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Res 1990,29, 1226-1234

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Gay, D.; Ray, W. H. Application of Singular Value Methods for
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Klema, V. C.; Laub, A. J. The Singular Value Decomposition: Its
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Singular Value Analysis Effects of Scaling. AIChE J . 1985, 31,
135-146.
Lau, H.; Alvarez, J.; Jensen, K. Synthesis of Control Structures by
Singular Value Analysis: Dynamic Measures of Sensitivity and
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Litz, L. Order Reduction of Linear State-Space Models via Optimal
Approximation. Proc. IFAC Symposium on Large Scale Systems;
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Moore, B. C. Principal Component Analysis in Linear Systems:
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Chemical Plants. A New Framework to Assess and Improve Ro-
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Received for review March 5, 1990
Accepted March 19, 1990

Fluidized Reactor Models.

1. For Bubbling Beds of Fine, Intermediate, and Large Particles.
2. For the Lean Phase: Freeboard and Fast Fluidization
Daizo Kunii
Fukui Institute of Technology, 3-6-1 Gakuen, Fukui City 910, Japan
Octave Levenspiel*
Chemical Engineering Department, Oregon State University, Coruallis, Oregon 97331 -2702

Part 1 presents reactor models for all regimes of behavior of dense bubbling fluidizing beds, and
the single parameter appearing throughout is the mean bubble size in the bed. The models are simple
in that they do not require numerical solution, and they reasonably fit the reported data for these
systems. Part 2 develops a freeboard entrainment reactor model to account for the extra conversion
taking place above the dense bubbling bed. This model extends naturally to fast fluidization and
other lean-phase contactors such as the circulating fluidized bed and suggests what type of information
is needed to make reliable reactor performance predictions in these systems.

Part 1. Dense Bubbling Fluidized Beds
To predict the behavior of a chemical reactor requires
information on the stoichiometry, thermodynamics, heat
and mass transfer, reaction rates, and lastly, flow or con-
tacting pattern of materials in the reactor. For fluidized
reactors it is the flow and contacting that cause particular
difficulties, and various modeling approaches have been
taken to account for this factor. In the early days, simple
contacting models such as plug flow, mixed flow, disper-
sion, and tanks in series were tried. Then, following the
lead of Toomey and Johnstone,’ 2-region models were
proposed. The aim of these models was to account for the
observed nonhomogeneity of fluidized beds, in effect, the
bubble and the dense phases. Over 30 distinctly different
models of this type have appeared in the literature.
The 1960s saw two major advances in the understanding
of gas/solid contacting in bubbling fluidized beds, firstly,
0888-588519012629-1226$02.50/ 0
Davidson’s analysis of the flow of gas within and in the
vicinity of a rising gas bubble and, secondly, Rowe’s finding
that a rising bubble was accompanied by a wake of solids
and that this was the main mechanism causing solid cir-
culation in a fluidized bed.
These developmenta led to a new class of reactor model,
the h y d r o d y n a m i c model, in which the bed behavior was
based on the characteristics of these rising bubbles. Over
a dozen of these models have been proposed but all for the
extreme of very fine particles in which the rising bubbles
are surrounded by very thin clouds of circulating gas. Why
this extreme? Because it is this that is often of practical
importance.
In this paper we first update one of the fine particle
models, the K-L model. We then extend the analysis to
the other contacting regimes, thus to beds of intermediate
particles in which bubbles are surrounded by thick over-
0 1990 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990 1227
Small particles Large particles
fast bubbles Intermediate slow bubbles
Ub >>Umf/Emf Ub -(I to 5) u m,f / & m, f u b <Umfl&mf
. .
Cloud1
Very thin bubb
clouds

. . .

1 I
.. 1
('4 (e)
Figure 1. Many combinations of assumptions adopted in developing

g
a gas/solid contacting model for dense bubbling fluidized beds.

lapping clouds and to large particle beds in which bubbles

are cloudless.
Finally, in fine-particle beds at high gas velocity, a
considerable amount of solids may be present in the ...............
freeboard above the dense bed. This is often the situation . . . . . ... .. . .. ..
in commercial operations where gas velocities are as much
as 100 times as high as needed to just fluidize the bed. In , . .... ..., ..... ....... ..
part 2 we present a simple model to account for the con-
version in this region of the vessel. It should be noted that . . . :;.. . . . .. ..
....... : I

this freeboard model, with appropriate parameter values,

should also reasonably represent the fast fluidized bed and
the circulating fluidized bed.
Assumptions of the Fine-Particle Bubbling Bed
Models. This is the region wherein the bubbles rise very
much faster than the gas that percolates through the
emulsion; hence, according to Davidson's analysis, the
rising bubbles are surrounded by thin clouds of recircu-
lating gas. Various combinations of assumptions may be
used to represent the contacting in this region, and re-
ferring to Figure 1 we have the following choices: (a)
bubble, cloud, and emulsion treated as separate regions,
bubble and cloud treated as a single region, cloud and
emulsion treated as a single region; (b) bubbles spherical
or nonspherical; (c) wake region accounted for or ignored;
(d) one mean bubble size in the bed, bubbles grow as they
rise in the bed but are of the same size at any level in the
bed, size distribution of bubbles at any level in the bed but
all growing as they rise; (e) solids in bubbles considered
or ignored.
Each one of the above alternative assumptions has been
included or has been recommended for inclusion, in a
reactor model. Here we choose a set of assumptions that
is simple enough to use without requiring numerical so-
lution but that reasonably reflects the essential behavior
of fluidized beds. Thus, we assume constant-sized
spherical bubbles accompanied by wakes; bubble, cloud,
and emulsion are treated as separate regions, with the
dense regions at close to minimum fluidizing conditions.
Dense Bed Models. Figure 2 indicates the models for
the three contacting regimes which will be developed in
this paper. First we have the fine particle model of Figure
2a. Here, as mentioned above, we have three regions, the
cloud being very thin, negligible upflow in the dense re-
gions, and gas interchange rates K b and Kcebetween re-
gions.
For beds of intermediate particles, the clouds sur-
rounding the bubbles are thick and overlap, see Figure 2b,
so the simplest reasonable representation of this type of
contacting is to assume two side-by-side regions with plug
flow of gas up each region and crossflow between regions.
Finally, for large-particle beds, see Figure 2c, flow
through the emulsion is faster than the rise velocity of
bubbles. As a result, the fluidizing gas uses the bubbles
t I t ' t t t
Figure 2. Gas flow pattern and assumptions chosen here for the
dense bubbling fluidized bed (a) of fine, (b) of intermediate, and (c)
of large particles.
un = 0 un = umf Un' umf
Figure 3. Nomenclature used for fixed and fluidized beds.
as shortcuts through the bed. The simplest reasonable
representation of this regime is to assume plug flow up the
bed with occasional shortcuts through bubbles.
We first develop the material balances and conversion
equations for these three contacting regimes; then we
compare the predictions of these models with the ideals
of plug and mixed flow and with experimental results
recently reported in the literature.
Material Balances for Bubbling Fluidized Beds.
Consider the contacting and nomenclature shown in Figure
3. Figure 3a shows the bed at rest, Figure 3b shows the
bed at minimum fluidizing conditions, and Figure 3c shows
the bubbling bed. A mass balance for the bed solids gives
Lm(l - Cm) = L&- €,f) = Lf(1- € 3 (1)
Experiment and observation show that rising bubbles
contain very little solid, so ignoring this and letting 6 be
the fraction of bubbles in the bed, we can write
tf = 6 + (1- ahmf or 1- et = (1- 6)(1 - e&)
(2)
The rise velocity of an isolated bubble relative to the
surrounding bed solids is given by Davidson and Harrison2
as
Ubr = 0.711(gdb)'/2 (3)
and in a bubbling fluidizing bed by
1228 Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990

+ Ubr

I\
ub = uo - umf (4) 0.7 I I I I I 1 I
Recent experiments by Werther and Hilligardt3 in beds '- Rounded catalyst
I
i
of various diameters show that the rise velocity of bubbles
in large diameter beds of small particles can be very much O6 VYAcrylic
granules
larger than predicted by eq 4, due primarily to gulf
streaming. On the basis of these measurements, we pro-
pose the following correlations:
For Geldart A solids with d, 5 1 m,
ub = 1.551(~,- umf)+
14.l(db + 0.005))d>32 + Ubr [m/s] (5)
For Geldart B solids with d, I 1 m, 'k'I 0.3
0.3 ~ Irregular

Ub = 1.6((u0- Umf) + Ubr [m/S] (6)

For small bed diameters, ub calculated from eqs 5 and 6 0.2

j
II !
may be smaller than that calculated from eq 4. In these \
Magnesite
Crished
cases, always use the larger value. coal
powder
Next the fraction of bed consisting of bubbles is de- 0.1
termined by the flow regime; thus, for slow bubbles, or u b
Umfltmf,
0 I I 1 1
0 100 200 300 400 500 600
dp (w)
Figure 4. Wake fraction (f,)of three-dimensional bubbles a t am-
For intermediate bubbles with thick clouds that may well bient conditions, evaluated from X-ray photographs by Rowe and
overlap, or umf/tmf< ub < 5ud/emf, we have a difficult to Partridge.* V, = wake volume, v b = bubble volume.
represent regime. Interpolating between the slow and fast where the wake fraction (f,)is found from the measure-
regimes, we have, approximately, ments reported by Rowe and Partridge* shown in Figure
4.
The interchange rate coefficient between regions i and
J is defined by Ki,
= (m3of gas flowing from i to j and also
fromj to i)/(m3hubble)(s) [s-l]. Hence, between bubble
when and cloud

For fast bubbles, or ub > 5ud/cmf, clouds are thin, and we

find
K ~ =, 4.5 - (y )+ (- 5.85 [&I (16)

and between cloud and emulsion

In vigorously bubbling beds where u, >> umf,we may take

(
K,, = 6.77 0.711~;;(g~db)~/~
as an approximation
6 = uo/ub (10)
Let us define the distribution of solids in the various re-
gions by In raising the gas velocity beyond umf,a bed of Geldart
yb, yc, ye = volume of solids dispersed in b, c, and e, A particles expands progressively for a while and only
respectively/volume of bubble (11) starts to bubble at a somewhat higher velocity, as high as
1 . 3 This~ ~point is called the minimum bubbling velocity,
A material balance for solids then relates these values umb Beyond Umb the bed collapses somewhat to a voidage
as follows: te, giving a superficial emulsion velocity of u,. These
6(?b + Yc + Ye) = 1 - f f = (1- c m f ) ( l - 6) (12) values, E , and u,,increase progressively with an increase
in pressure and with a decrease in particle size.
from which In situations where t, and u, (always larger than emf and
umf)are known, make the following changes in the above
(13) equations, umf* u, and tmf * t,, and proceed with the
above analysis, otherwise unchanged.
From experiment, yb is of the order of 10-2-10-3, with the The types of material balances presented above were
actual value being uncertain. So for our calculations to originally developed by Kunii and Levenspie15 drawing
come, and until more precise values are known, let us take heavily from the Davidson bubble theory, presented in
Davidson and Harrison? However, some of the expressions
Yb = 0.005 (14) summarized above differ from the original. These im-
With the wake included with the cloud region, we also have proved updated expressions come from new information
reported in the literature in the last 20 years. For more
details of the derivation of these expressions and for
supporting evidence for these changed expressions, in
particular for ub, see Kunii and Levenspiel.'

Reactor Model for Fine-Particle Bubbling Beds: u b
>> u mP Consider a first-order solid-catalyzed gas-phase
reaction. Per unit volume of catalyst (considered to be
nonporous), V,, we can write
- -
Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990 1229
bubble size with constant interchange coefficients, Kh and
K,, to represent the reactor. However, where the reaction
is very fast, most of the conversion occurs near the bottom
of the bed with its rapid bubble growth. In this situation,

--1 - -- K , C A ,
dlvA
V, dt
K, = [ m3 Of gas
m3 of so1id.s
] (18)
eq 23 may have to be integrated numerically by using
bubble size profiles in the bed with changing Kh and K,
values corresponding to these changing bubble sizes.
The overall reactor efficiency when compared to plug
flow is then
where K, is the reaction rate constant. This measure is
independent of bed voidage and particle size if pore dif-
fusion effects do not intrude; hence, it is useful for linking 'bed
- ( catalyst needed in plug flow
- catalyst needed in a fluidized bed
reactor performance of fixed beds to fluidized beds.
For a feed rate u (m3/s) of reactant gas CAi(mol/m3) to
a catalyst bed containing solids of volume V, (m3),inte- effective first-order rate const in fluidized bed
gration of the performance expression gives the outlet true first-order rate const
concentration CAo, or the outlet fractional conversion XA, (25)
as
for plug flow 1 - X A = C A o / C A i = exp(-K,~) A comparison of eq 19 with eq 23 then gives
(19)
cAo 1
for mixed flow 1 - XA= - =-
C A ~ 1 + K,T
where the reactor ability measure is -
1 %I
= ,' [ m3 of catalyst
] (21)
+

-
Note that the efficiency is a function of the reaction rate
(26)

T
U m3 of feed/s
and where the dimensionless reaction rate group is
i = m, f, mf
For reversible reactions, replace all C A values by CA -
CA,Wuilib and X A by X A / X A , e q u i E b in eqs 19 and 20 and
elsewhere, and the development throughout follows with-
out further change. Also, the performance expression
developed here assumes isothermal flow with negligible
density change on reaction. When these assumptions are
not reasonable, Levenspie17shows how to account for this.
Next, consider the fluidized bed reactor. For the fine-
particle system with its five reaction and mass-transfer
steps, the performance equation in its various forms is
For vigorously bubbling conditions, or uo>> umf,we may
use the approximation of eq 10. Thus, with eq 22, we get,
in slightly different form,
1 - X A = ex.( -K*) UO = exp[ - K 1f -L€f ] (23b)
-
constant. For slow reaction, 1;for very fast reaction,
'Ibed Y b d / ( l - tf)*
Reactor Model for Bubbling Beds for Intermediate
Particles or ud/ed < u b < 5(id/ed). With fairly large
(22) particles, roughly Geldart I3 solids, the bubbling bed may
behave somewhere between the extremes of very fast and
very slow bubbles. Here bubbles surrounded by large
overlapping clouds rise faster, but not much faster, than
the emulsion gas. These overlapping clouds may well
comprise the whole of the emulsion phase.
A simple model to represent this situation is sketched
in Figure 2b. It views the bed as consisting of two regions,
bubble and emulsion, with just one interchange coefficient,
Kbe,to represent the transfer of gas between regions. In
contrast to the fine particle model, here the upflow of gas
through the emulsion is not ignored.
For a first-order irreversible catalytic reaction, an ac-
counting of reactant gas A as it rises through these two
side-by-side regions gives
disappearance in bubble =
(reaction in bubble) + (transfer to the emulsion)
disappearance in emulsion =
(reaction in emulsion) + (transfer to the bubble)
In symbols the above word equations become

In these performance expressions, the effective rate con-

stant for the bubbling fluidized bed, Kf, is found to be
and

1
1
YbKr + dCAe
1 -(1 - 6)Umf -dz
=
Kf=[ L
Kbc +
YcKr + 1 1 1 [S-'] (24)
(1- 6)(1 - t m f ) K r C A e - h K b e ( C A b - CAJ (28)
- +-
Kce ~eKr In these expressions, the rise velocity of bubble gas, not
The details of the derivation of these expressions are all just the bubble, is
given by Kunii and Levenspiel? and the basic parameter ub* = u b + 3umf (29)
needed to make these conversion predictions is the "mean" and d is given by eq 8. In addition, since the emulsion
bubble size in the bed. consists primarily of cloud gas, the interchange coefficient
For these fine-particle beds, bubbles quickly reach an between phases can be approximated by the bulk flow term
equilibrium size not far above the distributor. Thus, when of K b c of eq 16. Thus,
the reaction is not extremely fast and occurs significantly
throughout the bed, one can reasonably use an average Kbe 4*5(umf/db) (30)
1230 Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990
Solving eqs 27 and 28 simultaneously subject to the
boundary condition
CAb = CAe = CAj at 2 = 0 (31)
gives the overall conversion of reactant gas as
where
and
ib(a))(i 5y2 1 - 6 - ub* (35)
Under normal fluidizing conditions, qz is much larger than
q l . This justifies dropping the last term of eq 32. Com-
paring with eqs 19 and 22 shows that the bubbling bed
approaches plug flow behavior when reaction becomes very
much slower than mass transfer.
Experimental data on the catalytic oxidation of carbon
monoxide in a bed of dense 325-pm alumina particles is
reasonably fitted by eq 32. This is shown in Figure 7.
Reactor Model for Large-Particle Bubbling Beds:
ub < ud/ed In vigorously bubbling beds of fine particles,
fast rising clouded bubbles with rapidly recirculating gas
carry most of the feed gas through the bed, while flow
through the emulsion is negligible. In contrast to this, in
bubbling large particle beds, the upflow of emulsion gas
is both rapid and faster than the rise velocity of bubbles,
or
%nf/fmf’ ub (36)
This is called the slow bubble bed. Let us consider a
reactor in this flow regime.
In overtaking the slower rising bubbles, the emulsion gas
uses these bubbles as a convenient low-resistance shortcut
through the bed. Therefore, a typical element of entering
reactant gas rises through emulsion, then bubble, and so
on, as shown in Figure 2c. In addition, we can reasonably
assume plug flow of gas through the bed.
At any level of the bed, the distribution of flow between
phases is
u d
= (flow through emulsion) + (flow through bubble)
= (1 - 6 ) U m f A + 6 ( u b + 3umf)A (37)
from which the bubble fraction is
(7)
Also, the fraction of gas passing through the emulsion and
contacting solids is, with eqs 7 and 37,
Ignoring the conversion in the bubble phase since so little
solid is present there, eq 38 represents the fraction of bed
solids contacted by every element of gas as it passes
through the bed. So, comparing with the plug flow ex-
pression of eq 9, the performance expression for a fluidized
bed in this regime is then
uAo
1 - XA = - = exp[-K,~(Frac)]
CAi
or
Compared to plug flow, the reactor efficiency is simply
Noting that tmf = 0.5 and u b Iud/cmfand that 6 cannot
reasonably exceed 0.25-0.35, eq 7 shows that this con-
tacting regime only exists when uo < 2 - 2 . 5 ~A~t higher
superficial gas velocities, channeling, slugging, and explo-
sive bubbling will replace ordinary bubbling behavior.
Comparison of Theory with Experiment
Figures 5 and 6 present experimental conversions found
by various investigators for fine-particle (Geldart A and
A/B) bubbling beds that do not contain baffles or inter-
nals. Figure 7 presents the findings on larger (Geldart B)
particle systems. These findings are compared to the
predictions of the fine-particle model (curves l),the in-
termediate-particle model (curve 2), and the large-particle
model (curve 3).
Note that as one uses smaller and smaller particles the
reactor performance deviates increasingly from plug flow.
For detailed calculations of these curves, see the examples
in Chapter 12 of Kunii and LevenspieL6
Overall the predictions of these models seem to rea-
sonably fit the data, and since the calculation procedure
needed to use these models is straightforward, these
models may be useful for design calculations and predic-
tions.
Part 2. Lean-Phase GadSolid Contacting:
Freeboard and Fast Fluidization
As shown in Figure 8, at high gas velocity and vigorous
fluidization, much solid may be present in the freeboard,
and as a consequence, a significant extent of conversion
of reactant may occur there. We here present a reactor
model to account for this. However, we preface the de-
velopment by noting that the model is built upon two
parameters, firstly, the distribution of solid density in the
freeboard and, secondly, the contacting efficiency in the
freeboard.
Let us first consider the density distributions: the
clusters of solids that are ejected into the freeboard pro-
gressively disperse or dissolve as they rise and then fall
back into the bed. Under conditions where most of the
 Ind. Eng.Chem. Res., Vol. 29, No. 7, 1990 1231
10 I 1 0

Geldan A panicles

05

7
x
- 02

01

0 05

Figure 7. Conversion in beds of Geldart B catalyst. Lines 1 are

calculated from the fast bubble model, eqs 23 and 24. Line 2 is
calculated from the intermediate bubble model, eq 32. Line 3 is
calculated from the slow bubble model, eq 39. The following infor-
I I mation is given in the order of symbol, d, (jtm); ud (m/s), d, (m),
20 40 60 L, (m), u, (m/s), distributor. For decomposition of ozone, sand,
Li (1.Ej ) WertherY ( 0 )108, 0.016, 1.0, 0.5, 0.15, perforated, d , = 6.7 mm;
K, 5 = -,K i = m, m f o r f.
UO (0) 108,0.016, 1.0, 0.5,0.14.25, porous; (0) 108,0.016,0.2,0.5,0.1,
Figure 5. Conversion in beds of very fine Geldart A catalyst. Lines porous. For oxidation of CO, dense alumina, Van den Aarsen? (A)
are calculated from eqs 23 and 24 of the fast bubble model, with ud 80, 0.018, 0.30,0.214.49,0.1, -; (A)325, 0.21, 0.30, 0.79,0.3-0.5, -.
= 0.006 m/s. The following information is given in the order of
symbol, reference, d, (rm), u d (m/s), dt (m), L, (m), u, (m/s). For CAmx
ozone decomposition: (0) Orcutt? 20-60, 0.0043, 0 . 1 0 . 1 5 , 0.71,
0.09-0.15; (0) Calderbanke (porous plate), 68,0.006,0.458,0.69,0.0

--,\-
43; ( 0 )Calderbanke (perforated plate), 68,0.006,0.458,0.69,0.043;
(0) Van Swaaij,lo -70, 0.005, 0.23, -, 0.12; @) Van swaaij,lo -70, P = Pbed e-'' ~1 -17 =- ( I - q b~
ed ~ . . ~ ~

0.005, 0.23, -, 0.20. For acetonitrile synthesis: (A)Ogasawara,"

74-150, 0.008,0.204, 0.35, 0.0044.18. -1
10 I
I I

Geldart A/B and B particles

I 1
I
-.
a -- Q __ .__-

0 Pbed Ps 0 obed 1
Density, p Contact efficiency q
CAi

Figure 8. Features of the reactor model for the freeboard region

above bubbling beds.

Li ( 1 -&i )
K, 7 =?,K
0
i = m, m f or f .
Figure 6. Conversion in beds of Geldart A/B and B catalyst. Lines
are calculated from eqs 23 and 24 of the fast bubble model with ud 0
L '&-o I 1 1 I I I 1
= 0.02 m/s. The following information is given in the order of 0 200 400 600 800
symbol, reference, d, (jtm), ud (m/s), dt (m), L, (m), u, (m/s). For
ozone decomposition: (0) Kobayashi,12 194, 0.021, 0.20, 0.1-1.0,
d, (w)
0.054.18; ( 0 )Potter,ls 117,0.017,0.23,0.1-0.4,0.06-0.08; (0) Cal- Figure 9. Decay constant for the exponential decrease of solid
derbank? 192,0.037,0.46,0.69,0.086; ( 0 )Van Swaaij?O --200,0.010, density in the freeboard 1,Chen et alJ1; 2, Bachovchin et al.=; 3,
0.30, -, 0.15. Hoggen et al.19; 4, Walsh et aL20; 5, Zhang et al."; 6, Nazemi et al.'*;
7. Lewis et al.16
ejected solids eventually return to the bed, Lewis et a1.I6 where p o is the density just above the surface of the dense
found that the density of solids in the freeboard falls off
exponentially with height with decay constant a, or bubbling bed, 9,prepared from reported literature
data, correlates this decay constant with particle size and
p = poeQz (41) gas velocity.
1232 Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990
101 I I I I
0.5 1 reasonably approximate the behavior of these systems.
- 0
0 0.2 04 06
Height from distributor, z (m)
(b)
Figure 10. Efficiency of contacting calculated from experiments on
the hydrogenation of ethylene which is injected at various levels into
a vigorously bubbling bed of fine catalyst (d = 62 Fm, umf= 0.002
m/s, u, = 0.305 m/s); from Miyauchi et al.$
Regarding the gas/solid contact efficiency, Miyauchi et
injected reactant gas at various levels into a vigorously
bubbling fluidized bed and measured the resulting con-
version at the vessel exit. Their results shown in Figure
10 indicate that the contact efficiency increases exponen-
tially to unity with rate constant a’ as the gas rises into
the freeboard from the bed surface, or
--- - (42)
- qbed
where qbedis the efficiency of contact at the bed surface,
given by eq 26 for fine-particle beds and by eq 40 for
large-particle beds. For their particular system, using four
different values of the reaction rate constant Kr, we find
a’ = 6.62 m-l.
For a first-order reaction taking place in a plug flow
reactor of voidage t, eq 18 becomes
(43)
However, in the freeboard, the contacting efficiency is not
100% and the solid fraction is low. Accounting for these
two additional factors, the first-order expression at any
height z becomes
(44)
Substituting eqs 41,42, and 43 into eq 44 and integrating
from just above the bed surface, CAo,p,, and at z =
0, to the top of the freeboard, CAexat z,, gives
(45)
In this equation, ii is the average gas velocity in the free-
board, often reasonably approximated by u,, p,/p, can be
approximated by (1- cf)bed, a is found from Figure 9, and
a ’ is found from Figure 10. Thus, the simplified equation
1
-
+ a’/a
Application to Turbulent Fluidized Bed Reactors.
(1 - e-(a+a’)ze)
1 (46)
To achieve high gas throughput, many commercial reactors
are designed for and are operated in the turbulent flow
regime. Although the bubbling bed model developed in
part 1 is not strictly applicable in this flow regime, exam-
ples of its successful use in the design and scale-up to
commercial-sized turbulent bed reactors suggest that it can
The very high gas velocities (relative to ud) in turbulent
beds generate a large dense splash zone of emulsion
clusters at the bed surface plus considerable solids in the
freeboard. This gives good gaslsolid contacting and ad-
ditional conversion of reactant in the freeboard. Because
of this, one may need to use both the dense bubbling bed
model and the freeboard model to reasonably represent
the turbulent fluidized bed reactor.
Application to Fast Fluidized Bed Reactors. Ex-
periments show that fast fluidized beds contain a lower
dense zone of voidage ef = 0.75-0.85. The contacting here
is somewhat like that of turbulent beds in that gas voids
accompanied by clumps of emulsion rise rapidly in the core
of the vessel while some emulsion descends along the wall
of the vessel. Above this dense zone is a progressively
leaner zone. So a simple approach to the modeling of fast
fluidized beds would first divide the reactor into these two
zones, a lower dense zone of height Lf and an upper free-
board zone of height ze.
For the lower dense zone, we define a coefficient Kbe’
to represent the interchange of gas between the fast rising
core region, which is lean in solids, and the slower moving
emulsion clumps and wall region. Then eq 24 for the
bubbling bed model simplifies to give
r 1
and the performance equation for this lower zone becomes,
analogous to eq 23,
For the upper freeboard zone, simply apply the free-
board model, which leads to the conversion expression of
eq 45 or eq 46. When used for fast fluidized beds, the
various physical quantities may fall in different ranges of
values. Thus,
6 = 0.6-0.9, representing the core fraction
po/ps = 0.15-0.25, ii 2 u,
= order of 0.01 (estd), ywdl= 0.1-0.2 (estd)
and a is the decay constant in the freeboard.
The fast fluidized bed is a complex system to study
experimentally; hence, there are very few reported mea-
surements of the physical quantities needed to apply this
or any other model, in particular, 6 and Kb‘. However,
preliminary estimates suggest that Kbe’ > 11s-l. Research
in the next few years should provide firmer information
on these fadors &s researchers focus on this type of reador.
-
Example. We plan to run a first-order gas-phase cat-
alytic reaction, A R with rate constant Kr = 10 m3 of
gas/(m3 of solid-s),in a pilot plant reactor 2.3 m high and
0.26-m i.d. Since the catalyst to be used is very fine (dp
= 68 pm) and the gas velocity will be many multiples of

minimum fluidization (u,= 0.3 m/s, ud = 0.006 m/s), we
expect considerable solids in the splash zone and freeboard
above the dense bed. Consequently, the reactor will be
fitted with an efficient cyclone to return any solids that
may be carried out of the bed.
During reactor operations, the bed height is expected
to be Lf = 1.1 m, the remaining z, = 1.2 m being the
freeboard.
(a) First, find the conversion of reactant XA,at the top
of the dense fluidized bed; (b) then determine the overall
conversion at the reactor exit, XAex.
Data. For the gas, 3 = 2 X mz/s. For the bed, t,
= 0.5, emf = 0.55, and L, = 0.7 m.
Since this is a fine-particle bed (Geldart A), bubbles
quickly grow to a small limiting size, db = 0.04 m.
Solution. (a) Conversion in the Dense Bed. First
let us see which model applies. Since u, = 5Oumfand, as
we shall see, ub z 123umf,we are dealing here with a
fine-particle bed with fast bubbles with very thin clouds.
Thus, the analysis leading to eqs 23 and 24 can safely be
used. So following the procedure outlined above for a
rather small diameter bed, we have from eqs 3 and 4 ubr
= 0.711(9.8x 0.04)1/2= 0.445 m/s and ub = 0.3 - 0.006 +
0.445 = 0.739 m/s. From eqs 10 and 12, 6 = u,/ub =
0.3/0.739 = 0.406 and 1 - tf = (1 - 0.406)(1- 0.55) = 0.267.
Next evaluate the interchange coefficients from eqs 16 and
17:
(4.5)(0.006) 5.85(2 x 10-5)1/29.81/4
Kh =
0.04
+ 0.045/4
= 3.26 s-'
K,, = 6.77
I(2 x 10-5)(0.55)(0.445)
0.043
= 1.873 s-I
Ind. Eng. Chem. Res., Vol. 29, No. 7, 1990 1233
information available today is that shown in Figure 10, so
we use it. Thus, a' = 6.62 m-l. Replacing in eq 46 gives
cAo
In - =
CAex
or
CAex/CAo = 0.0438
Thus,
CAex CAex cAo
- = -- = (0.0438)(0.350)= 0.0153
cAi cAo cAi
In summary, in terms of the conversion, at the top of the
dense bed, Xh = 1 - 0.350 = 65.0% and at the reactor exit,
X A e x = 1 - 0.015 = 98.5%.
Comment. This example shows that when the bed
height is insufficient for high conversion and when the
freeboard contains a considerable amount of solid then a
significant amount of reaction can take place above the
dense bed. This situation exists here because the flow of
gas through the bed is many multiples of umf,the bed is
probably approaching turbulent flow, much solid is present
in the freeboard, and the catalyst is very active (K, = 10
S-1).
With highly exothermic reactions, the dense bed pro-
vides good temperature control while the freeboard region
can experience large temperature variations. So, especially

Then the fraction of solids in the three regions is obtained

when selectivity is an important consideration, the reactor
should be designed so that very little reaction occurs in
the freeboard.
Nomenclature
from eqs 13-15 and Figure 4
a , a' = decay constants of clusters in the freeboard, m-l
')'b = 0.005 CA = concentration of reactant A, mol/m3
I 1
db = effective bubble diameter, m
yc = (1 - 0.55)
I 3
(0.445)(0.55)/0.006- 1
0.304
d, = mean particle diameter in the bed, m
d, = tube or vessel diameter, m
2J = molecular diffusion coefficient of gas, mz/s
g = acceleration of gravity, =9.8 m/s2
1 - 0.406
ye = (1 - 0.55) - (0.005 + 0.304) = 0.349 Kf = overall effective reaction rate constant in a fluidized bed,
0.406 S-1
Kij = gas interchange coefficient between regions i and j , based
Now consider the reaction. From eqs 24 and 23 we have on bubble volume, see eq 16, s-l
Kf = K , = rate constant for a first-order catalytic reaction, s-l
L = height of a bed of solids, m
r(0.005)(10) + -
' +
1
1 1 N A = moles of A
t = time
I 3'263 (0.304)(10)+ ,
-
' + 1 I= ub = bubble rise velocity in a bubbling fluidized bed, m/s
Ubr = rise velocity of a bubble with respect to the emulsion,
1.873 (0.34;)(1 O)]
m/s
0.706s-' u, = superficial gas velocity at minimum fluidizing conditions,
m/s
and u = volumetric gas feed rate, m3/s
V, = volume of catalyst, m3
cAo
-
cAi
= exp[ -
(0.706)(1.1)
0.739
]
= 0.350
XA = fractional conversion of reactant A
z = distance into the freeboard, or distance above the mean
surface of the fluidized bed, m
Hence, from eq 26, the reactor efficiency is ze = height of the freeboard, m
(0.7056)(0.4060) Greek Symbols
= 0.107
= (10)(0.2673) yi = volume of solids in phase i divided by the volume of
bubbles, see eq 11, m3 of solid/m3 of gas
This bubbling bed efficiency compares well with the ex- 6 = bubble fraction in the bed
perimental values reported in Figure 10. ci = void fraction of bed at i conditions
(b) Conversion in the Freeboard. To use eq 46 we p = density
need values for a and a'. For 68-pm particles, Figure 9 T = reactor ability measure, m3 of solid.s/m3 of feed
gives u,a = 0.6 s-l or a = 0.6/0.3 = 2 m-l. For a', the only 9 = conversion efficiency of the fluidized bed, see eq 25
1234 I n d . Eng. Chem. Res. 1990,29, 1234-1239

Subscripts al. In Fluidization; Davidson, J. F., Harrison, D., Eds.; Academic

Aex = reactant A at the reactor exit
Ai = reactant A entering the reactor
Ao = reactant A at the top of the bed and at the start of the
freeboard
b = bubble
bc = between bubble and cloud
be = between bubble and emulsion
c = cloud
ce = between cloud and emulsion
f = bubbling fluidized bed
m = fixed bed
mf = at minimum fluidizing conditions
o = at the top of the bed and at the start of the freeboard
Literature Cited
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Received for review January 17, 1990
Accepted February 12, 1990

A Proposed Numerical Algorithm for Solving Nonlinear Index Problems

Yonsoo C h u n g and A r t h u r W. Westerberg*
Engineering Design and Research Center and Department of Chemical Engineering, Carnegie Mellon
University, Pittsburgh, Pennsylvania 15213

In this paper, we present and demonstrate a numerical algorithm to detect and solve mixed systems
of nonlinear ordinary differential and algebraic equations that have an index problem. Symbolic
differentiation is used to generate the equations needed; symbolic elimination is not required as
in many other algorithms. We show that the so-called initialization and propagation problems are
in fact the same problem; they can therefore be handled by a common approach. Numerical as well
as structural singularities arising in index problems are accommodated. In principle, the algorithm
can be used with any integration scheme, including an explicit one. This algorithm is suitable for
solving index problems that previously could not be solved.

Introduction differentiation is always a straightforward step, the first

For the last decade, there has been exciting literture
building on the solution of initial value ordinary differ-
ential equation (ODE) problems, which are constrained
by algebraic equations. When these equations have an
“index problem”, Gear (1988) and Pantelides (1988a) have
shown that one can overcome the problem by appropriate
differentiation and algebraic manipulation of the original
equations to convert them to a form that does not have
the problem. For a large problem involving thousands of
equations, the issue is to (1) discover exactly which
equations to differentiate, (2) differentiate them, and (3)
carry out some required algebraic manipulations. While
0888-5885/90/ 2629-12 34$02.50/0 0 1990 American Chemical Society
and third steps can be difficult for problems with anything
but the simplest of structure-for example, linear. We
shall present in this paper a numerical algorithm that
makes the first and third steps straightforward to carry
out.
The Index Problem: An Example
Consider the following problem, which comprises a single
ODE constrained by a single algebraic equation:
XI’ = x2 (la)
XI = t2+ t + 2 Ob)