ^ ) become
type A a t q u i t e modest increases i n pressure. This i s good news
from a chemical r e a c t i o n engineering point of view and the
bubbling bed models continue to apply and only r e q u i r e the
changed d i v i s i o n of flow to be q u a n t i f i e d .
At pressures greater than about 80 bar some i n t e r e s t i n g
hydrodynamic changes occur. Bubbles begin to l o s e t h e i r i d e n t i t y
and a t q u i t e low gas v e l o c i t i e s the bed takes on the general
appearance of a " t u r b u l e n t " o r " f a s t f l u i d i s e d bed". This again
i s advantageous f o r r e a c t i o n engineering but few processes w i l l
be r e q u i r e d t o operate a t such high pressures.
I t u r n f i n a l l y to consider the d i r e c t i o n f u t u r e b a s i c
research should take. I t i s fundamental to the s t a t e o f f l u i d i s a t i o n that p a r t i c l e s are supported by the drag of f l o w i n g gas.
This f o r c e depends not only on the gas p r o p e r t i e s and v e l o c i t y
but a l s o on the p a r t i c l e spacing and arrangement. I n s p i t e of
the i n t e r e s t of f l u i d dynamicists
l i t t l e i s known about the
r e l a t i o n s h i p between p e r m e a b i l i t y , voidage and the flow c o n d i t
ions and yet i t i s t h i s that decides the d i v i s i o n of gas between
the phases w i t h important consequences f o r chemical r e a c t i o n . I t
i s evident that p a r t i c l e s i z e and s i z e d i s t r i b u t i o n are f a c t o r s
determining p e r m e a b i l i t y and that " f i n e s " are important i n t h i s
respect but i t i s d i f f i c u l t to understand why change of absolute
pressure should change voidage and p e r m e a b i l i t y .
Understanding
these things could g r e a t l y improve our a b i l i t y t o engineer f l u i d
i s e d bed chemical r e a c t o r s and t h i s should be a major object of
b a s i c research.
However deep our knowledge of the mechanism of f l u i d i s a t i o n
i t i s s a l u t a r y to pause and consider the freedom of choice a
chemical r e a c t i o n engineer w i l l have. Leaving aside d e t a i l s o f
mechanical design such as the d i s t r i b u t o r , b a f f l e s , heat exchang
ers and m a t e r i a l s of c o n s t r u c t i o n , the v a r i a b l e s are very l i m i t e d .
Gas d e n s i t y and v i s c o s i t y and p a r t i c l e d e n s i t y w i l l be determined
by chemistry and thermodynamics and the only major v a r i a b l e s
remaining are gas v e l o c i t y , bed height and p a r t i c l e s i z e and s i z e
d i s t r i b u t i o n . The f i r s t two are l a r g e l y f i x e d by production r a t e
and simple engineering c o n s i d e r a t i o n s and p a r t i c l e s i z e i s about
the only t h i n g l e f t to choose. I f we knew more about how to make
t h i s choice our designs might be much improved.
62
CHEMC
IAL REACTO
IN ENGN
IEERN
IG
L i s t of Symbols
cL
bubble diameter
JD
r e a c t o r diameter
bed height
volumetric flow
Q_.
bubble f l o w r a t e
r a t e i n t o the bed
Q.
i n t e r s t i t i a l flow rate
minimum f l u i d i s a t i o n flow r a t e
U ^
U ^
minimum f l u i d i s a t i o n flow v e l o c i t y
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
3.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
ROWE
Fluidized-Bed Reactors
63
1983
4
Fluidized-Bed Coal Combustion: Controlling
Parameters
A D E L F. SAROFIM
The factors controlling the performance of atmospheric-pressure fluidized-bed combustors (AFBC's) are
illustrated by order-of-magnitude calculations of the
design and operating variables for a hypothetical
100 MW boiler. Bed height, bed cross-sectional area,
immersed heat-transfer surface area, sorbent feed
size and rate, bed temperature, fluidizing velocity
and coal feed size are selected by consideration of
the fluids mechanics, heat transfer, and kinetics of
the governing gas-solid reactions. The fluid mechanics and heat transfer in AFBC's are shown to be
differ distinctly from those in more traditional
fluidized bed reactors.
t
66
C H E M I C A L REACTION ENGINEERING
H S)
2
to s u l f u r capture,
CaC0
CaO +
CaS0
S0 +
CaS0
+ CaO
S0 >
+ 1/2
1/2 0
+ 1/2
2
+ C0
CaS0
0 + CaS0
-> S 0
0 -> CaS0
2
and d e s t r u c t i o n ,
N 0
C 0
1 / 2
^
2
2
NO + CaS0 + CaS0 + 1/2
3
4.
SAROFiM
67
Table I .
D i f f e r e n c e s i n F l u i d i z a t i o n and Heat Transfer o f AFBC's
and F l u i d i z e d C a t a l y t i c Reactors (e.g. FCC s)
T
FCC
AFBC
particle(s)
heating
(1)
CHEMICAL
SPENT
SORBENT
REACTION
ENGINEERING
COAL
4.
SAROFiM
69
3 (-AH )n n
c
v>
-: = 0.028 h
*F
(3)
C H E M I C A L REACTION ENGINEERING
70
CaC0
S0
CaC0 .MgC0
3
2
3
1/2
S0
1/2
CaSO. +
4
0
C0
= -325 kj/mole
+ Mg0.CaS0
2C0
(4)
= - 2 1 0 kJ/mole
(5)
4.
SAROFiM
m/m oo
Figure 2 . Rate constant f o r the r e a c t i o n o f S O 2 w i t h c a l c i n e d
limestone as a f u n c t i o n o f m, the f r a c t i o n a l s u l f a t i o n , and
m/m , the f r a c t i o n a l s u l f a t i o n normalized w i t h i t s asymptotic
value (9.).
71
72
C H E M I C A L REACTION ENGINEERING
t h a t the maximum s u l f a t i o n m
of a v a r i e t y of limestones
00
decreased
4.
SAROFiM
1050
1100
1150
73
1200
Temperature (K)
74
CHEMICAL REACTION
ENGINEERING
4.
SAROFiM
75
dp (/im)
76
C H E M I C A L REACTION
ENGINEERING
d (m)
B
4.
SAROFiM
77
= 0.54
(u -u
o
m f
(h + 4 / T )
2 / 5
4 / 5
/g
(6)
1 / 5
m f
i s
-U2->l __
u ^
.
mf
mf
T N E
(7)
78
CHEMICAL REACTION
ENGINEERING
- [12 + 0.05
(1 + 2 0 ) ( ^ d p ) P r ]
(8)
( T
b - V
- /, I l/ - 1
b
w
<>
where i s the tube w a l l e m m i s i v i t y , and ^ i s the e f f e c t i v e emm i s s i v i t y of a plane formed by the s p h e r i c a l p a r t i c l e s . The con
t r i b u t i o n s to the heat t r a n s f e r by the above mechanisms i s shown
i n Figure 6. As p a r t i c l e diameter increases the conduction con
t r i b u t i o n given by the f i r s t term i n Eq. 8 f a l l s r a p i d l y but
compensation i s provided by the i n c r e a s e d convection c o n t r i b u t i o n
given by the second term, so that the t o t a l passes through a
minimum. The e f f e c t i v e heat t r a n s f e r c o e f f i c i e n t to the tubes
w i l l be s l i g h t l y lower than that given by Equations 8 and 9, since
4.
SAROFiM
79
contribu-
80
= W K(R)p(R)
input
s o l i d s withdrawal
d[p(R)R]
c
dR
net shrinkage
out o f s i z e range
where
F
F^
K(R)
p(R)
p (R)
R
R
W
W
Q
=
=
=
=
=
=
=
=
=
elutriation
3W p(R)R
c
(10)
R
growth w i t h i n
s i z e range
c o a l feed, kg/s
s o l i d s withdrawal r a t e , kg/s
e l u t r i a t i o n constant f o r p a r t i c l e s o f s i z e R, s"
f r a c t i o n of mass of c o a l i n s i z e range R t o R + dR,
p(R) f o r feed stream, m~l
p a r t i c l e radius, m
r a t e o f change o f p a r t i c l e r a d i u s , m/s
carbon l o a d i n g , kg
t o t a l s o l i d s i n bed, kg
4.
SAROFiM
81
23.2 MW
Qc*27.2 S
MW
50.4 MW
t
III MW
QF
Q =73 C MW
^
-T =644
6
1.3 MW
BED SOLIDS
I3MW 589K
298
AIR
PREHEAT
9.8 MW
= 515 m
h(T -Tw>
B
_ L . o
0.125 m
T'b
C H E M I C A L REACTION ENGINEERING
82
and
P
o l
-*-
= ShPC^
2
( 1 2 )
- f Vb
time of p a r t i c l e s of
i n i t i a l radius
R-^.
48ShPC
( 1 3 )
p
Sh * [2 +0.6
Re
1 / 2
Sc
1 / 3
(14)
4.
SAROFiM
83
( 1 6 )
(l+e)n(l+l/e)
W
=
9
Ahp (l- )
s
(17)
K / J
m
m W
c,s _ s ^
( 1 8 )
(19)
C H E M I C A L REACTION
84
ENGINEERING
(20)
d /2
3p(R)Wk ( u - u
c a mf)
n
3k (u -u -)
a mf .
(21)
1/4
3
( i>opt
48ShPCp(d*)
k (u -u ,)
c a mf
(22)
4.
85
SAROFiM
C0
(1
+ C=
- |)
(23)
2C0
+ C = xCO
(1 - x ) C 0
(24)
86
C H E M I C A L R E A C T I O N ENGINEERING
4.
SAROFiM
87
C H E M I C A L REACTION ENGINEERING
88
Using the data of Howard and coworkers (77) Borghi et a l (59) have
modeled the v o l a t i l e r e l e a s e rate f o r AFBC c o n d i t i o n s . Their pred i c t i o n f o r both the duration of a v o l a t i l e flame and the subsequent char burnout times have been confirmed by the experimental
measurements of Andrei (78). Sample r e s u l t s are shown i n Figure
8, which presents the c a l c u l a t e d ( s o l i d l i n e ) and measured (data
p o i n t s ) weight l o s s of
3 m i l l i m e t e r p a r t i c l e s burned i n 5 percent oxygen stream i n a f l u i d i z e d bed maintained a t 1173 K.
The
i n i t i a l steep drop i n weight i s due to v o l a t i l e e v o l u t i o n , and i t
i s followed by the slower char burnout stage. T h i r t y percent of
the weight of coal i s l o s t i n a p e r i o d of a l i t t l e under 4 seconds
for the 3 mm p a r t i c l e . For 1 mm p a r t i c l e s the time f o r d e v o l a t i l i z a t i o n i s under 1 second. These times can be compared w i t h the
estimates of the s o l i d c i r c u l a t i o n time of 3 to 6 seconds obtained
above. The v o l a t i l e r e l e a s e time i s therefore comparable to the
s o l i d c i r c u l a t i o n time and n e i t h e r the model of instantaneous or
distributed v o l a t i l e release i s v a l i d .
Park et a l (42) recognized the importance of modeling the
v o l a t i l e release i n AFBC s and developed a plume model based on
the instantaneous r e l e a s e of v o l a t i l e s and l a t e r a l d i f f u s i o n using
a d i f f u s i v i t y based on t r a c e r d i s p e r s i o n . Their model succeeded
i n showing the major importance of l a t e r a l d i f f u s i o n w i t h i n AFBC*s
i n determining feed p o i n t l o c a t i o n . Stubingdon and Davidson (79)
however showed that the combustion of hydrocarbons, which are a
v a l i d surrogate f o r c o a l v o l a t i l e s , i s governed by molecular d i f f u s i o n which i s considerably lower than the r a d i a l d i f f u s i o n
obtained from t r a c e r s t u d i e s .
(The t r a c e r s t u d i e s apparently
provide a measure of the meandering of a laminar stream without
mixing at the molecular l e v e l needed f o r r e a c t i o n ) . The mechanism
for r a d i a l d i s p e r s i o n i s due to
s o l i d and not gas d i f f u s i o n .
A s l i g h t v a r i a n t on the plume model of Park et a l (42) i s shown
i n F i g . 9. Coal p a r t i c l e s i n j e c t e d a t the bottom of the bed are
convected upward and d i f f u s e r a d i a l l y as a consequence of bubble
motion. V o l a t i l e s w i l l be r e l e a s e d at a decaying r a t e f o r s e v e r a l
seconds, depending upon p a r t i c l e s i z e and bed temperature. The
radius r of the c r o s s - s e c t i o n over which the v o l a t i l e s are r e leased i s determined by the s o l i d d i f f u s i v i t y P .
To a f i r s t
approximation
1
r = ifuZt
(25)
(26)
The mechanism of s o l i d d i s p e r s i o n i s complex and p o o r l y understood so that Eq. 26 represents only a f i r s t approximation. For
4.
SAROFiM
89
C H E M I C A L REACTION ENGINEERING
90
2 f -f
Trr _ y a
2~
1+e
(27)
+ NO + 1/4
=
2
+
2
3 / 2
28>
( *
4.
SAROFiM
91
+ xCO + ( l - x ) C 0
(29)
(30)
C H E M I C A L REACTION
92
ENGINEERING
4.
SAROFiM
93
Concluding Comments
The above c o n s i d e r a t i o n o f the f a c t o r s that govern the
design and operation o f the f i r s t generation of AFBC s provide
an a p p r e c i a t i o n f o r the parameters t h a t c o n s t r a i n t h e i r perform
ance. There i s c l e a r l y opportunity f o r improvement, p a r t i c u l a r l y
w i t h respect t o reducing the amounts o f sorbent used f o r s u l f u r
capture, reducing the number of c o a l feed p o i n t s , reducing the
l o s s o f carbon f i n e s , and changing heat l o a d without v a r y i n g bed
temperature. A number o f f l u i d i z e d bed combustors o f advanced
design have been developed o r are under i n v e s t i g a t i o n . These
i n c l u d e f a s t f l u i d i z e d beds, p r e s s u r i z e d beds, m u l t i - s t a g e beds,
c i r c u l a t i n g beds, and r o t a t i n g beds. The f a s t - f l u i d i z e d r e
c i r c u l a t i n g bed i s f u r t h e s t developed of those advanced concepts,
and has already been commercialized.
From a fundamental standpoint, the order o f magnitude e s t i
mates of many o f the parameters i n the bed was intended t o
i n d i c a t e which processes were important.
There i s c l e a r l y a need
f o r a b e t t e r understanding o f the processes that govern ( i ) par
t i c l e c i r c u l a t i o n and e l u t r i a t i o n i n l a r g e p a r t i c l e systems,
( i i ) g r a i n growth f o r purposes o f improving stone u t i l i z a t i o n ,
( i i i ) the generation and burnout o f f i n e carbon p a r t i c l e s .
An attempt was made i n the p r e s e n t a t i o n t o show the complex
i n t e r a c t i o n between the d i f f e r e n t processes occuring i n the bed.
For example, sorbent u t i l i z a t i o n may a f f e c t N 0 through the
formation o f CaSO^ and bed pressure drop through the dependence of
s o l i d d e n s i t y on extent of s u l f a t i o n ; carbon burning times deter
mine the carbon l o a d i n g i n the bed which i n turn governs both
the amount of f i n e char p a r t i c l e generation and the r e d u c t i o n of
NO; the carbon f i n e s i n f l u e n c e the e l u t r i a t i o n r a t e s of coarser
p a r t i c l e s ; the carbon monoxide i n f l u e n c e s the carbon p a r t i c l e
temperature overshoot and a l s o p a r t i c i p a t e s i n the surface c a t a
l y z e d r e d u c t i o n o f NO. Such i n t e r a c t i o n s add t o the challenges
of modeling t h i s c l a s s o f chemical r e a c t o r s .
Legend of Symbols
bed c r o s s e c t i o n a l area, m
spacing between c o a l feed p o i n t s , ra
Cp
i n l e t oxygen c o n c e n t r a t i o n , mole/m
94
C H E M I C A L R E A C T I O N ENGINEERING
Legend o f SymbolsContinued
d^
bubble diameter, m
d^
i n i t i a l diameter of char p a r t i c l e , m
dp
bed p a r t i c l e diameter, m
d*
gas-phase d i f f u s i v i t y , m /s
2
d i f f u s i o n c o e f f i c i e n t s f o r s o l i d s i n emulsion phase, m /s
V
V
excess a i r , f r a c t i o n of s t o i c h i o m e t r i c
f r a c t i o n of s t o i c h i o m e t r i c
coal feed
F^
a i r requirement
a i r used as c a r r i e r gas f o r
c o a l feed r a t e , Kg/s
s o l i d s withdrawal r a t e , Kg/s
2
grativational acceleration,
m/s
height of bed, m
2
h^
-^
k
K(R)
2
o
cm/s
m^
4.
SAROFiM
95
Legend o f SymbolsContinued
m
c o a l feed r a t e , Kg/s
p(R)
radius of v o l a t i l e plume, m
p a r t i c l e radius, m
R^
p a r t i c l e r a d i u s o f monodisperse feed, m
Re
r a t e of change of p a r t i c l e r a d i u s , m/s
Sc
Schmidt number
Sh
t
t
Sherwood number
residence time, s
p a r t i c l e burnout time, s
absolute temperature, K. S u b s c r i p t s b, w r e f e r t o bed and
tube w a l l temperature, r e s p e c t i v e l y
u^
bubble r i s e v e l o c i t y , m/s
u
U
u
m
i n
emulsion phase
minimum f l u i d i z i n g v e l o c i t y , m/s
mr
f l u i d i z i n g v e l o c i t y , m/s
p a r t i c l e t e r m i n a l v e l o c i t y , m/s
3
c
W
^2
mole f r a c t i o n of oxygen
96
CHEMICAL
REACTION
ENGINEERING
Legend o f SymbolsContinued
bed v o i d f r a c t i o n
mf
v o i
d f r a c t i o n a t minimum f l u i d i z i n g v e l o c i t y
f r a c t i o n a l e f f i c i e n c y o f conversion of thermal t o e l e c t r i c a l
energy
fan e f f i c i e n c y
3
carbon d e n s i t y , Kg/m
3
bed s o l i d d e n s i t y , Kg/m
s
2
4
Stefan-Boltzmann constant, W/(m )(K )
c h a r a c t e r i s t i c h e a t i n g time o f p a r t i c l e s , s
Acknowledgments
The above overview has drawn on background developed as p a r t
of an i n t e r d i s c i p l i n a r y program on f l u i d i z e d bed combustion a t MIT
funded by DOE, w i t h p a r t i a l support from Stone and Webster E n g i
n e e r i n g Corp, The authors i s indebted t o h i s students and c o l
leagues f o r h i s education on many aspects o f the problem especially
to Janos M. Beer, C h r i s t o s Georgakis, and Leon R. Glicksman whose
views are r e f l e c t e d , a l b e i t through a g l a s s d a r k l y , i n the paper.
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
4.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
SAROFIM
97
98
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
C H E M I C A L REACTION
ENGINEERING
4.
67.
63.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
31.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
SAROFIM
99
100
C H E M I C A L REACTION
ENGINEERING
94.
1983
5
Current Problems in Polymerization Reaction
Engineering
W. HARMON R A Y
Polymerization reaction engineering is an important area in the process industry with many diverse
and challenging design problems. In this survey, an
introduction to some of the key design d i f f i c u l t i e s
is followed by several specific examples i l l u s t r a t ing some of the intriguing and exotic phenomena
arising routinely in polymerization reactors. A
survey of the recent literature indicates a strong
upsurge of interest in these problems.
102
C H E M I C A L REACTION ENGINEERING
Capacity, millions
1980s 1981
Resin
Mid-1980s
of l b per yr.
1981
Change
P o l y e t h y l e n e , low-density
38,047
31,702
20.0%
Polyvinyl chloride
35,339
32,430
8.9
Polyethylene, high-density
22,895
18,071
26.7
Polypropylene
17,809
15,631
13.9
Polystyrene
17,626
16,491
6.9
10
P o l y e t h y l e n e , l i n e a r low-density
8,081
2,669
202.8
Acrylonitrile-butadiene-styrene
4,662
4,374
6.6
Isocyanates
4,270
3,634
17.4
Polyols*
4,255
4,246
0.2
10
Unsaturated
3,538
3,516
0.6
Other
TOTAL
polyesters
8,006
7,359
164,528
140,123
8.8
17.4%
a Used as i n d i c a t o r s f o r d e r i v a t i v e polyurethanes.
b includes a c r y l i c s ,
amino r e s i n s , c e l l u l o s i c s , f l u o r o p o l y m e r s , p h e n o l i c s , p o l y a c e t a l s ,
p o l y c a r b o n a t e s , polyphenylene o x i d e , s t y r e n e - a c r y l o n i t r i l e .
5.
RAY
103
Author(s)
T o
Reference
i c
Keane (1972)
Ray (1972)
K e i i (1972)
A l b r i g h t (1974)
Min and Ray (1974)
Gerrens (1976)
Bouton and Chappelear
(1976)
S i n g l e Phase P o l y m e r i z a t i o n
Mathematical M o d e l l i n g
Ziegler-Natta Polymerization
Polymerization Processes (Monograph)
Emulsion P o l y m e r i z a t i o n
P o l y m e r i z a t i o n Reactions and Reactors
Continuous Reactors (ed. volume)
Piirma
Emulsion P o l y m e r i z a t i o n
and Gardon
(1976)
Ray and Laurence (1977)
Poehlein and Dougherty
(1977)
Schildknecht and S k e i s t
(1977)
Henderson and Bouton
(1979)
Boor
(1979)
Gerrens (1980, 1981,
1982 )
Odian (1981)
Ray (19 81)
Bassett and Hamielec
(1982)
Piirma (1982)
E l - A a s s e r and
Vanderhoff
(1982)
Sebastian and
Biesenberger
Quirk (1983)
(ed. volume)
3
4
5
6
7
8
9
10
P o l y m e r i z a t i o n Reaction Engineering
Continuous Emulsion P o l y m e r i z a t i o n
11
12
P o l y m e r i z a t i o n Processes
13
P o l y m e r i z a t i o n Reactors
(ed. values)
(ed. volume)
14
O l e f i n Polymerization
P o l y m e r i z a t i o n Technology
15
16-18
Polymerization Kinetics
P o l y m e r i z a t i o n Reactor Dynamics
Emulsion P o l y m e r i z a t i o n (ed. volume)
19
20
21
Emulsion P o l y m e r i z a t i o n
Emulsion P o l y m e r i z a t i o n
22
23
(ed. volume)
(ed. volume)
P o l y m e r i z a t i o n Engineering
24
Ziegler-Natta Polymerization
25
(1983)
P o l y m e r i z a t i o n K i n e t i c s and Reactor
Design
104
C H E M I C A L REACTION ENGINEERING
Table I I I .
Monomer Addition:
A.
Free Radical
* 2R
1
\
kd
R
+ M
initiation
1
Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org
Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch005
+ M
7~+ +1
*P
P
+A
P^g^tion
+M
f
^
M
^t^**
chain transfer
+ M^ disproportionate )
m ^
Vtermination
k
tc
" M_.
combination
initiation
+ M
* n+l
propagation
m 1 n4m
propagation
medium
2.
Suspension
c. P r e c i p i t a t i o n
( b u l k and
solution)
b.
Heterogeneous
a. E m u l s i o n
1. H o m o g e n e o u s
( b u l k and s o l u t i o n )
Reaction
K I N E T I C MECHANISMS AND
radical
Vinyl
(PVC)
polymers
V i n y l polymers
( S t y r e n e , PVC)
V i n y l polymers
( S t y r e n e , PVC)
V i n y l polymers
(Styrene,
LDPE)
Free
P o l y a m i d es
(Nylon
interfac i a l
poly . )
Polyesters,
Polyamides
(PET,
Nylon)
Polyethers
(Ethylene
ox i d e)
Polyacetals
(formaldehyde)
Vinyls
(iso-butylene-buty1
rubber)
Condensation
mechanism
Polyolef ins
with
insoluble
catalyst
( L i q u i d and
gas p h a s e
processes f o r
HDPE, L L D P E ,
polypropylene)
Polyolefins
with
soluble
catalyst
(ethylenepropylene
copolymers)
Coord i n a t i o n
Catalysis
I N P O L Y M E R I Z A T I O N REACTORS
Ionic
Kinetic
TABLE IV
106
CHEMICAL
REACTION
ENGINEERING
-21.2
-19.5
-17.6
-16.7
-22.9
-18.0
-21.2
-18.5
-13.2
-18.4
- 7.4
5. RAY
107
C H E M I C A L REACTION ENGINEERING
Color, C l a r i t y
MOLECULAR ARCHITECTURE
Average M o l e c u l a r
Weight and Molecular
Weight D i s t r i b u t i o n
(or Melt Index,
Viscosity, etc.)
MW
Polymer Composition
and Composition
Distribution
nlOO
Melting P o i n t
Corrosion
Resistance
Abrasion
Resistance
Chain Sequence
Distribution
Degree of Chain
Branching
Density
-A-A-B-A-A-A-B-Ba.
Linear:
I II !! I
-c-c-c-c-c-c-
I IIII I
Impact Resistance
b.
Temperature
Stability
Branched :
-C-C-C-C-C-C-
Swellability
P l a s t i c i z e r Uptake
Spray Drying
Characteristics
Coating and
Adhesion P r o p e r t i e s
Stereoregularity
(Tacticity)
a.
Isotactic:
-C-C-C-C-C-C-C-
A
b.
Syndiotactic:
A
-c-c-c-c-c-
I
A
c.
I
A
Atactic:
A
-c-c-c-c-c-c-c-
Average P a r t i c l e
Size D i s t r i b u t i o n
Size
P a r t i a l P o r o s i t y and
Surface Area
38
37
36
ho 39
Fluidized bed
(Double) Loop
35
3k
CO
33
32
31
30
Table V I I .
29
28
27
26
25
Extruder
2k
23
Mixer + conveyor
22
21
Continuous tube
18
16
15
<u
13
BR
Piston
12
Semibatch
11
10
Practice.
Precipitation
polymerization
Solid-phase polycondensation
Interfacial polycondensation
Solution or melt-polycondensation
p. y
Emulsion polymerization
Solution polymerization
Precipitation
polymeri zation
Bead polymerization
<
JJ
Solution polymerization
Polymerization reactions
Reactor C o n f i g u r a t i o n s Found i n I n d u s t r i a l
110
C H E M I C A L REACTION ENGINEERING
Table V I I I .
Topic
References
(26-48)
Biesenberger, Johnson, T i r r e l l
(49-60)
(61-94)
Polycondensation
(95-124)
(125-135)
(136-147)
Tubular Polymerization
Reactors
(148-166, 246)
(167-184)
Suspension Polymerization
Reichert
(206-217)
Emulsion Polymerization
(21-23_, 160,
201-205,
TTff-TBT)
5.
RAY
Some Current
111
Research Problems
S o l u t i o n Polymerization i n a CSTR. Although many polymerizat i o n reactors i n use by industry have the residence time d i s t r i bution of a CSTR, they may not, at f i r s t glance, have the
appearance of a CSTR ( c f . Figure 1). Nevertheless, CSTR models,
perhaps with some allowance f o r imperfect micromixing, are
s u c c e s s f u l l y employed to d e s c r i b e these r e a c t o r s . Thus the
behavior of the CSTR i s of great p r a c t i c a l i n t e r e s t .
Recent studies of CSTR s f o r bulk or s o l u t i o n f r e e r a d i c a l
polymerization i n d i c a t e the p o s s i b i l i t y of m u l t i p l e steady s t a t e s
(e.g.; 20,137-139,145-147). The f a c t that t h i s occurs should not
be s u r p r i s i n g given the l a r g e heat e v o l u t i o n and d i f f i c u l t heat
t r a n s f e r c h a r a c t e r i s t i c of polymerization r e a c t o r s . However,
there are dramatic new t w i s t s to these phenomena even i n simple
s o l u t i o n polymerization.
For example, a u t o c a t a l y t i c k i n e t i c s
lead to the existence of m u l t i p l e steady states even under
isothermal reactor c o n d i t i o n s . Figure 2 (taken from (145))
i l l u s t r a t e s t h i s f o r the case of methyl methacrylate
polymerizat i o n i n e t h y l acetate solvent c a r r i e d out at the b o i l i n g point
of the r e a c t i n g l i q u i d . Note that the model p r e d i c t i o n s and the
steady s t a t e experiments agree that there i s i g n i t i o n to a
high conversion, inoperable, steady s t a t e at a c e r t a i n
residence time f o r solvent f r a c t i o n s l e s s than ~40%.
The upper
steady s t a t e i s inoperable due to the extremely high v i s c o s i t i e s
at such high conversions.
In the laboratory, i g n i t i o n which was
allowed to proceed to t h i s upper steady s t a t e r e s u l t e d i n a
reactor f i l l e d with s o l i d polymer. The p r a c t i c a l consequence
of t h i s f o r the i n d u s t r i a l r e a c t o r i s that even with p e r f e c t
temperature c o n t r o l (an u n l i k e l y event a f t e r i g n i t i o n has
occurred), the r e a c t o r w i l l i g n i t e i n t o a "runaway" c o n d i t i o n f o r
c e r t a i n combinations of solvent concentration and r e a c t o r
residence time. I f only temperature measurements are being
taken, the operator would not be aware of the runaway u n t i l the
a g i t a t o r motor blew a fuse, or the g r e a t l y increased r a t e of
r e a c t i o n exceeded the c o o l i n g system capacity and caused a sharp
increase i n temperature and pressure i n the r e a c t o r .
1
112
C H E M I C A L REACTION ENGINEERING
[1
El
m
m
m
flf
m
m
Tower cascade
11 1
Ring disc
Stirred tank-tower
combination
Polymer
Catalyst
solvent .
Catalyst
ethylene Polymer
powder
Gaseous monomer
Monomer Catalyst
CSTR
(Double) Loop
I.Oj
20
30
20
J
40
I
60
L
80
40
100
50
I I I I j
10
(3
20
30
40
50
F i g u r e 2. Isothermal p o l y m e r i z a t i o n o f
methyl methacrylate i n a CSTR (1U5).
a. P r e d i c t e d steady-state monomer conver
s i o n v s . r e a c t o r residence time f o r t h e
s o l u t i o n p o l y m e r i z a t i o n o f MMA. i n e t h y l
acetate a t 86 C. b. Steady-state and
dynamic experiments f o r the i s o t h e r m a l s o l u
t i o n p o l y m e r i z a t i o n o f MMA i n e t h y l acetate
( s o l v e n t f r a c t i o n 0 ) () steady s t a t e s ,
Co) non-steady s t a t e s , c. Steady-state con
v e r s i o n v s . CSTR residence time f o r s o l v e n t
f r a c t i o n o f 50%.
10
B O U N D S -J"*
1.0 r
E X P E C T E D ERROR
S'
S'
>
114
C H E M I C A L REACTION ENGINEERING
with
^ f ^
determines
5.
RAY
115
8.888
45
688
758
98
1858
188.8
R 58.8
fi
U
R
.
1858
RESIDENCE TIME
Figure 3. E f f e c t o f feed temperature on steady-state o p e r a t i o n
f o r MMA p o l y m e r i z a t i o n (lV7_) Base case,
23 C
21 C
; and T = 25 c
.
U
116
C H E M I C A L REACTION ENGINEERING
8.5H
I I I '0|
25
I I I ! [ 1 1 I 1 j I 1
58
75
I > I I
j I I I I
125
158
188
&Qv^O
rj^^
58 H
-J_
I I I j I I I I [ I I 1 I j I I I I I j I I I I
25
50
75
108
125
150
RESIOENCE TIME ( M I N )
Figure U. A comparison o f the steady-state v i n y l acetate model
and experimental data (1U7). T~ = 20 C; T = 25 C;
= 0.50;
I = O.OUlT m o l e / l i t . 0 - s t a b l e steady s t a t e ; and 0 - unstable
transient.
Q
5.
RAY
111
Monomer
H2O
Emulsifier
Initiator
Polymerizing
Emulsion
Figure 5 A continuous
reactor.
s t i r r e d tank emulstion p o l y m e r i z a t i o n
118
C H E M I C A L REACTION
ENGINEERING
() S t y r o i / g Latex
K)0
80
&0
40
20
% Conversion
5. RAY
119
100-1
1 0
2 0
3 0
Residence Time
4 0
5 0
6 0
(min)
120
CHEMICAL
REACTION
ENGINEERING
i n d u s t r i a l p r a c t i c e ( c f . (20,253,254) f o r a d i s c u s s i o n of t h i s ) .
Experimental r e s u l t s from our l a b o r a t o r y (201,202) shown i n
Figure 8 provide only one example of t h i s troublesome problem.
There i s great i n t e r e s t i n developing a q u a n t i t a t i v e understanding of the fundamental nature of these o s c i l l a t i o n s so that
reactor design c r i t e r i a f o r a v o i d i n g them can be developed.
Recent developments by Rawlings (255) would seem to provide a
f i r s t step i n t h i s d i r e c t i o n .
S o l i d - C a t a l y z e d O l e f i n P o l y m e r i z a t i o n . A t h i r d area where
extremely c h a l l e n g i n g p o l y m e r i z a t i o n r e a c t i o n engineering
problems a r i s e i s i n t r a n s i t i o n - m e t a l c a t a l y z e d polymerization
of o l e f i n s such as ethylene, propylene and t h e i r copolymers.
There i s great controversy at present over issues such as ( i )
which f a c t o r s c o n t r o l the molecular weight d i s t r i b u t i o n and
t a c t i c i t y , ( i i ) what causes the d e c l i n e i n c a t a l y s t a c t i v i t y
observed i n these r e a c t o r s , and ( i i i ) what p h y s i c a l phenomena
are o c c u r r i n g i n the pores and on the c a t a l y s t s u r f a c e .
Unambiguous measurements are few, so t h e o r i e s abound. For example,
o l e f i n p o l y m e r i z a t i o n with a Z i e g l e r - N a t t a type c a t a l y s t y i e l d s
narrow molecular weight d i s t r i b u t i o n s when the system i s
homogeneous and very broad molecular weight d i s t r i b u t i o n s when
the p o l y m e r i z a t i o n becomes heterogeneous.
Has the nature of the
c a t a l y s t changed so that some s i t e s are producing short chains
while other s i t e s produce long chains? Or, has the increased
heat and mass t r a n s f e r r e s i s t a n c e of the heterogeneous polymeriz a t i o n produced the great nonuniformity i n polymer chain length?
To produce some answers to these and other questions requires
a combination of mathematical modelling and d i a g n o s t i c experimentation.
There i s some concensus that the p h y s i c a l p i c t u r e
i n s i d e the growing polymer p a r t i c l e i s as f o l l o w s . For
heterogeneous c a t a l y t i c systems polymerization occurs on the
c a t a l y s t s u r f a c e producing polymer chains which f i l l the pores
and grow out from the a c t i v e s u r f a c e . The c a t a l y s t p a r t i c l e
f r a c t u r e s i n t o t i n y fragments as the pores are ruptured by
growing polymer. Monomer, which must d i f f u s e to the c a t a l y s t
surface to be c a t a l y t i c a l l y i n s e r t e d i n t o the polymer chain, sees
an i n c r e a s i n g path f o r d i f f u s i o n as p o l y m e r i z a t i o n progresses
and the c a t a l y s t fragments become more and more encapsulated by
polymer. C l e a r l y t h i s i s a very complex p h y s i c a l s i t u a t i o n and
simple models are not adequate to represent a l l the important
phenomena. Therefore a number of r a t h e r complex models f o r the
c a t a l y s t p a r t i c l e have been developed and t e s t e d computationally
with r e a l i s t i c parameters f o r heat and mass t r a n s f e r as w e l l as
k i n e t i c s . F i g u r e 9 i l l u s t r a t e s some of these models while
Figure 10 (taken from (256)) shows the p r e d i c t e d propylene
monomer c o n c e n t r a t i o n p r o f i l e to be expected i n a polypropylene
polymer p a r t i c l e over a 4 hour period i n a s l u r r y batch r e a c t o r .
Figure 11 i n d i c a t e s the corresponding molecular weight d i s t r i b u t i o n to be expected.
As described i n d e t a i l elsewhere (121,122,
124,256,257), these extensive modelling s t u d i e s show that
5.
RAY
Continuous p o l y m e r i z a t i o n ,
Run 15, R e c i p e 8,
Example o f o s c i l l a t o r y b e h a v i o r
[ S ] - 0 . 0 2 mo l e s / l - w a t e
[I]
- 0.01 mo l e s / l - w a t <
121
in
CSTR,
<3
r i i i
""
300
400
5 00
300
40
500
1 1 1
1 1 1 1
00
rf
f i l l
00
1 1 1 1
SO
'300
300
90
I I I I I
600
7O0
MINUTES
122
CHEMICAL
REACTION
ENGINEERING
S C M
P C M
F M
M Q
GROWTH
Figure 9. Schematic i l l u s t r a t i o n o f p a r t i c l e d i s i n t e g r a t i o n and
the p o s t u l a t e d morphological models; SCM ( s o l i d core model),
PCM (polymeric core model), PFM (polymeric flow model), and
MGM ( m u l t i g r a i n model).
5.
RAY
5-
123
5
Y
I
R
ft
IHE, HOURS
IHE/ HOURS
124
CHEMICAL
REACTION
ENGINEERING
5.
RAY
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
126
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
CHEMICAL
REACTION
ENGINEERING
5.
RAY
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
127
128
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
C H E M I C A L R E A C T I O N ENGINEERING
Munoz-Escalona, .; Villamizar, C.; Frias, P. in "StructureProperty Relationships of Polymeric Solid", Plenum, NY, 1982.
Munoz-Escalona, .; Parada, A. J. Crystal Growth 1980, 48,
250.
Franz, H.; Meyer, H.; Reichert, K.-H. Polymer 1981, 22,
226.
Reichert, . H. Angw. Makromol. Chem. 1981, 94, 1.
Michale, R.; Reichert, . H. Can. J. Chem. Eng. 1981, 59,
602.
Hogan, J. P.; Norwood, D. D.; Ayres, C. A. J. Appl. Poly.
Sci. Appl. Poly. Sci. Symp. 1981, 36, 49.
Vermel', Ye. Ye.; Zakharov, V. .; Bukatova, . K.;
Shkurina, G. P.; Yechevskaya, L. G.; Moroz, . M.;
Sudakova, S. V. Poly. Sci. USSR 1980, 22, 23.
Pino, P.; Mlhaupt, R. Angew. Chem. Int. Ed. Engl. 1980, 19,
857.
Reichert, . H. Proc. MMI Symp. Transition Metal Catal.
Poly. 1981
Doi, Y.; Ueki, S.; Tamura, S.; Nagahara, S.; Keii, T.
Polymer 1982, 23, 258.
McDaniel, M. P. J. Poly. Sci. Poly. Chem. 1981, 19, 1967.
Sailors, H. R.; Hogan, J. P. J. Macromol. Sci-Chem. 1981,
A15, 1377.
Zakharov, V. A. Kinet. Katal. 1980, 21, 892.
Likholobov, V. .; Ermakov, Yu. I. Kinet. Katal. 1980, 21,
904.
Hoff, R. E.; Pullukat, T. J.; Shida, M. J. Appl. Poly. Sci.
1981, 26, 2927.
Vermel', . E.; Zakharov, V. .; Fenelonov, V. B.;
Zaikovskii, V. I.; Zagrafskaya, R. V.; Moroz, . M.;
Bukatov, G. D. Kinet. Katal. 1981, 22, 480.
Brockmeier, N. F. MMI Symp. Transition Metal Catal. Poly.
1081.
Brockmeier, N. F.; Lin, C. . .I.Ch..
Meeting Houston
1979.
Doi, Y.; Nishimura, Y.; Keii, T. Polymer 1981, 22, 469.
Tsutsui, T.; Tanaka, R. Polymer 1980, 21, 1351.
Doi, Y.; Ueki, S.; Keii, T. Macromol. 1979, 12, 814.
Doi, Y.; Takada, M.; Keii, T. Bull. Chem. Soc. Japan 1979,
52, 1902.
Nagel, E. J.; Kirillov, V. .; Ray, W. H. I&EC Product Res.
& Dev. 1980, 19, 372.
Taylor, T. W.; Choi, K. Y.; Yuan, H.-G.; Ray, W. H. Proc.
Int. Symp. Transition Metal Catal. Poly. (Gordon & Breach),
1982.
Yuan, H. G.; Taylor, T. W., Choi, . Y.; Ray, W. H. J
Appl. Poly. Sci. 1982, 27, 1691.
Choi, . Y.; Taylor, T. W.; Ray, W. H. Proc. 1982 IUPAC
Macro., Aug. 1982.
Yamamoto, K. J. Macromol. Sci.-Chem. 1982, A17, 415.
5.
RAY
126.
127.
128.
129.
130.
131.
132.
133.
134.
135.
136.
137.
138.
139.
140.
141.
142.
143.
144.
145.
146.
147.
148.
149.
150.
151.
152.
153.
154.
155.
156.
157.
129
130
158.
159.
160.
161.
162.
163.
164.
165.
166.
167.
168.
169.
170.
171.
172.
173.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
C H E M I C A L REACTION ENGINEERING
5.
RAY
185.
186.
187.
188.
189.
190.
191.
192.
193.
194.
195.
196.
197.
198.
199.
200.
201.
202.
203.
204.
205.
206.
207.
208.
209.
210.
211.
212.
213.
214.
215.
131
132
C H E M I C A L REACTION
ENGINEERING
216.
217.
5. R A Y
133
6
Mixing in Chemical Reactors
JACQUES V I L L E R M A U X
136
C H E M I C A L REACTION
ENGINEERING
papers, which appeared a few years ago or while the present was i n
p r e p a r a t i o n (J_-6) .
Instead o f d u p l i c a t i n g these reviews and r a t h e r than present
i n g an exhaustive l i t e r a t u r e survey, I have chosen t o emphasize
the points which seem the most c r i t i c a l and c o n t r o v e r s i a l , or
those where s i g n i f i c a n t progress has been made i n recent years,
and to give personal views on these s u b j e c t s . In doing so, I ac
cept the r i s k that t h i s review may appear p a r t i a l or incomplete to
those authors whose (sometimes e x c e l l e n t ) papers w i l l be l e f t out.
That mixing i n chemical reactors i s also a problem of v i t a l
importance to i n d u s t r y appears i n some, too r a r e , papers d e s c r i b
i n g the e f f e c t of a g i t a t i o n on y i e l d i n p i l o t p l a n t reactors (7.)
or the d i f f i c u l t i e s of conserving a good s e l e c t i v i t y when s c a l i n g
up a mixing device to the commercial s c a l e (8).
I t i s a p i t y that
p r o p r i e t a r y requirements r e s t r a i n the p u b l i c a t i o n of such indus
t r i a l case s t u d i e s , whose a n a l y s i s would be o f the g r e a t e s t i n t e r
est t o t h e o r i c i a n s o f mixing. But t h i s i s a general problem i n
Chemical Reaction Engineering. Nevertheless, i t i s encouraging to
see i n d u s t r i a l p a r t i c i p a n t s attending meetings and g i v i n g t h e i r
o p i n i o n about the relevance of research topics and about what
should be done to improve our knowledge i n the f i e l d (9,10). This
should prevent "too many academics pursuing too many non-problems"
(Jl).
The l a s t point that should be o u t l i n e d i n t h i s i n t r o d u c t i o n
i s that mixing i n chemical reactors r e a l l y c o n s t i t u t e s an o r i g i n a l
chapter of Chemical Reaction Engineering. Since the p i o n e e r i n g
work of Danckwerts ( 12) , Zwietering (13) and others, i t i s c l e a r
that chemical r e a c t i o n engineering c o n s t i t u t e s a s c i e n t i f i c d i s c i
p l i n e with i t s own methods. The RTD and the segregation concepts
f o r i n s t a n c e , have completely renewed the d e s c r i p t i o n of the beha
v i o u r of r e a c t i n g mixtures i n r e a c t o r s . I am convinced that f u t u r e
progress can be expected i n pursuing novel concepts rather than i n
more s o p h i s t i c a t e d combinations of chemical k i n e t i c s and f l u i d me
chanics. Of course t h i s doesn't mean that we must neglect the con
t r i b u t i o n of the l a t t e r d i s c i p l i n e , as w i l l be seen below.
D e f i n i t i o n and c h a r a c t e r i z a t i o n of the degree of mixing
A d e f i n i t i o n of mixing i s proposed i n many papers and t e x t
books (14, 15, 16, 2),
and t h i s point w i l l not be discussed here.
Several c r i t e r i a are used f o r a q u a n t i t a t i v e c h a r a c t e r i z a t i o n of
the " q u a l i t y of mixing". These have been r e c a l l e d by Hiby (17). In
a non-uniform mixture, l e t p(C) be the l o c a l c o n c e n t r a t i o n d i s t r i
b u t i o n of a species. p(C) may be c h a r a c t e r i z e d by i t s mean C, its_
variance
and the average value AC of the d e v i a t i o n AC = |C - C|
from the mean. From these q u a n t i t i e s , s e v e r a l c r i t e r i a may be de
f i n e d (17), namely 6 = AC/C, 6
= A C / C and = /C. Another
critrium i s = AC/AC , where AC
i s the value o f Sc before mix
i n g (or at the reactorinlet).
Smarting from two_streams o f ( r e
duced) c o n c e n t r a t i o n 0 and 1, then AC = 2 C ( l - C).
The
m a x
max
6.
VILLERMAUX
137
I n t e n s i t y of Segregation d e f i n e d by Danckwerts
is
I = ^/
= o / C ( l - C) , but / = / bas a l s o been used. I f
two species A and are mixed, the d e f i n i t i o n of I becomes 02)
*s
"~ A B^Ao*^Bo* R e l a t i o n s h i p s between a l l these i n d i c e s are
obvious. Their common property i s that the s m a l l e r they are, the
b e t t e r the q u a l i t y of the mixture. The corresponding degrees of
homogeneity may a l s o be defined as 1 - , 1 - 6 , 1 - / J , e t c . . .
Mixing times are the times r e q u i r e d f o r 6, or , or I to
f a l l from t h e i r i n i t i a l value (before m i x i n g ) , down to some pres
c r i b e d small value ( f o r instance 0.05
or 0 . 0 1 ) . We s h a l l see that
i n Lagrangian coordinates, - /(do /dt) i s a l s o a mixing time.
The e s t i m a t i o n of mixing times i n s t i r r e d tanks w i l l be discussed
i n a further Section.
The s c a l e of segregation gives i n f o r m a t i o n on the s i z e of se
gregated regions. Let c(x) and c(x+r) be the f l u c t u a t i n g concen
t r a t i o n s at p o i n t s and x+r (c = C - C), then the a u t o c o r r e l a t i o n
f u n c t i o n of c o n c e n t r a t i o n i s (2):g (r) = c(x) c ( x + r ) / o .
The s c a l e of segregation i s then defined as :
2
8 s ( r ) dr
C H E M I C A L REACTION ENGINEERING
138
dp the mean age at " p o i n t " and Var denotes the variance of the
d i s t r i b u t i o n s over a l l " p o i n t s " or a l l molecules i n the r e a c t o r .
J = 1 i n a t o t a l l y segregated mixture ( a l l the ages are the same
w i t h i n a " p o i n t " = ) and J takes a minimum value depending on
the residence time d i s t r i b u t i o n when mixing e a r l i n e s s i s at a mi
nimum. J i s s t i l l a very popular q u a n t i t y i n the l i t e r a t u r e where
i t i s used by many authors to compare t h e i r micromixing models.
However I t h i n k that w h i l s t i t c o n s t i t u t e s some u s e f u l reference
for mixing e a r l i n e s s , i t i s of l i t t l e i n t e r e s t f o r the design of
chemical r e a c t o r s as i t cannot be measured d i r e c t l y nor be used
for a s t r a i g h t f o r w a r d c a l c u l a t i o n of chemical conversion.
Another i n d i r e c t mixing index was proposed by Ogawa et a l .
(25, 26), based on i n f o r m a t i o n theory and on the e s t i m a t i o n of the
"entropy" of a mixture. This "entropy" i s defined from the t r a c e r
d i s t r i b u t i o n among zones i n the r e a c t o r as = - V?
In p^,
where V* i s the reduced volume of zone i and p i t h e i = l
" p r o b a b i l i t y " of occurence of the t r a c e r i n zone i (see reference
(25) f o r more d e t a i l s ) . As mixing proceeds, the degree of homoge
n e i t y of the mixture i s defined as = H/H^, where H^ i s the f i n a l
entropy of the homogeneous mixture. This method was used to study
the mixing r a t e i n s t i r r e d v e s s e l s . M was p l o t t e d as a f u n c t i o n of
time from a record of the concentrations at v a r i o u s places i n the
v e s s e l . This allowed a comparison of e f f i c i e n c y of d i f f e r e n t a g i
t a t o r s (26). As an i n t e r e s t i n g g e n e r a l i z a t i o n , the macromixing ho
mogeneity i n a continuous r e a c t o r having a RTD E ( t ) may be defined
as (25) : M = - J " E ( t ) In E ( t ) dt,from which i t i s seen that M= 0
i n a plug flow r e a c t o r and M = 1 i n a continuous s t i r r e d r e a c t o r .
E u l e r i a n approach: M i x i n g and
Turbulence
6.
viLLERMAUX
139
1/3
2/3
(3-1)
f o r gases
Se
1/3
2/3
il
1/2
In Sc
for liquids
(3-2)
1 / 3
constant
dissipation
time
Kolmogorov m i c r o s c a l e
Viscous
Taylor
.2
A l l directions
Taylor microscale
Spectra
energy d i s s i p a t i o n
= 10
rt
dt
= (
3
2
...2
~,2
/)
10
3/2
dt
dk,
f
lOv
,1/2
B a t c h e l o r m i c r o s c a l e _
)dk
E(k.)dk.
1
1
E(k,)
k, E ( k
dk,
E(k,)
E(k.)
direction
<*L ,
@bv
1/2
1 M
(5)/)
/
s i
microscale
-/
time c o n s t a n t
dissipation
intensity
microscale
/)
Se
Corrsin
Small
Corrsin
Corrsin
Segregation
Segregation
-1
"
E (k)
s
dr
dk
dk
2
'
s
12<
dk
E (k)
dk
,2
de
dt
(Corrsin)
g(r)
/ V >
E(k)
de*
dt
5)
1
,2
= 2
(&^/)^
12$c'
c'
E (k)
g(r)
c(x) c(x+r)
,2
(c )
Concentration C = C + c
Homogeneous I s o t r o p i c Turbulence
du'
dt
u(x+r)
,2
f ( r ) dr
E(Q)
,
,2
30 v u'
= 30
u'
E ( k ) , One
/2
u(x)
(uV
=f
energy o f t u r b u l e n t motion
Turbulent
Kinetic
f(r)
autocorrelation
Macroscale
u' =
U - U + u
Mean square f l u c t u a t i o n
Velocity
Table I .
w
m
W
25
>
>
PI
4^
6.
VILLERMAUX
141
dl
(3-3)
dt
142
C H E M I C A L REACTION ENGINEERING
- ~
- " 2
(C
' B
A B
A B
(3-5)
C
Ao* Bo
6.
viLLERMAUX
143
144
C H E M I C A L REACTION
ENGINEERING
(RTD)
6.
145
viLLERMAUX
Generalization
Reference
steady
transient, periodical
(0(56)
Volume
constant
variable, periodical
ly variable
(0(56)
(58) (59)
Density
constant
variable
(0(56)
convective
dispersive
(0(57)
Flow regime
Inlet/Outlet
Number of
Inlets/Outlets
1/1
Semi-batch r e a c t o r
2/1
n/n
1/0 ,
2/0 *
( 0 ( 5 6 ) (60)
(61)(62)(1)
(56)
| f + V.C*5> + ? = 0
at
The
(5-1)
l o c a l age d i s t r i b u t i o n f u n c t i o n i s defined as f = /. f i s
146
C H E M I C A L REACTION
ENGINEERING
Figure 1. The BPT (bundle o f p a r a l l e l tubes) model. The f l o w r a t e i n a tube w i t h residence time between t and t
^
dQ = E ( t )dt . The f l u i d flows i n the tubes at constant v e l o c i t y .
A l l p a r t i c l e s on a v e r t i c a l have the same age. The h e i g h t o f the
p i l e i s Q. The l o c u s o f tube e x t r e m i t i e s i s a p i c t u r e o f F-curve
ts
E(t) d t ) . Olson and Stout a l s o make use o f such a model
/
i n t h e i r review (177).
s
6.
viLLERMAUX
147
o u t
o u t
\ a. o u t n,out
V
^
d"t
}+
( 5
"
3 )
where
i s the n^ti order moment of E ( t , t ) and that o f
I(a,t).
These equations a l l o w v a r i o u s s p e c i a l cases t o be t r e a t e d .
This l i n k s the n ^ order moment of the RTD to the n-l*-* order mo
ment of the IAD.
The IAD I ( a , t ) i n a chemical r e a c t o r i s s p e c i a l l y i n t e r e s t i n g
and i t does not seem that s u f f i c i e n t a t t e n t i o n has been p a i d t o
the p o s s i b i l i t i e s o f f e r e d by t h i s f u n c t i o n . For i n s t a n c e , l e t us
consider a semi-batch r e a c t o r , and l e t Q(t) be the feed f l o w r a t e
of an incompressible f l u i d . The instantaneous f l u i d volume i s
V = J Q i t ^ d t ' , from which the IAD i s w r i t t e n I ( a , t ) = Q(t-a)/V.
I ( a , t ) can be used to c a l c u l a t e the chemical conversion i n d i f f e
rent segregation s t a t e s . Consider a species of c o n c e n t r a t i o n C
produced w i t h the r a t e n t . I f the mixture i s assumed to be w e l l mi
xed a t the molecular s c a l e , one obtains the f a m i l i a r mass balance
equation
s
QC
in
+&V =
(VC)
(5-4)
_ = & ,
a = 0, C - C . ( t - a )
B
(5-5)
C_(a,t) I ( a , t ) da
y
(5-6)
JD
Society Library
1155 16th St. N. W.
In Chemical ReactionWashington,
EngineeringPlenary
D.C.Lectures;
20036Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
148
out
o u t
9 F
wn
n a v e
9 t
C _(t) =
out
C f t , C. ( t - t )1
( t ,t) dt
B [s' m
s J out s'
s
v
(5-7)
SC
3
c
t o
o n t
(., )
t
Qut
o u t
( t ) = C(X = 0,t)
6.
viLLERMAUX
149
S s r
o f :
k F
< j>
c
( 5
9 )
(5-10)
t i
150
C H E M I C A L REACTION
ENGINEERING
6.
VILLERMAUX
151
models
152
CHEMICAL
REACTION
ENGINEERING
C
0
( c
j B
E ( a )
- r ^
- & . ( C .
da
C.
j ,B
"
C.
jo
- i
- V
6.
viLLERMAUX
153
ts+dts ts
+dX
DISCHARGE
yzQ t<0
154
C H E M I C A L REACTION
ENGINEERING
i s : d^Q = Q A ( X , t ) d X d t
where A ( X , t ) i s a mixing f u n c t i o n
which can a l s o be expressed from the RTD by i n t r o d u c i n g h ( X , t ) :
A ( X , t ) = h ( X , t ) E ( t ) . For a given l i f e expectancy , the f r a c
t i o n of f l u i d i n the Min.Mix. s t a t e i s s and the complementary
f r a c t i o n 1 - s i s i n the Max.Mix. s t a t e . From (6-4) and f i g u r e 4,
s(X,t ) = s(0,t ) + j
h(X,t )dX (6-3)
where one may have
s ( t , t ) 1 (tube inet) and s ( 0 , t ) 0 (tube O u t l e t ) . s ( X , t ) ,
also w r i t t e n s(X,a) i s known as the "segregation f u n c t i o n "
although, as the above remark i n d i c a t e s , "segregation of ages"
would be b e t t e r . In our p a r t i c u l a r tube, the flowrate of the Max.
Mix. f l u i d i s d Q
= Q g(X)dX with g(X) = } A ( X , t ) d t =
J~ h ( X , t ) E ( t ) d t . In the whole r e a c t o r , the Max.Mix flowrate i s
thence Q
= J " g(X')
dX .
This t r a n s f e r between two environments can a l s o be described
as a Lagrangian process where a small band of volume
d^Max
^Max ^ moves with a constant v e l o c i t y along the X axis i n
the d i r e c t i o n of decreasing X. Spencer et a l . (68) consider t h i s
volume as an "accumulator" whose dimensionless volume was d e f i
ned by
s
M a x
m a x
f
A (-z, - t ) dz
z
(6-4)
I
dt
A(-z,-t)
i,B
C ( z ) , t-z
k
C. dz +31
(6-5)
6. viLLERMAUX
155
c.(A) - c . ( x , t )
ac.
3a
1
where C.() =
j
1 - F(X)
w
(6-6)
m
C.(X,t) E ( t ) dt
j
b
S
b
(6-7)
156
SU.a)
6.
VILLERMAUX
157
158
C H E M I C A L R E A C T I O N ENGINEERING
Q.
6.
VILLERMAUX
159
d u l i Ig and I
f o r the E.E. and the L.E. r e s p e c t i v e l y , and the
"segregation parameter R x [s = e x p ( - R t ) ] . The reader w i l l
understand that with a l i t t l e imagination an almost endless s u i t e
of models of t h i s k i n d can be conceived.
In the models c i t e d above, i n t e r a c t i o n between the e n v i r o n
ments from the two feedstreams was modelled by a C-D mechanism.
The IEM Model can also be used f o r t h i s purpose. Equation (6-6)
s t i l l holds but the mean value Cj(A) at a given l i f e expectancy
must comprise both feedstreams 1 and 2 :
L
11
l - FM
FAX)
C j l
( A , t ) a, E
s
l (
t )
s
dt
(6-8)
C (X,t ) a
j 2
E ( t ) dt
2
with a = Q /(Q + Q ) , ^ ( ) = a
E ( t ) d t and s i m i l a r d e f i
n i t i o n s f o r feestream 2.
I now come to a very important observation. We have seen that
i n t e r a c t i o n between the environments (or between the p a r t i c l e s
themselves i f t h i s i s assumed equivalent to segregation decay)
could be represented by d i f f e r e n t one parameter models, e.g.
- The C-D model, parameter I =
- The IEM model, parameter T / t
- The Models of Ng and R i p p i n , parameter R T
- The Shrinking-Aggregate Model (71), parameter /te
160
C H E M I C A L REACTION ENGINEERING
E.E.1
E.E.2
Qi
6.
VILLERMAUX
161
162
C H E M I C A L REACTION
ENGINEERING
Figure 8. Equivalence between the C-D model and the IEM model.
Instantaneous r e a c t i o n between two unmixed feedstreams o f A and
i n s t o i c h i o m e t r i c amount i n a CSTR (33).
Figure 9
Bo
6.
VILLERMAUX
2 3 4 5
10
163
20 30 50
Figure 10. Equivalence between the C-D model and t h e IEM model.
Reactor w i t h two i n l e t s having d i f f e r e n t RTDs e q u i v a l e n t t o t h a t
o f 2 and 6 tanks i n s e r i e s , r e s p e c t i v e l y . Unmixed feedstreams o f
A and (equal f l o w r a t e s ) , second-order r e a c t i o n , C^ =8
A
^
e l e a v e n and Tobgy (77) f o r ?he C-D model.
k C
T r
164
C H E M I C A L REACTION
ENGINEERING
6.
VILLERMAUX
165
1. D i s t r i b u t i o n o f one f l u i d through the other and u n i f o r m i z a t i o n of average composition without decreasing l o c a l concentra
tion variations.
2. Reduction of s i z e of the regions of uniform composition
and increase of contact between regions of d i f f e r e n t composition.
3. Mixing by molecular d i f f u s i o n .
Stage 1 i s c l e a r l y macromixing. Let us review the models pro
posed f o r the l a s t two processes (32).
P u r e l y convective mixing. An important c o n t r i b u t i o n t o the
s o l u t i o n of t h i s problem was given by O t t i n o , Ranz and coworkers
(99-106) i n the l a s t three years. However, the a b s t r a c t c h a r a c t e r
o f the mathematical formalism used i n these papers might d i s c o u r
age p r a c t i t i o n e r s who are not very f a m i l i a r w i t h t e n s o r a n a l y s i s ,
although the u n d e r l y i n g concepts are f i n a l l y r a t h e r simple. The
theory considers only convective mixing under the i n f l u e n c e of the
v e l o c i t y f i e l d . D i f f u s i o n i s f u r t h e r superimposed on to the p a t t e r n
created by convection. The main i d e a i s that once the v e l o c i t y
f i e l d i n s i d e the r e a c t o r i s known, i t i s p o s s i b l e t o p r e d i c t the
deformation of any m a t e r i a l p o r t i o n of f l u i d as a f u n c t i o n of the
Lagrangian time attached to t h i s element. Two q u a n t i t i e s are of
s p e c i a l i n t e r e s t : the m a t e r i a l time r a t e of change of l i n e a r
s t r e t c h , and that of area s t r e t c h . Let L = V.lf =
.1 be the v e l o
c i t y g r a d i e n t . From t h i s , we may d e f i n e the ^
i
s t r e t c h i n g tensor D = (1/2)(L + L ) and the v o r t i c i t y tensor
Q = (1/2)(L - L ) . The fundamental r e l a t i o n s h i p s e s t a b l i s h e d by
O t t i n o , Ranz e t a l . (99^, 101, 103, 105) are then f o r the r a t e of
change o f l i n e a r s t r e t c h (/)
and area s t r e t c h ( ?), respec
tively:
x
= D :
/ = V.U - D : n n
(7-1)
/a = - / = - D : n n
(7-2)
166
C H E M I C A L REACTION
ENGINEERING
1 / 2
= ( /2)
1 / 2
(7-3)
->- -D : n
->
D :
( = D)
( /2)
1 / 2
= , Uy = - ay, U
1 / 2
(7-5)
= 0, laminae i n i
exp(- at)
(7-6)
3) S t r e t c h i n g at constant v e l o c i t y (
= 0)
= - G t / ( 1 + G t ) and = 6 (1 + G t ) "
2) Stagnation flow ( U
t i a l l y normal to Oy) (104)
= G / ( l + Gt), U
= 0,
(7-7)
6.
VILLERMAUX
167
1 / 3
^- ^
e
I/O
= 726W
-1/3
S
276^
/"7 Q\
,
%
i n l i q u i d s (Se ^ 1000).
i s the f a m i l i a r Kolmogorov m i c r o s c a l e
(see above).
The dependence of t on experimental parameters
i s thus t ^ t
<)-2/3
problems remain to be s o l ved : How to estimate the i n i t i a l s i z e Z of the aggregates ? Is i t
p r o p o r t i o n a l to the i n i t i a l v e l o c i t y U of the f l u i d as i t has been
assumed i n s t i r r e d r e a c t o r s (71) ? What i s the expression of the
energy d i s s i p a t i o n r a t e ? As already pointed out, i t seems necessary to introduce e f f i c i e n c i e s j and 2 f o r the u t i l i z a t i o n of mecha
n i c a l energy and k i n e t i c energy d i s s i p a t i o n r e s p e c t i v e l y (71, 108)
= j ] + 2 2 * These are questions f o r f u r t h e r research.
e
Mixing by molecular d i f f u s i o n .
This i s the u l t i m a t e and f i
n a l l y the only process r e a l l y able to mix the components of a f l u i d
to the molecular s c a l e . The time constant f o r t h i s process i s the
d i f f u s i o n time tp = \/<&. y i s a shape f a c t o r and L i s the r a t i o
of the volume to the e x t e r n a l surface area of the p a r t i c l e . For
instance l e t us consider v a r i o u s shapes : slabs (thickness 2 R , case
of l a m e l l a r s t r u c t u r e with s t r i a t i o n thickness 6 = 2 R ) , long cy
l i n d e r s (diameter 2 R , case of filamentous s t r u c t u r e ) , and spheres
(diameter 2 R , case of s p h e r i c a l aggregates).
I t can be.shown (110) that
2
= {HH
'
(p 0(
+
P +
3)&
168
C H E M I C A L R E A C T I O N ENGINEERING
1 / 4
1 / 4
1 / 3
Table I I I
Experimental parameters : = 10
ms
,3=10
/> =
T
t
3/2
1/2
/(3> )
=2
= /2
|/)
1 / 3
= (2/)
Case 2 : = 10 Watts
kg""
L = 0.1 m
(small r e a c t o r )
32 ym
70 ym
18 ym
1 6 ym
1 s
0.3 s
\l = <2>/)
1/2
0.2 s
0.9 s
1/2
, Sc = 10
Case 1 : = 1 Watt
kg
L = 0.3 m
(large r e a c t o r )
s
Kolmogorov
Corrsin
A
ms
0.45 10" s
1.4 10~" s
5
3.5 10" s
6.
VILLERMAUX
169
t n
R i
170
C H E M I C A L REACTION
= /
Jo
JL^
H t < )
or =S>
dt
ENGINEERING
(7-10)
T h i s
i s
a n
6.
VILLERMAUX
Figure 11.
and the IEM
reaction i n
for perfect
second-order
111
172
l
&2
A +
R, R +
S. The curves represent t h e average con
c e n t r a t i o n s v s . (reduced) time i n a s p h e r i c a l p a r t i c l e immersed
i n a bath o f constant composition (C^ 0.105, C = 0 ) . I n i t i a l
concentrations i n the p a r t i c l e : C
= 0, CBO = 1> R
0
k C g R / ^ = 2 f o r A and R. cannot d i f f u s e w i t h i n the p a r t i c l e
(S> = 0 ) . k-^/k^ = 10. F- represents the t o t a l production o f R
(equivalent c o n c e n t r a t i o n i n the p a r t i c l e ) . B a s i s f o r the e q u i
valence t . - t . = 0 L / j ; = 3/5, L = R/3 (sphere). The
agreement i s s a t i s f a c t o r y . I n much " s t i f f e r " c o n d i t i o n s
(k^> > k ) , the agreement i s always good f o r the o v e r a l l produc
t i o n o f R, even i f the i n d i v i d u a l c o n c e n t r a t i o n p r o f i l e s become
different.
=
///
f
t /t
R
0.1
10
6.
VILLERMAUX
173
m i c r o
1 / 2
- 1
174
C H E M I C A L REACTION ENGINEERING
6.
VILLERMAUX
175
1 1
The S t i r r e d Tank
A review on mixing i n chemical r e a c t o r s would be incomplete
without an account of recent progress i n the understanding of the
working of s t i r r e d tanks, which remain the b a s i c devices f o r indus
t r i a l mixing.
I n t e r n a l c i r c u l a t i o n p a t t e r n s and turbulence. Sasakura e t
a l . (138) and Rachez e t a l . (139) i n v e s t i g a t e d i n t e r n a l age d i s t r i
butions by means of t r a c e r s and proposed r e p r e s e n t a t i v e models o f
the c i r c u l a t i o n p a t t e r n . Bryant and coworkers (135, 140, 141) and
Reuss s t u d i e d more s p e c i f i c a l l y c i r c u l a t i o n times i n l a r g e s t i r r e d
tanks by using r a d i o f l o w - f o l l o w e r s (aiming a t a p p l i c a t i o n s f o r
fermenters > 0.5 m ). They showed that c i r c u l a t i o n times t were
log-normally d i s t r i b u t e d :
3
f(t )
c
exp
/2-ot
In t -
c
/2
c
and n a t u r a l variance s being given by
z
176
C H E M I C A L REACTION
ENGINEERING
(8-2)
(8-3)
e (d/d ) *
m
and f o r p r o p e l l e r s
N0
(d/d )
6.
VILLERMAUX
177
quasi-exhaustive surveys by J o s h i e t a l . f o r g a s - l i q u i d r e a c t o r s
(150) and T a v l a r i d e s and Stamatoudis f o r l i q u i d - l i q u i d r e a c t o r s
05, 40 . J o s h i e t a l . gave a thorough comparison of c o r r e l a t i o n s
for N0 . This product seems to increase w i t h the gas-flowrate.
L i t t l e i s yet known about the s t a t e of mixing of the dispersed gas
and on the i n f l u e n c e of s o l i d i n suspension.
T a v l a r i d e s presents a s o p h i s t i c a t e d model f o r r e p r e s e n t i n g
coalescence and breakage of d r o p l e t s i n l i q u i d - l i q u i d d i s p e r s i o n s .
The model r e l i e s on the p o p u l a t i o n balance equation and s t i l l r e
q u i r e s the adjustment of 6 parameters. The s o l u t i o n of such equa
t i o n s i s d i f f i c u l t and r e q u i r e s the use of Monte-Carlo methods
(151) . The e f f e c t of coalescence and break-up of d r o p l e t s on the
y i e l d of chemical r e a c t i o n s was s t u d i e d by V i l l e r m a u x (33). M i c r o mixing e f f e c t s may occur even i n batch r e a c t o r s i f there i s a drop
s i z e d i s t r i b u t i o n and mass-transfer c o n t r o l . Although p r a c t i c a l
r u l e s f o r the design and scale-up of l i q u i d - l i q u i d r e a c t o r s are
a v a i l a b l e as Oldshue showed i n the case of a l k y l a t i o n ( 152), many
problems remain unsolved (.5) : mass t r a n s f e r e f f e c t s , high hold-up
f r a c t i o n s (> 20 % ) , l a r g e d e n s i t y d i f f e r e n c e s , high v i s c o s i t i e s ,
i n f l u e n c e of s u r f a c t a n t s .
178
C H E M I C A L REACTION ENGINEERING
6.
VILLERMAUX
179
> 2R
k
R + M
*> R
k
Initiation
Propagation
t P
R +
> + R
Transfer to Polymer
k
R + R
-> +
Termination ( D i s p o r p o r t i o n a t i o n )
General c o n c l u s i o n
The end of t h i s survey leaves us w i t h the f e e l i n g that r e
search on mixing i n chemical r e a c t o r s i s a very l i v e l y area, where
problems have been attacked from s e v e r a l d i r e c t i o n s (turbulence
theory, RTD and mixing e a r l i n e s s , segregation and micromixing . . . ) .
I f the major concepts have been i d e n t i f i e d , there i s s t i l l a need
f o r a u n i f i e d theory a l l o w i n g a - p r i o r i p r e d i c t i o n s from the s o l e
knowledge of physicochemical p r o p e r t i e s and operating parameters,
even i f encouraging progress has been made i n t h i s d i r e c t i o n .
Without r e p e a t i n g the conclusions drawn at the end of each
180
Q2
, Q6 , 0.8
04
,X
Figure ih.
Free r a d i c a l p o l y m e r i z a t i o n i n a CSTR. D i s p e r s i o n
Index DI v s . conversion X.
S - segregated flow, M = w e l l - m i c r O mixed flow, I = l i n e a r p o l y m e r i z a t i o n k = 5 x L mol"- * h
k
= 1,5 x 10
L mol" h " , k = 0.033 1' , f = 0.5, A = 3 x 10"
mol L
, S =7.12
mol L"" ( s o l v e n t ) , M = 3.56 mol L " .
Curves
2 t o U:
T r a n s f e r t o polymer. 2 : k p = 3-5 x 1 0 mol L " h
,
3 : k
= 1.05 x I0h
I T m o l " h " , k : k p = 1.05 10 L
mol"
h"* , A = 3 x 10
mol L " , k = 0.33 h "
(other parameters un
changed) .
1
t p
3.0i
DI
S
2-5
'~
s'
. /
^ '
/
__/ N-100
RPM
(o)N-300
x)
/ ^
^-----*
L -
HOURS
Figure 15.
E f f e c t of segregation on p o l y m e r i z a t i o n of styrene
i n cyclohexane s o l u t i o n . Standard CSTR with h b a f f l e s and a
6-blade t u r b i n e , V = 670 cm , = 75 C.
D i s p e r s i o n Index DI
vs. space time. Influence o f a g i t a t i o n speed. Curves S (segre
gated flow) and M (we11-micromixed flow) c a l c u l a t e d from batch
experiments^ I n i t i a t o r : PERKADOX l 6 , A = 0.033 mol I T ,
k
= 5 x 10" s " , f = 0.85; M = 6.65 mol L " , S = 2.22 mol I T .
3
6.
VILLERMAUX
181
182
CHEMICAL
Literature
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2.
3.
4.
5.
6.
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8.
9.
10.
11.
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21.
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25.
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27.
28.
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30.
31.
32.
33.
REACTION
ENGINEERING
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6.
VILLERMAUX
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186
C H E M I C A L REACTION
ENGINEERING
INDEX
Background, h i s t o r i c a l survey
of mathematics
1-15
Baffles
f l u i d bed r e a c t o r , design.... 40f
f u l l - s c a l e cold flow model
design
44
Band-aging in methanol-togasol ine process
25-27
Batch s t i r r e d tank,
polymerization r e a c t i o n s . . . 109t
Batchelor microscale,
homogeneous i s o t r o p i c
turbulence
138-41
Bead polymerization
109t
BedSee also F l u i d bed
Bed, in f l u i d bed r e a c t o r
c r o s s - s e c t i o n a l area
68,72-78
density of s o l i d s
67-69
height
50-55, 67-69
length and gas r e c y c l e
system
34
temperature
69-73
weight
67-69
Belousov-Zhabotinsky
r e a c t i o n in continuous
flow s t i r r e d tank r e a c t o r . . 143
B i f u r c a t i o n , Hopf
13-14
B i f u r c a t i o n diagrams
11-12
189
In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
190
CHEMICAL REACTION
ENGINEERING
C a t i o n i c polymerization
reactions
103-7
C e l l models, mixing theory
176
Chain t r a n s f e r in
polymerization r e a c t i o n s . . 103-7
Chaotic behavior
13
Chemical r e a c t i o n and
mixing
169-70
Chemical r e a c t o r s S e e Reactors
Circulation
of c a t a l y s t f o r f u l l - s c a l e
cold flow model
44
in s t i r r e d tanks, i n t e r n a l
pattern
176-77
Closure problem
141
Coal
19
Coal combustion
reactions
66,87-90
r e a c t o r s , f l u i d bed
55-56
atmospheric pressure
controlling
parameters
65-93
feed diameter s e l e c t i o n . . . 80-87
feed l o c a t i o n
87-90
f l u i d mechanics
66,72-78
heat t r a n s f e r
66,78-87
Coal-to-gasoline v i a
methanol
20f
Coalescence-dispersion
process
142
Coalescence-dispersion process,
random model, mixing
theory
156-64
Coke formation in methanolto-gasoline conversion 25-27,42t
Cold flow model, f u l l - s c a l e ,
b a f f l e design and c a t a l y s t
circulation
44
Combination termination in
polymerization r e a c t i o n s . . 103-7
Combustion, c o a l , using f l u i d bed
atmospheric pressure
c o n t r o l l i n g parameters.. 65-93
bed c r o s s - s e c t i o n a l
area and flow regime.... 72-78
bed height and pressure
drop
67-69
bed temperature
69-73
carbon combustion
efficiency
80-87
f l u i d mechanics
72-78
heat of r e a c t i o n
69
immersed tubes and flow
regimes
92-93
particle size
69-73
reactions
66
reactors
55-56
INDEX
191
Combustion, c o a l , using f l u i d
bedContinued
s u l f u r capture
69-73
volatile evolution
87-90
Commercialization
of methanolto-gasol ine process
32-44
of, polymerization r e a c t o r s . . . 109t
Concentration
oxygen, and carbon combustion
efficiency
82-83
propylene, p r o f i l e s in the
m u l t i g r a i n model f o r
c a t a l y t i c polymerization
120-24
solvent, in polymerization
reactions
110-15
Concentration d i s t r i b u t i o n
136
Concentration f l u c t u a t i o n s ,
turbulence theory
138-40
Concentration macroscale
137
Condensation polymerization... 103-7
Conductive f l u x e s and heat
t r a n s f e r in atmospheric
pressure f l u i d bed
combustor
78-80
Configuration of z e o l i t e
c a t a l y s t f o r methanolto-gasol ine process
21-23
Constructive theory of
p a r t i t i o n s , Sylvester
3
Continuous fermentor
12
Continuous flow reactor
steady s t a t e , mixtures with
v a r i a b l e density
148-49
s t i r r e d tank
49
Belousov-Zhabotinsky
reaction
143
polymerization r e a c t i o n s . . 109t
emulsion
114-20
free r a d i c a l
178-79
isothermal, of methyl
methacrylate
113f
solution
110-14
Continuous f r e e r a d i c a l
polymerization, mixing
theory
178-79
Convective f l u x e s , heat
t r a n s f e r , atmospheric
pressure f l u i d bed
combustor
78-80
Convective mixing
165-66
Convergence and i n f i n i t e s i m a l
numbers
8
Conversion, steady-state
monomer, vs. reactor
residence time in s o l u t i o n
polymerization
113f
192
CHEMICAL REACTION
Dehydration r e a c t o r
commercial f i x e d bed plant
design
37-39
in methanol-to-gasoline
processes, product
yields
42t
Density
of atmospheric pressure
f l u i d bed combustors.... 67-93
of b a f f l e s
f o r f u l l - s c a l e cold flow
mode1.................... 44
f o r f l u i d i z e d bed r e a c t o r . . 4 0 f
of bed s o l i d s in atmospheric
pressure f l u i d i z e d bed
combustor
67-69
of continuous flow s t i r r e d
tank emulsion
polymerization r e a c t o r . . . 117f
of dehydration r e a c t o r
37-39
of f i x e d bed r e a c t o r s . . . . 27,37-39
of methanol-to-gasoline
reactor
23-32
of multibed r e a c t o r
29f
of polymer r e a c t o r
103-7
probability functions
141-42
and residence time
d i s t r i b u t i o n theory
145t
and steady-state
continuous r e a c t o r s . . . . 148-49
of v a r i a b l e s in f l u i d i z e d
bed r e a c t o r
62
Diameter
of bubbles in atmospheric
pressure f l u i d bed
combustor
75-77
of coal feed in atmospheric
pressure f l u i d bed
combustor, s e l e c t i o n . . . . 80-87
of p a r t i c l e s
in f l u i d bed r e a c t o r s
55
in f l u i d bed r e a c t o r s ,
convective and r a d i a t i v e
c o n t r i b u t i o n s to heat
transfer
78
of pores in s u l f a t i o n of
limestone
70-73
D i f f e r e n t i a l equations in
chemical r e a c t o r theory.... 13
Diffusion
of ash, c o n t r o l i n
atmospheric pressure
f l u i d bed combustor
87
e x t e r n a l , vs. k i n e t i c s in
carbon combustion
85
molecular, in mixing
166-69
of oxygen and carbon
combustion e f f i c i e n c y . . . 82-83
ENGINEERING
193
INDEX
Extruder, polymerization
reactions
109t
194
CHEMICAL REACTION
F l u i d bed r e a c t o r s
Continued
carbon combustion
efficiency
80-87
c o n t r o l l i n g parameters.... 65-93
flow regimes and immersed
tubes
92-93
f l u i d mechanics
66,72-78
heat t r a n s f e r
66,78-87
particle size
69-73
s u l f u r capture
69-73
volatile evolution
87-90
for methanol-to-gasoline
process
28f,30-32,40-44
p i l o t plant scale-up
40-43
F l u i d mechanics, determination
of bed c r o s s - s e c t i o n a l
area and flow regime in
atmospheric pressure f l u i d
bed combustor
72-78
F l u i d p a r t i c l e s , mechanism o f
interaction
164-75
F l u i d i z a t i o n and heat t r a n s f e r
d i f f e r e n c e s of atmospheric
pressure f l u i d bed
combustors and f l u i d
catalytic reactors
67
F l u i d i z a t i o n v e l o c i t y in f l u i d
bed r e a c t o r s
52-56,72-78
Fluxes, conductive and
convective, heat t r a n s f e r
in an atmospheric pressure
f l u i d bed combustor
78-80
Formaldehyde, heats of
polymerization
106t
Formation
of bubbles in f l u i d bed
reactor, x-ray
photograph
58-60
of durene in methanol-togasol ine process
25-27
of n i t r i c oxide in coal
combustion
66
Formation k i n e t i c s o f
methanol-to-gasoline
process
23-25
Fragmentation of p a r t i c l e s in
an atmospheric pressure
f l u i d bed combustor
87
Free r a d i c a l polymerization
mixing theory
178-79
reactions
103-7
Freeboard r e a c t i o n s in an
atmospheric pressure f l u i d
bed combustor
92
Fuel flow r a t e in an
atmospheric pressure f l u i d
bed combustor
69
ENGINEERING
Gas
l i g h t , methanol-to-gasoline
processes
42t
n a t u r a l , conversion to
gasoline v i a methanol.... 20f
Gas phase
alchemy
3-4
c i r c u l a t i o n , f l u i d i z e d bed
reactor
50-62
Corrsin microscale, mixing
theory
139-41
flow, atmospheric pressure
f l u i d bed combustor
74-78
mixing, atmospheric
pressure f l u i d bed
combustor
77-78
r e c y c l e system and bed
length
34
v e l o c i t y , atmospheric
pressure f l u i d bed
combustors vs. f l u i d i z e d
c a t a l y t i c crackers
66-67
v e l o c i t y , f l u i d bed
reactors
52,55-56
G a s i f i c a t i o n , carbon, in f l u i d
bed combustors
85
Gasoline
manufacture from methanol... 19-46
treating
37,38f
y i e l d in scaled-up f i x e d bed
reactor
35t,42t
G i l d e r s l e e v e , B a s i l Lanneau.... 2-3
Grain model, calcium oxide.... 70-72
H
Heat exchange
in c a t a l y t i c r e a c t o r s
67
in tubular r e a c t o r s in a
methanol-to-gasoline
process
32
Heat of r e a c t i o n
combustion, atmospheric
pressure f l u i d bed
combustor
69
conversion, limestone to
calcium s u l f a t e
69-73
polymerization
106t
in a s t i r r e d tank r e a c t o r . . . . 14
Heat removal, polymerization
reactions
106
Heat sink, isothermal, tubular
reactors
32
Heat t r a n s f e r
in an atmospheric pressure
f l u i d bed combustor.. 67,78-80
195
INDEX
Heat t r a n s f e r C o n t i n u e d
in an atmospheric pressure
f l u i d bed combustor vs.
fluidized catalytic
reactors
67
in a f l u i d bed
30
in nonadiabatic r e a c t o r s . . 28f,29f
in a s t i r r e d tank reactor.... 14
Heavy gasoline t r e a t i n g
technology
37,38f
Height
bed
and bubble s i z e in a f l u i d
bed r e a c t o r
50-55
and pressure drop in an
atmospheric pressure
f l u i d bed combustor... 67-69
freeboard, in an atmospheric
pressure f l u i d bed
combustor
92
Heterogeneous media,
polymerization
105t
Heterogeneous r e a c t o r s ,
isothermal
149
H i s t o r i c a l survey of
mathematics
1-15
Homogeneity degree, mixing
theory
137
Homogeneous isothermal
reactors
149
Homogeneous i s o t r o p i c
turbulence
138-40
Homogeneous media,
polymerization
105t
Hopf b i f u r c a t i o n
13-14
Horizontal scale-up of f l u i d
bed r e a c t o r s
40-42
Hydrocarbons
conversion r e a c t i o n of
methanol
23-25
y i e l d in scaled-up f i x e d
bed reactor
35t,42t
Hyperreal numbers
8
I
Immersed tubes and flow
regimes in an atmospheric
pressure f l u i d bed
combustor
92-93
Indices
mixing
136-44
segregation, Danckwerts.... 136-38
IndustrySee Commercialization
Inert t r a c e r and mixing
161-64
I n f i n i t e and i n f i n i t e s i m a l
numbers
7-8
I n i t i a t i o n of polymerization
reactions
103-7,177-79
Inlet(s)
number and mixing
149
temperature
f i x e d bed reactor
35t,42t
product y i e l d s from
methanol-to-gasoline
processes
42t
residence time d i s t r i b u t i o n
theory
145t
Instantaneous i n t e r n a l age
d i s t r i b u t i o n , population
balance method
147-48
Integers, hyperreal
8
I n t e n s i t y of segregation,
definition
136-37,140t
I n t e r a c t i o n by exchange with
the mean model.... 156-64,169-71
Interaction of p a r t i c l e s ,
models
156-75
I n t e r f a c i a l polycondensation... 109t
Internal age d i s t r i b u t i o n ,
instantaneous, population
balance method
147-48
Internal b a f f l e s , design in
f l u i d bed r e a c t o r
40f
Internal c i r c u l a t i o n patterns
in s t i r r e d tanks
175-76
Ionic polymerization
reactions
103-7
Isobutane, f i r s t c y c l e y i e l d
in a scaled-up f i x e d bed
reactor
35t,42t
Isocyanates, world c a p a c i t y
and expected growth
102t
Isomerization of durene
37
Isothermal heat sink, tubular
reactors...................
32
Isothermal heterogeneous and
homogeneous r e a c t o r s
149
Isothermal polymerization
of methyl methacrylate in a
continuous flow s t i r r e d
tank r e a c t o r , m u l t i p l i c i t y . . . . 113f,114,118f,121f
reactor conditions
Ill
Isothermal, non-, uncontrolled
nonadiabatic s t i r r e d tank
reactor with a s i n g l e
exothermic r e a c t i o n
13-14
I s o t r o p i c homogeneous
turbulence
138-40
196
CHEMICAL REACTION
K i n e t i c energy of turbulent
motion, homogeneous
i s o t r o p i c turbulence
138-41
Kinetics
of carbon combustion
85
of methanol-to-gasoline
process
23-25
of mixing
169-71
of polymerization.,.. 103-7,178-80
of s u l f a t i o n of limestone... 69-73
Kolmogorov microscale,
homogeneous i s o t r o p i c
turbulence
138-41
L
Lagrangian approach and mixing
theory
164-75
Leaving environment and mixing
theory
151-64
Length of bed and gas r e c y c l e
system.
34
Light gas, product y i e l d s from
methanol-to-gasoline
processes
42t
Limestone
reduction of nitrogen oxide.. 91
as sorbent in atmospheric
pressure f l u i d bed
combustor
69-73
L i q u i d phase and C o r r s i n
microscale f o r mixing
theory
139-41
Local age d i s t r i b u t i o n
function
145,147
L o c i , Hopf b i f u r c a t i o n
14
M
Macroscale
homogeneous i s o t r o p i c
turbulence
138-41
mixing and residence time
distributions
144-51
Magnesium limestone,
sulfation
69-73
Mass t r a n s f e r models f o r
carbon combustion
84-85
Mathematics, h i s t o r i c a l
survey
1-15
Maximum mixedness, d e f i n i t i o n . . . 151
Mean square f l u c t u a t i o n ,
homogeneous i s o t r o p i c
turbulence
138-41
ENGINEERING
Mechanics, f l u i d , i n
atmospheric pressure
f l u i d i z e d bed combustor... 72-78
Mechanisms
coal combustion
66
i n t e r a c t i o n , micromixing in
the p h y s i c a l space
164-75
methanol-to-gasoline
process
23-25
in polymerization r e a c t o r s ,
kinetics
105t
of s o l i d d i s p e r s i o n , coal
combustion
88-90
s u l f a t i o n of limestone
69-73
Media, r e a c t i o n , employed in
polymerization r e a c t o r s . . . . 105t
Melt polycondensation
109t
Methane, f i r s t c y c l e y i e l d ,
scaled-up f i x e d bed
reactor
35t,42t
Methanol-to-gasoline process
reactor design
23-32
scale-up and
commercialization
32-44
space v e l o c i t y , in a
scaled-up f i x e d bed
reactor
35t,42t
zeolite catalysts
19-23
Methyl a c r y l a t e , heats of
polymerization
106t
Methyl methacrylate
heats of polymerization
106t
isothermal polymerization in
a continuous flow
s t i r r e d tank
reactor
113f,114,118
M e t r i c a l theory of "phonetic
syzygy," S y l v e s t e r
2
Microscale, mixing
phenomena
137,164-75
Minimum mixedness, d e f i n i t i o n . . 151
Mixing
135-81
d e f i n i t i o n and
c h a r a c t e r i z a t i o n of
degree
136-38
e a r l i n e s s in the age
domain
151-64
entropy
138
Eulerian approach
138-44
in a f l u i d bed r e a c t o r
52
of gas in an atmospheric
pressure f l u i d bed
combustor
77-78
macro-, and residence time
distributions
144-51
by molecular d i f f u s i o n
167-70
INDEX
197
Mi xi n g Continued
for polymerization
reactions
106
and segregation at the
microscopic level
164-75
static
176-78
in s t i r r e d tank r e a c t o r s . . . 175-77
times
137
Molecular d i f f u s i o n , mixing.. 167-70
Molten s a l t c o o l i n g
32
Moment equation, population
balance method
147-48
Monomers
heats of polymerization
106t
linkage
109t
Monte Carlo method, mixing
theory
156-59
Morphological models and
particle disintegration,
polymerization
122f
Motion, turbulent, k i n e t i c
energy and homogeneous
i s o t r o p i c turbulence
138-41
Multibed designs
29f
M u l t i g r a i n model,
polymerization
122f
M u l t i p l i c i t y , multiphase
s t i r r e d tank reactor.. 14,175-76
OctaneContinued
y i e l d in scaled-up f i x e d bed
reactor
35t,42t
O l e f i n polymerization,
solid-catalyzed
120-24
Operating conditions of
reactor and residence time
d i s t r i b u t i o n theory
1451
Oscillatory solution, stirred
tank r e a c t o r
14
Outlet
for methanol-to-gasoline
dehydration r e a c t o r
42t
residence time d i s t r i b u t i o n
theory
145t
temperature, in a scaled-up
f i x e d bed r e a c t o r
35t,42t
Oxidant, dominant, carbon
combustion
85
Oxidation of bound nitrogen in
coal
90-92
Oxygen
atom c o n f i g u r a t i o n in a
s i l i c e o u s framework,
zeolite catalyst
21-22
concentration and
d i f f u s i v i t y , carbon
combustion e f f i c i e n c y . . . 82-83
19,20f
165-66
153-64
66
90-92
28f
13-14
7-8
105t
0
Octane
blending q u a l i t y , durene.... 25-27
P a r a f f i n s , methanol conversion
products
23
P a r a l l e l model of Weinstein
and Adler
154f
Particles
definition
163
diameter
55,69-73,78-80
flow in f l u i d bed r e a c t o r . . . 50-62
fragmentation in atmospheric
pressure f l u i d bed
combustor
87
heating in atmospheric
pressure f l u i d bed
combustors vs. f l u i d i z e d
c a t a l y t i c crackers
66-67
mixing in f l u i d bed
reactors
52
models
of i n t e r a c t i o n
156-64
of polymerization,
disintegration
122f
Partitions, constructive
theory, Sylvester
3
Phase behavior
c o m p a t i b i l i t y in f l u i d bed
reactor
59-62
198
CHEMICAL REACTION
ENGINEERING
28f,29f
27
Radial flow in a d i a b a t i c
reactors
28f,29f
Random coalescence-dispersion
model, mixing theory
156-64
Rate of a t t r i t i o n and carbon
combustion e f f i c i e n c y
83-85
Rate of c o o l i n g in a s t i r r e d
tank r e a c t o r
14
Rate of flow
See a l s o Flow r a t e
in an atmospheric pressure
f l u i d bed combustor
67-69
in the bundle of p a r a l l e l
tubes model
145-46
in a f l u i d bed r e a c t o r
50-55
Rate of heat t r a n s f e r ,
atmospheric pressure f l u i d
bed combustors vs.
fluidized catalytic
crackers
66-67
Rate of r e a c t i o n
b i f u r c a t i o n diagrams
11-12
carbon g a s i f i c a t i o n
85
reduction of nitrogen oxide.. 91
s u l f a t i o n of limestone
70-73
Rate of s o l i d ( s ) withdrawal and
carbon combustion
efficiency
80-82
Reactant mixing
135-80
Reaction, exothermic, s i n g l e ,
uncontrolled nonadiabatic
s t i r r e d tank r e a c t o r ,
nonisothermal system
13-14
INDEX
199
Recycle operation
and bed length
34
in f i x e d bed r e a c t o r s . . 27,35t,42t
Reduction of nitrogen oxide... 91-92
Residence time d i s t r i b u t i o n s
and macromixing
144-51
Reynolds number, p a r t i c l e
66
R u s s e l l , Bertrand
9
S
S a l t , molten, c o o l i n g
32
Scale-up
See a l s o Commercialization
of f i x e d bed r e a c t o r s
27
of f l u i d bed r e a c t o r s ,
h o r i z o n t a l and
vertical
40-42
of methanol-to-gasoline
process
32-44
of polymerization r e a c t o r s . . . 109t
Segregation
by chemical methods,
identification
170-75
index, Danckwerts
136-38,161
intens i t y , def in i t ion..136-37,140t
and mixing at the
microscopic l e v e l
164-75
and polymerization of
styrene in cyclohexane
solution
178-80
Semibatch r e a c t o r
m u l t i g r a i n model p r e d i c t i o n s
for propylene
polymerization
120-24
polymerization r e a c t i o n s
109t
residence time d i s t r i b u t i o n
theory
145t
Separations i n f i x e d bed
methanol-to-gasoline
process
38f
Separator temperature in
scaled-up f i x e d bed
reactor
35t,42t
Shape, molecular, and mixing
theory
167-70
Shape-selective z e o l i t e
catalysts for a
methanol-to-gasoline
process
19-23
Sherwood number and carbon
combustion e f f i c i e n c y
82-83
Shrinking aggregate model 159,166-67
S i l i c e o u s framework, oxygen
atoms in z e o l i t e
catalyst
21-22
S i n g u l a r i t y theory
11-12
200
CHEMICAL REACTION
Size
bubble, in f l u i d bed
reactor
50
coal feed, f o r optimum
carbon combustion
efficiency
84-85
p a r t i c l e , in an atmospheric
pressure f l u i d i z e d bed
combustor
66-73
pore
70
Solid(s)
bed, density, atmospheric
pressure f l u i d i z e d bed
combustor
67-69
d i s p e r s i o n mechanism f o r
coal combustion.
88-90
mixing
178
o l e f i n polymerization
catalysis
120-24
polycondensation
109t
withdrawal rate and carbon
combustion e f f i c i e n c y . . . 80-82
S o l u b i l i t y and polymerization
reactions
106
Solution polymerization in a
continuous flow s t i r r e d
tank r e a c t o r
110-14
Solvent concentration in
polymerization
110-15
Spectra and homogeneous
i s o t r o p i c turbulence
138-41
Spencer and Leshaw model...153f,158f
S t a b i l i t y regions in a s t i r r e d
tank reactor
14
State of matter, gas, and
alchemy
3-4
S t a t i c mixers
176-78
Steady state conditions i n
continuous s t i r r e d tank
reactors
14,110-14,148-49
Steam d e a c t i v a t i o n of the
c a t a l y s t in methanol
conversion
23
S t i r r e d tank reactors
13-14
and mixing theory
175-77
multiphase
176-78
f o r polymerization
reactions
109t,117f
turbulent k i n e t i c energy
and segregation
dissipation
139-41
Structure of a z e o l i t e
c a t a l y s t f o r a methanolto-gasol ine process
21-23
Styrene
emulsion polymerization in a
continuous flow s t i r r e d
tank reactor
117f
ENGINEERING
Sty r e n e C o n t i nued
heats of polymerization
106t
segregation e f f e c t on
polymerization
179-80
Styrene-acry Ion i t r i l e butadiene polymer, world
c a p a c i t y and expected
growth
102t
S u l f a t i o n and s u l f u r capture
in an atmospheric pressure
f l u i d i z e d bed
combustor
66,69-73
Surface of r e a c t o r s , and
polymerization r e a c t i o n s . . . 106
Suspension in polymerization... 105t
S y l v e s t e r , James Joseph,
metrical theory
1-3
Tank reactor
See a l s o S t i r r e d tank
reactors
uncontrolled nonadiabatic
nonisothermal system
with a s i n g l e exothermic
reaction
13-14
Taylor microscale, homogeneous
i s o t r o p i c turbulence
138-41
Temperature
bed in an atmospheric
pressure f l u i d bed
combustor
69-73
o u t l e t and i n l e t , product
y i e l d s from
methanol-to-gasoline
processes
42t
reactor
and f l u i d i z a t i o n
60-62
methanol-to-gasoline
process
26f,43f
polymerization
110-15
tubular, c o n t r o l . . . .
32
Terminal v e l o c i t y in an
atmospheric pressure f l u i d
bed combustor
72-78
Termination,
polymerization
103-7,178-80
1,2,4,5-Tetramethylbenzene
formation, methanol-togasol ine process
25-27
Theory of p a r t i t i o n s ,
constructive, Sylvester....
3
Thermal to e l e c t r i c a l energy,
e f f i c i e n c y of conversion,
atmospheric pressure
f l u i d i z e d bed combustor.... 69
Thermal time d i s t r i b u t i o n
149
201
INDEX
Three-envronment model,
mixing theory
159
Time constant, C o r r s i n ,
Taylor, and viscous
d i s s i p a t i o n , homogeneous
i s o t r o p i c turbulence
138-41
Time d i s t r i b u t i o n s , residence,
and macromixing
144-51
Times of mixing
137
Tower and s t i r r e d tank
cascade, polymerization
reactions
109t
Tracer, i n e r t , and mixing.... 160-63
Transfer of heat in an
atmospheric pressure
f l u i d i z e d bed combustor... 78-80
Transfer models
mass, and carbon
combustion
84-85
po lymer i z a t ion
178-80
Transversal d i s p e r s i o n
c o e f f i c i e n t , tubular
reactors
142
Trommsdorf e f f e c t
114
Tube(s)
area s e l e c t i o n f o r an
atmospheric pressure
f l u i d bed combustor
78-80
bundle of p a r a l l e l , model.. 145-57
e x t r e m i t i e s , locus
146f
immersed, and flow regimes,
atmospheric pressure
f l u i d bed combustor
92-93
Tubular r e a c t o r s
32,141-43
Turbulence
E u l e r i a n approach
137-44
s t i r r e d tanks
175-76
Two-phase bubble model
53-58
Two-stage f i x e d bed r e a c t o r s . . . . 3If
U
Uncontrolled nonadiabatic
s t i r r e d tank r e a c t o r
with a s i n g l e exothermic
reaction
Unsaturated p o l y e s t e r s , world
c a p a c i t y and expected
growth
Veloci t y C o n t i n u e d
of emulsion, in an
atmospheric pressure
f l u i d bed combustor
77
f l u c t u a t i o n s , and turbulence
theory
- 138-40
of f l u i d i z a t i o n . 52-56, 66-67,72-78
gradient, and mixing theory.. 164
methanol, in a scaled-up
f i x e d bed r e a c t o r
35t,42t
V e r t i c a l scale-up of f l u i d
bed r e a c t o r s
40-42
Villermaux and Z o u l a l i a n
model
154f
V i n y l polymers, polymerization
mechanism
105t,106t,115t
Viscous d i s s i p a t i o n ,
homogeneous i s o t r o p i c
turbulence
138-41
V o l a t i l e e v o l u t i o n in an
atmospheric pressure f l u i d
bed combustor
87-92
Volume and residence time
d i s t r i b u t i o n theory
145t
Volume, accumulator, and
mixing theory
154
Volumetric expansion, s u l f u r
capture
69-73
Volumetric f l o w r a t e ,
atmospheric pressure
f l u i d bed combustor
69,72-78
W
Water
formation in a methanol-togasol ine process
23-25
y i e l d in a scaled-up f i x e d
bed r e a c t o r
35t,42t
Weight of bed in an
atmospheric pressure
f l u i d i z e d bed combustor... 67-69
Weinstein and Adler p a r a l l e l
model
154f
13-14
102t
58-60
Y
Y i e l d s of products from
methanol-to-gasoline
processes
42t
CHEMICAL REACTION
202
ENGINEERING
152