Monoliths in Heterogeneous Catalysis

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Monoliths in Heterogeneous Catalysis
Andrzej Cybulski a; Jacob A. Moulijn a
a
Faculteit der Scheikundige Technologie en der Materiaalkunde Vakgroep
Chemische Procestechnologie Julianalaan, Technische Universiteit Delft. The
Netherlands
To cite this Article: Cybulski, Andrzej and Moulijn, Jacob A. , 'Monoliths in

Heterogeneous Catalysis', Catalysis Reviews, 36:2, 179 - 270
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. 36(2). 179-270 (1994)
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and A.
Technische
Faculteit Scheikundige Technologie en
Chemische
Julianalaan 136. 2628 The
. .......................................... 180
I1 . OF ...................... 183
A. ............................................... 183
. ................................. 188
C. .................................. 189
. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
I11. OF ............... 198
A. ..................................... 198
. .................................... 218
. OF ................. 222
A. ..................................... 222
. GasLiquid .................................... 242
V. .......................................... 251
A. ..................................... 251
. Gas/Liquid .................................... 254
..................................... 258
*To whom should be .

179
0 1994 by .
180
......................................... 258
............................................. 261
catalysts; catalysts;
lithic
The use of catalysts in the chemical has been con-

Conventional fixed-bed have some obvious dis-
advantages such as of kinds (including a nonuni-
access of to the catalytic high in the
bed, etc. catalysts as as elimination of these
setbacks is Two basic kinds of catalysts can be dis-
tinguished:
1. packings with catalytically active sim-
in design to those used in distillation and columns
static Good examples of catalysts of this kind
those by developed by column pack-
ings and static As in packed beds, is an intensive
convective mass the of
these packings. packing catalysts and the con-
taining them not within the scope of this
2. catalysts continuous which con-
tain many small, mostly passages. metallic
is coated with a of in which active
dients between these passages can
if walls The catalytically active is
on inside the walls of these passages. mass
can only by diffusion the of the
walls.
This is focused on the use of monolithic typical
catalytic in and syntheses.
technology and not The classification of
monolithic is as in Table 1. should be em-
phasized that of the class 3.2 often lose the advantage of low
and since they usually contain a catalyst bed within
a zone.
the sake of simplicity, the monolithic is confined
to with walls (subclass 3.1 in Table 1). to
common with walls
(subclass 3.2 in Table 1). The monolith(ic)
181
1
Classification of
1.
1.1. Single passage (cell
1.2.
2.
2.1.
2.2.
3. of contacting
3.1. of into channels
3.2. passages
4. of
4.1. Steady state (e.g., combustion of components of off-gases)
4.2.
changes (e.g., flow, monoliths)
Oscillations (e.g., flow of gashquid channels)
to a monolithic that is, a which is

usually with a of that as a catalyst
in the sense in catalysis.
catalysts have found many applications in com-
bustion; example, as of engine exhausts, the
of off-gases, and the combustion of fuels gas
etc. on catalytic combustion, in-
cluding the use of monoliths, have been published in the last decade [l-
41. less has been on applications of monoliths not
combustion. One on this subject was published by
andoust and [5]. catalysts a of new
possibilities chemical including the selectivity of
complex and elimination of the above-mentioned setbacks of fixed
bed
A detailed the state of the in the late 1950s testing
yet without catalytic was published by John-
son et a]. [6]. The applications of monolithic cat-
alysts discussed by et al. [7] of acid
tail gas, and by et al. [8,9] exhaust emission
in the late investigations on monoliths expanded by manu-
and those emissions of
amounts of gases. The main focusing on mon-
oliths was low This fact was both auto-
mobile and off-gas conventional catalytic
would cause an of the unit.
opments in both and metallic monolithic
sulted in an of stable monoliths of
182
that met the high of combustion units. 1975

the equipped with catalytic became available. wab

estimated that in 1985 100 million catalytic in
use in the U.S. [lo]. A high efficiency of catalytic wa5
as by the in Fig. 1 [2]. now
has been focused on the combustion applications of monoliths, including
emission and fuels heating systems and stations.
Flow, mass, and heat conditions the same
a monolith due to the high of size and
of individual monolith passages. This the of
of hot spots of
packed catalyst beds. this only applies adiabatic
which in monoliths. cat-
alysts, exhibiting noneven velocity and ?
have a advantage to conventional fixed catalyst beds,

namely, much heat Flytzani-Stephanopoulos
et al. [ll, 121 studied steam of in metallic coated
monoliths. was to such an extent that contents of
in the gas outflowing the monolithic
up to five times than those in packed beds.
catalysts consist of a with a thin and uni-
catalytic which makes the diffusion
low. As is shown in this a specific gadliquid flow in
monolith channels, the mass gaseous
~ 100-
rn
10
0
YI
.-
m
E
W
0.01 0.1 1 10 100
/kg
1. Emission 2, by of
cel
183
is significantly as well. can affect the selectivity of

complex
and metallic can also be in bulk,
which accessibility these
applications. All these make monolithic catalysts not
only in combustion but also a of
11.
of available monoliths shown in Table

2 [1, 3, 5 , 131, while those of the used the of
established and developmental monoliths given in Table 3.
made of metal, and can be subdi-
vided into and
and metallic have been developed emission con-
That is why the emphasis has been on the development of
with good such as high shock,
and Axial above 20 and
suitable (open of 30-40%; size of 5-15
km) also to meet demands automotive monolithic cata-
lysts.
has been found to be the most
combustion applications. can be made with channels
of small opening, each by thin webs (0.15 +
mm) of a good mechanical 9475 of Glass,
the axial amounts to 20.7 The
expansion coefficient is low. This makes the stable at
changes. on expansion of sup-
included, shown in Fig. 2 [14]. physical
of monolithic given in Table 4 [El. some high-
applications the use of is, limited by its
low melting point (1735
The shock of can be by
developing a This can be achieved by heat
by components, example, aluminum
titanate added to mullite. Obviously, the
mechanical of the monolith, which is the highest
compositions 35
The disadvantage of monoliths is low conduc-
tivity, which excludes them applications heat exchange with
the walls is needed. in
this delays ignition and moves the ignition point the end of the
Downloaded By: [The University
2
of Some
shock
name limit,
Lava Lithia-alumina-silica 843 1367 ***
Company) LTE 1470 *** **
795 1470 *** **
** ** 0
mullite 784 1730
:x * W
1700
96% alumina 614 1810 G:
Glass
titanate
9475 1470
1920
***
**
:%
*
:ii
* z
P
** *** z
9480 1720 U
1970 * ** z
* ** 0
Alumina 1870
9406 2120 * **
2470 ** ** z
du de Alumina 1770 * **
& Company 1620 * **
1670 ** **
Company 1920 * **
& Company 1470 *** **
Company Silicon 387 1920 ** *** 2
Silicon 384 1810 **
Alumina **
1670 *** **
1670 *** **
et Composites Silicon 1720 in ** :k * *
2070 ** ***
Silicon 1470 in ** ***
1770 ** ***
1720 * **
Alumina 2220 * **
Camet Stainless steel Camet ***
1670 ***
Johnson 1520 *** **
Emitec, Nippon Yakin
, excellent; **, *,
186
3
of
Name Composition cost Notes
Alumina y-A1,03 Low common high
SSiO, The lowest

expansion
- * 2A1,03. SSi0,-
2A1,0,. 2Si0,
alumi- .
nate-spinel
Good
Silicon Sic Low-high not self-bond

easily
Silicon Si,N, Low- high not self-bond
easily
Spinel * A1,0,
Titania TiO,
Zeolites A1,0,-Si02
Can be used at tem-
high above
2480
spinel A1,0,
- mullite .SiO,
Stainless steel Low
Low
9 50
X
/ 9406
20 9480
i,
F
X
100 300 500 700 900

OC
2. Typical expansion monoliths.

with 14.
187
4
of
Code
9480
9475 9482 9483 EX-68

Compositional +
phase assemblage mullite
Open % 33 50 42 0 37
size, pm 3-4 12 21 - 3.8
Coeff. of expansion, 10 12 12 36 31
(300-1275 x
Axial 21 10 10.5
-1725 -1725 -1725 -1725 -1725
monolith. instance, the heat conductivity of 30% is

0.1 m-* alumina it is due to the
heat conductivity of alumina itself.
monoliths made of stainless steel (Camet) steel alloys
such as (5.5% Al, 22% 0.5% Co) and (0.5-12% Al,
20% 0.1-3% Y). The of aluminum containing alloys is made
to the of the alumina with which the
is made of foils of thickness 50-125 p,m
available.
The of metallic is
limit to 1670 than that of (up to 2470 the
conductivity of metals is than that of to
the high voidage, the mass of metallic monoliths and capacity
than monoliths. the ignition of a
in metallic monoliths.
of less emission
because of and stability. The stability
is mostly limited by phase which at
they difficult to than
monoliths, which a well-developed technique exists.
monoliths suitable chemical applica-
tions. physical given in Table 5 [13]. Some of them
available et Composites, Glass,
and Sumitomo.
The walls of the monolithic have to be with a
which can as an catalytic The
of the must be adopted to the application
paying attention to the of this to the Usually
188
5
size temp. limit

(m2k) (nm)
?-Alumina 180-200 3.5 923
80- 100 14.0 1273
alumina (6, 8,
Alumina Silica 130- 160 10.0 1273
(93%-7%)
Silica 150- 160 823
Titania (anatase) 50 9.0 823
alumina is applied, possibly mixed with small amounts of oxides.

The content of the 5 to 20 wt% with to the monolith
monoliths mainly by
techniques. The method of and the choice of
influence the and of the monolith.
involves a with a of
ganic oxides and salts, and it with
and stacking with accompanying and
finally calcining the at high A sheet can
be in ways, to obtain a passages
a monolith. can also be in the
of is no size limit
the monolith itself.
The vast of monoliths by
finely is kneaded with and This
plastic is subsequently and calcined. The
of monoliths is up to 25 cm but machined assemblies can also
be supplied of a specified size on example, the di-
mensions of catalysts diam. 15 cm and length 1 m.
can be stacked to any bed length.
Structural Characteristics
monoliths consist of of high open

of 30-45% open The
is in Fig. 3 [14] with to
monoliths; the mean size of of codes 9475,
9480, and 9406 3.5, 2.6, and 4.9 pm, The washcoat con-
nections with the via thin in small easy to
189
1 10 1.0 0.10 0.010
3. of
14.
when A of the of (10 pm) im-

adhesion of the to the
monoliths by a
45% to 65% [5]. The size is with
the mean size than that of
y-alumina it amounts to 3.5 m-9. The of these monoliths
30 titania-silica) to 200 m2 g- y-alumina).
difficult to than mono-
liths. The of monoliths is exemplified in Figs. 4 and 5
[11*
with a that constitutes a
catalytic compounds. Usually the has a well-developed
(100-200 g-) because it is designed to the specific
of The specific of is only
0.1-2 m2 g-. The of 2.5
to 40 m2 8-l. The the must be selected to
meet catalytic and to to the should
have to that of the
The detailed of the washcoat (this is explained in Sec.
must be adjusted to the use of the monolith.
and [16-191 out an extensive the
best thickness and of catalysis automobile emission
C. Configurations
consist of of channels in
in (see Fig. 6). The shape
of the channels may
190
4. Scanning of a silicate monolith

duced by a technique: (a) The of the onto
which the oxides the (b)
showing the highly and the of the monolith.
with 1.
ezoidal, hexagonal (honeycomb monoliths), sinusoidal, etc. Sections of

a of some typical monoliths shown in Fig. 7; the shape of
the monolithic block can be adapted to the case
of automobile it is usually oval while off-
gas it is
The cell density, y1, monoliths 9 to 470 cells
inch, while metallic monoliths, it 18 to 600 cells
inch, depending on the size of the opening and the thickness of
the wall. The calculating the cell density and the voidage
of monoliths, as a function of the side length, D , and the wall
thickness, 6,, given in Table 6 [l]. The and
191
5 . Scanning (a) A monolith made by

which has 35% and a mean of 6 pm. (b) An
alumina made by metal oxidation technique, with a of 10%; it
has a less and than the
monolith shown in (a). with 1.
unit volume, u, to 6, and by the

foilowing given in Table 6:
a
" - (1 - fi)
Open 60% to 80%

metallic this quantity 90%. The open
192
6. monoliths of Camet. with of

Camet C o . , USA.
metallic the wall thickness. Values of geo-

and voidage of monoliths wall thickness
and pitches (the distance between the points in adjacent cells
of the same shown in Figs. 8 and 9 [20].
monoliths may be assembled in a cell
has been [21] that a can significantly
the this the cells
positioned at the of the cells in the
and the smallest cells at the end of the as shown in
10 [3].
The of the channels affects the flow as well as the mass and
heat and consequently, the of mon-
olithic the channels given by the
[21] equation:
193
7. Typical cell of monoliths. 1 with

13.
6
of with Cell Shapes
Cell n E
+ +
2.3/(0 + Sw)2 (D - +
1.15/(0 + 6,)' (D - +
0.38/(0 + (D+ + Sw)2
1 + 0.0445 ~
(3)
L
Values of the limiting channel

given in Table 7 [22].
and heat channels the subject of the-
analysis by Shah and London [22]and Young and Finlayson [23].
Table 8 gives asymptotic values of the Nusselt and values con-
stant B in the by et al. [24]:
= B
( (4)
194
2500
300
6 :
2000
\
E
cu 100
1500
E
.. im
1000
6,= 1
500
1 2 3 4 5 6
Pitch, mm
8. of monoliths channels
vs. pitch size; cpsi = cells inch, 6, = wall thickness
100
1 2 3 4 5 6
Pitch, mm
9. Voidaize of monoliths channels vs. size.
195
10. monolithic cell

3, by of
7
Limiting Channel
Limiting
in Eq. (3)]
64.00
Ellipse; 1ength:width = 2 77.09
plates 96.00
1ength:width = 4 72.93
56.92
53.33
Sinusoidal; amp1itude:width = 1 52.40
60.22
[25]studied the influence of channel on the

found that, a of 99%, elongated
exhibited the best that is, the length of such a monolith was
the Gulati [26] studied how channel affected the
shock of monoliths. found that the expansion coef-
ficient of a cell must be than that of a
cell to the equivalent shock a
given monolith size and The expansion coefficient high-
density has to be to maintain the same shock
[27] found that the mechanical and ignition time in
is to cell density and the wall thickness.
is no simple to the question as to which ge-
196
8
Channel
Asymptotic Nu value
constant wall
[C in Eq. (37)]
Constant
in Eq. (4) 23 22
3.657
Ellipse; 1ength:width = 2 3.742
plates 7.540
1ength:width = 4 1.38 4.441 4.439
1ength:width = 2 1.23 3.392 3.391
1.16 2.978 2.976
0.86 2.491 2.470
Sinusoidal 2.470
3.660
is the best. The must be studied with to the specific

to meet its specific
Catalysts
two basic kinds of monolithic catalysts: (1) coated-type

catalysts and (2) catalysts. The methods of
them in Fig. 1 1 .
of catalytic components into the monolith is
by adding these components to the which the
monolith is to be subsequently and calcined. Special must be
taken at the calcination stage because of possible melting of the catalytic
compounds and with the monolith the
such catalysts is that a significant amount of active component
is located deep in the some of it is inside closed
This makes the diffusion path to active sites ac-
cessibility Catalytic oxides, can also be deposited
onto the of the the of a
bond between the and the catalytic is
monoliths can be in such a way that pelleted
catalysts Also in this case, catalytic compounds
less evenly the walls of the monolith. The walls
about 10 times than the washcoat of mon-
oliths. This elongates the way of at least to the of the catalytic
catalysts usually via an step

197
I I
H I
I I I
4
TY Pe
a s
11. of monolithic catalysts.
called washcoating, which consists of depositing the of

onto the of the monolithic Active
can be into the the washcoating step
the washcoat has been deposited, using any well-known technique.
198
I 1
12. Coated-type catalyst automotive emissions
Washcoating is usually by the monolith into contact

with: (1) a of fine of a (2) a
solution containing the metal ion, with possible subsequent
itation; (3) a sol of the compound (which is followed by gelation),
with subsequent of the obtained The typical
coating of a catalyst automotive emission is shown in
Fig. 12.
The most widely used washcoat is y-alumina. high-tem-
applications such as combustion, phase to a-alu-
mina with concomitant can when exceed 1170
is no of monolithic catalysts used
in the chemical because usually chosen.
111.
have been widely used emission and this is well

documented. both implemented into com-
mon and still at the developmental stage, in Ta-
ble 9.
Gas-
1. Control and Combustion

catalysts found applications in emission
and combustion. oxidation utilized to cut down con-
of pollutants in off-gases (CO,
9
Used as
Composition of monolithic
catalyst Notes
of CO, NO, and steel alloy; Flow up to 30 kg 21
y-alumina; + < 600) [lo, 131
engine exhausts 900-1200 [14,281
~9,301
of steel alloy; to 20,000-100,000 h - ' t41
containing pollutants 500-1000 u31
off-
gases
Combustion of ethene 413-666 ~311
Catalytic combustion of = 3-60 m [41
fuels gas (3304, ( 3 2 0 , 400-2200 0.1-1.3
Catalytic combustion of Finned metal tubes;
fuels y-alumina
Oxidation SO, -
of ~321
heat exchange system
Oxidation of ammonia 50% C0304, 48% 523-983 [33, 341
2% T i 0 2
Oxidation of a-Alumina CuO, 773-873 [351
Co304,
biphenyls
Oxidation of -
of ethanol - [371
9. Continued !z
Composition of monolithic
catalyst Notes
of cumene - -
Steam 2000-4000 h-'
=
?-Alumina; Ni = 1089-1200
Tinlet
= 810
0.1
of NO, in V-Ti < 5000
flue gases 523-673
Alumina tit'ania; V,05,
Fe,O,, COO, CUO,
NiO,
titania-silica; = 30,000 h-' 1401
Cu, Fe, V 423-873
Ex-20, = 15,000-45,000 h-' [411
leached washcoated; 423-877
Titania; = 5,000-30,000
373-573
= 10,000-40,000
y-alumina; 523-723 p i 7.0
Cell density: 35, 37
y-alumina; Ni and 46.5 cells/cm2
Alumina Ni = 15,000-50,000 h-'
648-498 0.14-2.5
Ni 36 cells/cm2
473-673 0.69
Shallow bed of the Ni Channel width 5 m m

catalyst (0.35-0.42 mm in 463-513 0.1-1.2
diam) at the passages walls conc. CO,, Co, =
0.19-4 ~ 0 1 % atm.
;
of 512 (55% mullite, 30% 36 cells/cm2
benzene Si02, 15% A1203); 10-1500 g h mol-'
of a-AlzO,; 523-623 atm.
cyclohexane 100-1800 g
373-413
= 0.001-0.05 m
y-Al,O,; Ni 40-1750 g h mol-'
373-553
of Glass/silica/alumina/fi Gas- liquid
acid 310-357 0.116-0.420
of See above Gas-liquid

and 343-375 0.592-0.984

2-ethylhexenal 413-433 0.400
alk 323 0.400
y-Alumina; Gas-liquid
of thiophene 509-523 3.0-4.0
y-Alumina; Gas-liquid
of dibenzothiophene 542-573 6-8
and of ?-Alumina; Gas -liquid
oiVsynthoil 644 10.2
of = 20-100
a-methylst 303-323
202
although must also be used to the content of

some components oxides). this section with

to the complete combustion of components in flue gases
discussed while in Sec.
adiabatically such as oxidation in
monoliths, a multiplicity of steady states can take place. This
inates a sigmoidal the heat gen-
and a line the heat the catalyst
to the gas flowing the channel (see Fig. 13). The
points of the two lines define a steady state in which heat evolved is balanced
by heat the catalyst to the gas. Within a
of the catalyst points possible, the mid-
dle one being unstable to any Upon heating, the catalyst
to the of the heat
the point of one only, it jumps immediately to
the to the of the heat
This point is called the ignition light-off
(T,,,, in Fig. 13). When the the
phenomena will be and a
will at the extinction
E H t g
?
CI
I
..
a,
CI
a
I
.
r
a
a,
I
Temperature
13. of heat and heat vs. catalyst
203
conditions, the of the monolith

will slowly with the distance the gas inlet to the channel until the
ignition is this oxidation in a
kinetic Then the of the monolith jumps up and, con-
sequently, the becomes fast, and the is mass
The jump may exceed the adiabatic
if the mass diffusivity is than the heat diffusivity, which is
equivalent to a Lewis than unity. This is in Fig.
14. With as a fuel the adiabatic can be exceeded
by than 100".
The activation of catalytic oxidation than
those of homogeneous combustions. with the
the of homogeneous oxidation may become with
that of the catalytic Then autoignition of the
This can take place the catalyst even with lean outside
flammable limits. The can thus be
than the of catalytic oxidation. When the bulk gas
the autoignition point, a homogeneous
the whole and the of oxidation exponentially,
as shown in Fig. 15.
The location of the light-off point depends on the conductivity
of the monolith of low conductivity the distance
between the ignition point and the inlet is than that metallic
_--_______-______
a
L
,
3
+-,
cb
L
Q)
a.
E
a,
I-
+
Distance
14. Axial in the monolith channel.
204
Temperature
15. vs.
at the same conditions. The of the monolith

the cold state is, metallic
a. Control. have been successfullj
applied as engines to the content of
monoxide, and oxides in exhaust gases. A typical
monolith used in catalytic has channels of a of 1- 1.5 mm
and a wall thickness of 0.15-0.25 mm, washcoated with a
25-50 pm thick. is contained in a stainless steel 10-15 cm diam
and 15-20 cm long, connected to exhaust pipes 4-6 cm diam by
cones. The gas flow is in the exhaust pipe to the mon .
olith, with a of 5,000-8,000, the flow pulsates
gas flow in the monolith give
20 to 400, which indicates a flow at all times. The above
design of a catalytic induces flow at the inle:
to the monolith due to gas expansion and in the cones
The flow at the line is than at the wall. This i:,
in Fig. 16 [59] an flow of a symmet-
supplied monolith of the design; the maximum
velocity is 5 times than the lowest one.
flow catalytic shown in Fig. l 7
[601*
The velocity at the inlet has many conse-
quences. A the cold is Also it cause\
aging and at the axis of the The chan-
neling can be by using flow in the expansion
205
16. Flow of a catalytic of typical design: (a)

of function; (b) velocity
cone. A of devices flow equalization have been in the

[38, 611. Flow equalizing, in a simul-
taneous in
automotive catalysts made of
and metal alloys. monoliths in an adiabatic
mode while metallic monoliths exhibit noneven
monoliths have a open and mass,
which and light-off A of
in metallic and monoliths is shown in Fig. 18 [62].
washcoated with y-alumina with base
metal oxides. The washcoat is 100-200 m2 Catalytic
components such as of metals deposited onto the
of the washcoat by
The main pollutants in the exhausts monoxide (about 90%),
and oxides. contact with a catalyst
these compounds into dioxide, and
in the following
2co -
+ 0 2 2c02
2 N 0 , + 2xCO + N2 + 2xC02
These accompanied by oxidation of a of
dioxide, also in exhausts, to Optimum
206
I
0 2 4 6 8 10
Durchmesser [ c m ]
17. Velocity a catalytic of the outlined

with 60. Geschwindigkeit: ve
locity; mass flow
of the mentioned pollutants can only be achieved when

in a of adfuel [63]. On the side
only NO, is with monoxide in the exhaust whilt
lean of the engine only monoxide and
The best catalyst is attained when the
is which is equivalent to h = 1 (see h-window in Fig.
19). [41] showed that, in addition, the of
and monolithic catalysts (with EX-20 is
sensitive to poisons, and and mod-
sensitive to changes in space velocity. stability of thest-
catalysts was a must be emphasized that, by law,
207
200 400 600 800 1000 1200

PER
18. in metallic and monoliths. with

62.
100
80
s.
60
.-
L
a,
> 40
0
20
ratio
19. in a catalyst.
208
high to the of the

U.S., may emit no than 1.9 g NOz mile, 3.4 g CO mile,

and 0.5 g mile.
and of the catalyst to ex-
ceeding 1000 leads to loss of noble metal and even
of the catalyst is less susceptible to
than Automotive catalysts poisoned by lead, and
(poisoning by is
who in on this subject
to the many [1-3, 10, 13, 29, 301.
b. catalysts have been used
to components and monoxide in off-
gases plants such as phenol plants, mills, phthalic and
maleic plants, ethylene oxide plants, synthetic plants, veg-
etable oil plants [lo], and catalytic [64]. The
polluting components of the gases mainly mon-
oxide, dioxide, and oxides. Catalysts used gas
ations essentially the same as those When cat-
alyst blocks needed, individual monoliths packed in a and
a of can be stacked in a block.
to the design and of units,
data by [64] given below. The total exhaust of the
Catadiene unit in a Texas plant was 545,000 m3 h - ' and
contained significant amounts of monoxide, butane, and butadiene.
To meet two catalytic units
built containing catalytic boxes of placed in
vessels than 2.4 m diam. The conical inlet sections about 5 m
long to gas the of the
monolith. The heat the was in a waste heat
to plant steam.
Off-gases of the ethylene oxidation unit of a
complex on the Gulf Coast in a catalytic 2.4 m
diam and 6.1 m in length [64]. The gas consisted mainly of with
low of ethylene, dioxide, and oxygen. was
heated to 470 combustion the to 870 The
system has been in than 10 and the savings,
to combustion, have exceeded the total capital and op-
costs the
Lab and field tests [64] a metal, alumina-sup-
catalyst on a thin-wall monolith have that the
catalyst is suitable oxidation of monoxide and nonmethane hy-
in gas exhaust gases. Aging of the catalyst is
indicating a design of the gas system and absence of
catalyst poisons.
Usually, of gases up to 570 is although mon-
209
olithic catalysts can be at as well. No

heating, except in the would be needed in flow

They seem in this but no such applications of
monoliths have been yet. Space velocities 7 to 30 s - l .
As mentioned in Sec. oxide emission can be ef-
fectively only in a of of
acting pollutants in engine exhausts. does not if oxygen is in excess,
which is the case flue gases of acid plants. The oxide
content must be in so-called selective catalytic
ammonia is mostly used as a agent. NO, is then into
and following the
4N0 + + O2+. 4N2 + (8)
with the of the optimal
conditions [65]. Obviously, oxygen can enhance the of NO with
ammonia, which has been [40]. the
of with above 720 because of am-
monia oxidation.
NO, is becoming and acute because of
Today, allow emissions of 350 and 250
NO, on liquid and gaseous fuel, These
limits have been to 75 and 60 ppm, 1994. The
limits gas was cut down to 9 ppm NO,
1993.
At the moment, than 20 acid plants equipped with mon-
olithic catalysts units in [13]. A flowsheet of
simultaneous catalytic and of
flue gases (containing NO, and SO2) in an oxidizing is shown
in Fig. 20. Two catalysts installed in in the same
The final of this and acids.
of low cell densities (with openings 3 to 6 mm) applied
of gases at plants. This is due to the
high content of dust in the gases. dust to be in
the monolith, the would of the
action of the dust catalysts
and V205 into TiOl in anatase some
cases and catalysts containing Fe203,COO,
used. in blocks of about 1 m diam.
usually to compensate catalyst deactivation,
dust blocking, and mixing of ammonia with the
flue gases must be attained the gas the monolith to minimize
the effects of this The selective of
NO, is out on a scale; as of now, about 56,000 of
catalyst has been installed in Japan and combined, equivalent to
$800 million sales of catalyst. About 1to 1.5 m3 of catalyst is needed
210
20. The simultaneous catalytic

and of flue gases.
1 of capacity. A typical station has the

of 800 have to be installed,
about 1000 m3, typically containing monolithic catalysts [ 161.
methods which give between the
dicted and data have been out [42, 66, 671.
hensive on the and of oxides have been
published [68, 691.
An monolithic system, based on a
has been developed by
[70-721. A monolith is used to components
a gas to heat continuously. The of the
is shown in Fig. 21. the of the section, a gas is heated
a hot monolith and the of ignition. Thus the
of the monolith is only as a heat
The monolith in the is with catalytic species. When
the combustion of C-components and the tem-
of the gas heat of combustion of these com-
ponents is insufficient to attain a balance, an additional fuel may
be outside the monolith and hot combustion gas added to the top
of the monolith. The hot gases flow down the monolith
in the second section. They cooled while the monolith, especially in the
is heated up. This can be utilized in many
The system has been successfully used
combustion, etc. Units of high and size
available. example, the monolith of mass 1130 tons and diam
19.5 m was supplied in 1987 to the station in
ca. 1.5 million m'/h
21 1
21. monolithic
c. Catalytic Combustion. The use of catalytic combustion

is attention. This technology is
to be one of the most effective ways NO, emissions.
at well below 1900 (which is easily in adiabatic com-
bustion), above which of oxides and oxy-
gen becomes significant. at than
these homogeneous gas combustion. The highest tem-
is by the of the catalyst. de-
veloped the system with a catalyst that can withstand
up to 1600 2000 h. [73]. The Johnson catalytic
unit may be continuously at up to 1700 [74].
fuels have been catalytically with high effi-
ciency, beginning with (low heating value) gases. fuel, No. 2
distillate oil, synthetic coal gas, diesel fuel, Jet A fuel, and fuel
oxidations in monolithic have been investigated [75-791. Cata-
lytic combustion of heavy distillates, oils, and synthetic fuels has
also been No. 6 oil and blends of oil also
combusted catalytically [80-831. The efficiency of catalytic combustion in
monoliths is excellent, as is shown in Fig. 22 [SO].
The gas catalytic combustion system developed by Johnson
[74] is shown in Fig. 23. consists of zones. the
section a small flame is used to the combustion by
212
No.2 el
22. Efficiency of catalytic combustion
400
83, Gulf
TYPE
Co., all
141
180 1 0 120
some fuels.
I with
I -
- +
-
rt;- -
FROM
COHPRESSOR
-1-
23. The Johnson combustion with
74.
the inlet gases they the catalyst. The fuel is not

completely and the flame is quenched by a
flow to minimize of oxides in the flame. the catalytic
section, catalytic combustion takes place at a low
which does not of oxides. The system is designed
213
and so that the gas leaving the catalyst still contains

fuel to an excessive in the catalytic zone. Com-

bustion of the fuel is completed in the zone by a chain
The system has been successfully tested using diesel fuel, wide cut
gasoline, gas, and containing
monoxide- methane.
has been by Tucci [83], as shown in
Fig. 24. the the monolith con-
by the aidfuel so that oxidation of the fuel is achieved.
The low in this section NO, The
gas leaving section C-1 is mixed with the flow, cooled, and
passed into a second stage When at
fuel the unit emits a minimum of pollutants. Advantages of this
system the of between the combustion stages
and a maximum gas than in the Johnson unit.
have been designed to combine the high
action of with the low NO, levels of conventional
catalytic They have, not found common applications.
Use of catalytic gas in the
of monoxide in exhausts by a 10. NO, the
was of 2 of magnitude [74,78]. These monolithic
by enhanced flame stability as with
The at of a combustion unit of

design is low but can significantly in the case of
fluctuations the stability of monolithic
catalysts is of The washcoat can with the
phase This may in enclosing catalytic
components into closed even in of the catalyst.
24. Conceptual design of a multistage combustion system.

with 83, Gulf Co., all
214
use of catalytically active of has been

suggested [2], even at the cost of This,

need not be as high as typical chemical applications. is a
ising in this can be used at up to 2490
is to most metals, and exhibits a
in platinum is used as a catalytic species, the tem-
must not exceed 1450-1500 to escaping the
catalyst Catalytic gas can now achieve
combustion of than 35 million kJ m-' h k ' .
have also found an application in combustions
[2] an design of a steam
by Latty [84]. this system an emulsion of heavy oil and was
with excess without soot the of
investigation. most designs, finned tubes with the washcoat
used in which the catalytic species was
2.
Flytzani-Stephanopoulos and Voecks [ 11, 121 investigated steam
of n-hexane in Ni catalysts by and
washcoated with y-alumina. have shown [12] that the ce-
was not stable when used the bed. A
of the solid was at conditions common in steam
This instability was caused by damaging of the washcoat
-
-.- U
* 2.5
S.V. = Zoo0
,1
'
- 17009
1 1800
- 1
800
112 1-112 3-114 5-114 7-112
POSITION IN in. TC IN BED.
25. Steam of n-hexane catalyst; T, = 1200

= 2000 [12].
215
-.-.- a
S.V. - a 3.0
TI 1000F
5-
1, IWXIF-
1- lrn -
V
5 0.5- 8
&&-
mu-
1m-
g 1m-
a1 - E 1200-
- \ iim-
\bH14 loo0 -
900-
I
P01 2I-m
4-1/11 8-114 12-318
POSITION IN TC IN
26. Steam of n-hexane took place;

T, = 1200 = 2000 [12].
and by subsequent of the silica by steam. The combi-

nation of a metal monolith (at the inlet) and a monolith the
exit) was also investigated. This monolith was found to have
heat than the conventional catalyst
bed and to to those of the packed bed.
the of the monolith changed in time, due to
and plugging of monolith channels.
of deposits the monolith caused complete physical
of of the monolith. The metal monolith sections
in condition.
studies of steam of n-hexane 1111 out
using only honeycomb monoliths of density 250 cpsi, washcoated
with y-A1203and with nickel. As a a
G-90C catalyst was used. Again, a significant in heat
was found. This is to to a catalyst
as to pellets. 25 and 26 [ll] the su-
heat of the monolith. the
of the always the monolithic catalyst
than the packed bed, the same heat inputs the wall.
3.
monoliths have been used in studies on meth-
anation using a catalyst [43]. based on equiv-
alent metal loadings the pellets and the monolithic catalyst. 27
216
c
J
0
I 4
E (a)
.
&, 0.26
-
- - 1.0
-
Y)
0)
*
0
E
0.24 -
? 2
Q 0
t
6022- - 0.9 $
.-0
2
6
s0z 0.20- 0
0
: 0.10. I I I -0.8
c I
3
.o
0.10-
al 1 -
.GI
E0 - 0.09 - - 1.00 -f
gg
5 5 000- - 0.95 cn"
a& 1 -
27. and selectivities: (a) packed bed; (b)
monolith [43].
shows the and selectivity both types of catalyst. The

activity of the pelleted catalyst is initially high, then slightly, and
finally its high level. The monolith shows a constant
but slightly activity. to these the selectivity of
the monolithic catalyst is (97%) and constant time while
that of the pelleted catalyst in time to a value of 83%.
typical space velocities estimated both catalysts and was
found to be 2 of magnitude the monolith. A
kinetic was the monolithic cata-
lyst.
Nickel on mostly, metallic washcoated with
alumina was subjected to study by et al. [44] and and
tholomew [45]. The specific activity of monolithic catalysts at a
low was found to be 2 to 5 times that of
catalysts. evidence has been that diffusion
in monolithic catalysts was substantially less than in pellets. At
high and high space velocities, the monolithic catalyst showed
217
100
90
80
70
I
0
C 60
.C
VI
a>
l
C
50
0
V
&I
W
U
40
W
Q
30
20
10
475 500 525 550 575 600 625 650 675 700 725 750
(V.)
28. 1000 50,000 h - l ; A, CO

0, CO, [44].
a 20-100% activity which was to the low mass

shown in Fig. 28. monolithic catalysts
active and selective all and in the
investigated. A Ni catalyst [44] was used kinetic
studies, in a kinetic of the
type. Low diffusion of a monolithic catalyst with a thin
alumina enabled the to the kinetics of this
fast and highly
et al. [46] studied methanation using a passage
to the monolith contained a shallow catalyst
bed at the wall. The bed was the gas by a The
obtained sufficiently to explo-
as at in a much
4. HydrogenationlDehydrogenation
of benzene and of cyclohexane in
monoliths was studied by and
monoliths washcoated with alumina used with nickel platinum as
218
the active species. based on an Eley- mechanism

and kinetic estimated. Again the use-

fulness of monolithic catalyst kinetic investigations diffusion resis-
tance) was indicated. coefficients evaluated as well.
5. Oxidation
and Sheintuch [32] optimized an monolithic
of a type SO, oxidation. The modeling
was not, based on data. and kinetics of
ammonia oxidation on a cobalt catalyst of type (a-alumina
and Ti02) was the subject of by et al. [33, 341. The
a qualitative between calculated and
axial Subbana et al. [35] investigated the catalytic
oxidation of biphenyls in a monolithic system. Ce-
supplied by used to make Co,O,, and
CuO catalysts. The not et al.
[31, 851 studied ethene combustion in the of a platinum catalyst.
They the of empty and packed wall
undeveloped, developing, and fully developed flow. A good
between calculated and was found.
B. GaslLiquid
the attention of because of

beneficial flow at flow conditions, namely the so-called seg-
mented flow. The of slugs in the flow in a of the
axial and in an of mixing in the channels.
mass between the continuous phase and the wall in slug flow
is significantly enhanced as with continuous flow. This is discussed
in detail in Sec. the mode of op-
segmented flow) opens optimization.
the most studied gadliquid in mono-
lithic of the on this subject was at the
of Technology, Sweden. was focused on
monoliths with channels of sinusoidal shape. and
[51] studied of acid in a
monolith in the segmented flow The effectiveness the
monolithic catalyst 0.081 to 0.115 while 5-mm in
a bed, it amounted to 0.021-0.024. This can be to the
diffusion length in the monolith (0.15 mm) than in pellets (2.5 mm
in a typical bed). the whole the effectiveness
is still due to the access of to some
of the catalytic
et al. [52] out of
219
and in monolithic with segmented flow.

was also with the aim of data the

evaluation of mass coefficients in the monolith. The con-
cluded that the dominating mass step is the
I
7000 - 0
0 2.5 5 7. 10 125 IS
kr
29. of 2-ethylhexenal: p = 8 433 + , 2-ethyl-

hexenal; e,2-ethylhexanol; and (b) monolith
53 with kind Ltd.
OX3
220
1.o-
8
6
10-
8
6
4
0 .2 .4 .6 .a I 1.2
C
lo2
30. vs. gas flow at 313 [58].
the gas plugs to the channel wall. one this

mode to 70% of the total Obviously,
segmented flow gives the best mass conditions. The
mass coefficient 0.00014 to 0.00023 m
and [53] studied of 2-ethylhexenal
in a monolith; also The monolithic
much as is shown in Fig. 29, but such a
was due to deactivation of the catalyst
of has been put on
using monoliths of [54].A
of both phases the was found to be
of An in a con-
stant capacity of pilot plant and indicating no scaleup
effects. the capacity in the case of flow of
the was 30-50% than that of flow at the same
velocity. The high between phases in
combination with the thin liquid film in the high
of the monolithic catalyst with segmented flow.
and [58] investigated of a-methylsty-
into cumene using a monolith coated with (1% of active
metal). They studied the upflow and downflow of
The liquid flow was 0.5 to 3.4-10-3 m and the gas
flow was up to 1.2.10-* m s s ' . The a mon-
olith at upflow of and a slight sensitivity of
the to the liquid flow between in
221
l L_
n 00 0.4 0.8 1.2
SIQ 106
24
0 0.4 0.8 12 1.6 2.0 2.4 2.8 3.2
SIQ 106
31. and extent as a function of

of oil: 643 102 0, pellets; A, monolith; (a)
oil, and (b) synthoil liquid. with 57.
1981, Chemical Society.
222
the monolith and the bed is shown in Fig. 30. The monolithic catalyst
is to pellets at a gas flow

Competitive of thiophene and cyclohexene was the sub-
ject of by and Gahne [SS]. The kinetic
found to be in a good with the data in the
The effect of diffusion limitations was evaluated as negligible on the basis
of the Weisz modulus, which amounted to 0.32. Thus, the monolithic
is an excellent in Ed-
vinsson and [56] used a monolithic catalyst to
of dibenzothiophene They
estimated kinetic in a model. The
of of was that of thiophene.
Soni and [S7] studied and
fication of oil and Synthoil liquid in monolithic and
bed These on the unit basis.
of some in Fig. 31. The monolithic catalyst
activity was than that pellets. This was due to the
in and the diffusion length;
monoliths these quantities 8.0 nm and 0.114 mm 3.3 nm and
1 mm Effectiveness the monolith and
found to be 0.94 and 0.216,
et al. [86] made an attempt to oxidize phenol in using
a monolithic of the monolithic at low
little but substantial of phenol. Con-
was unaffected by flow of liquid but showed a max-
imum a gas flow This maximum may be to the
bubble flow to segmented flow.
1.
Since the combustion of pollutants in exhaust was the most
application of monoliths models these
developed and these modeled most extensively.
these models do not models
except in the of the kinetic and the values of the model
Young and Finlayson 1871 an extensive model
monoliths; have simulated the of
monoliths using modified models. Young and Finlayson have classified the
models as shown in Table 10. some lumped
flow should be combined with of inside
the solid. the model of which has not been included in this table.
223
10
of
and conduction
Fluid flow model in and washcoat
~
Lumped
11-A
111-A Finite
with the designation A by a finite of axial conduction

and diffusion in the solid. models without the designation A, axial con-
duction diffusion in the solid is neglected (assumed to be equal to
A analysis led the to some justified simplifications as
follows:
1. Axial diffusion of mass and heat in the fluid is neglected. The axial
diffusion may be neglected than 50,
which is the case in monoliths catalytic
2. The converter is symmetrical. data show that the
flow is not the same in each channel, but use of effective
makes the initial velocity less even; no
have been
3. The thermal accumulation f o r the fluid is neglected. This may be
neglected since the of the fluid to solid capacities is
0.0007.
4. The mass accumulation thefluid is neglected. This may be done
since the time in the 0.003 to 0.02
s, while the time constant is 2 s.
5. The transient response velocity is neglected, since velocity changes
will in the of t = l.Sr;p/p == 0.002 s.
6. The transient response mass in the catalytic layer neglected.
This may be done when the of to mass time constant
is monolith this is of the of lo',
which is much than the of 1 suggested by
and Finlayson [88].
As equations the fluid the following
assumptions have been made:
1. coupling is neglected, and the effective multicomponent
diffusivity is used.
2. The fluid assumed to be constant the
section of the channel; the gas is ideal with a constant
mass.
3. The is negligible.
224 Jh
Catalytic combustions usually in an adi-

abatic mode. heat mass and momentum balance equations the

fluid in models 11, and [87]:
a the in (10) may be ne-

glected because the of the catalytic is by some
of magnitude. the steady state the above equations can be
into:
and the length and of the channel,

and y in a channel t is
the dimensionless axial ( F ) is the flux, is the
mole of component i , is the viscosity of fluid, is the density
of fluid, and is the mass of the
may be assumed to be constant as they only by
15% a 200 change oxidations in and
models 1 and of lumped flow, heat and mass balance equations

by the Eqs. (12) and (13) the channel section
and by defining Nusselt and in the usual way; they
become :
Nusselt and must be specified a and usually

assumed constant along the channel, although they may in position
and time with the peak at the ignition point. This assumption gives
225
to some between axial obtained

lumped and flow models.

in the solid in the to
the channel axis may be neglected if [d(1 - * [A&] > 20 [89]. mon-
olithic the is about 50, and the has
been neglected. Thus, the heat balance in the solid the state
a channel monolith, which is the most commonly used
monolith, is given by the following equation model
5 = n is the unit point a two-

dimensional (ri)is the the catalytic
and is the at the solid given by:
-
=
4E
The +
6,/4) is the length of the wall in
equations can be
Assuming that heat conduction is fast enough that no
develop the Eq. (17) models
and 11-A any becomes:
is constant the channel

When the axial conduction in the solid is neglected, which is to some
extent justified monoliths, the balance the solid
(models and 11) becomes:
mass balance in a is the usual

and diffusion in a slab is taken:
+- ri = 0
@s.i
226
with conditions:
= d6,. is no that diffusion axially to anti

the can be neglected; the is valid in channels.
The mass balance a in model 111-A is:
<= (r,) is the the whole catalytic

that is, the including diffusion effects,
and Y5., = 1 <=,. Assuming infinitely fast diffusion, one obtains
the following models and
+ - (nV Yf.i) = 0
2
Neglecting axial diffusion and the the mass balance in models
and becomes:
The initial conditions model 111-A

T, = 5)
TJ(O)(<, and Ys,l = e) t = 0 (265
At the fluid/solid
Yf.,
= Y,.] and Tf = (27 I
The conditions in a
(28 1
The conditions in the axial depend on the of the

inlet and outlet which modeled by assuming they ideally
tanks. and mass balances in the inlet (6 = 0) yield:
227
and mass coefficients used to heat be-

tween the solid and the fluid at the inlet (< = 0):
Nusselt and defined by means of as the

length. At the outlet (< = 1):
can be used as exchanges of well-

developed heat that a a heat
The with walls that have been
modeled by and Wei [90-921 using cell models the
of was to monoliths filled with pelletized catalyst.
They found a between data and data
calculated by means of the cell model.
2.
a. usually out in
a flow except combustions gas the
nolds 2000 to 3000, indicating and
flow. monoliths the effect might be
sometimes expected to be significant, especially flow.
effects studied by et al. [31]
and Wendland [93]. and [31] investigated the com-
bustion of ethene in a honeycomb which consisted of
and of the same length, which the de-
velopment of a velocity feeding the monolith at the noncatalytic
side, the flow had been fully developed when gas the catalytic
of the monolith. the NO, the gas the
monolith met the catalytic the flow was undeveloped.
of shown in Fig. 32. Use of a evaluated kinetic
constant = 1.28) in calculations fully developed flow gave
1. An of to 2.7 in between
the calculated and This indicates that an effective
constant the taking place in the developing flow should be
than twice as much as the value.
Wendland [93] studied the oxidation of monoxide and
flow conditions typical engine use was made of
segment monoliths instead of one times as long as the individual
segments, which in a of CO and by
228
-- - :
:
:
Da 1.28. I 1.09
0 Da = 1.28. E 1.09
1 :Da 1.28. 1.09

2.3.4 : Da 2.7. = 1.09
R)
32. effect in highly active monolith; combustion of etheni.

(Co = 300-500 ppm, 400 with 31.
1978, Chemical Society.
and 33%, suggested that individual segment\ I
the benefit segmenting would be since the of thl:

length of zones developing flow to the total length of the monolith was
et al. [94] have also found a significant of .k
monolith when cutting the monolith into (up to) 16 slices and
them with spacing of 3 mm with an
of 45". CO 50% the continuous monolith to
than 90% the sliced monolith at = 100 with essentially no
penalty.
Young [89] by simulation that of the fully devel-
oped velocity with a developing conditions as in an
gives a maximum of only 7%. thl:
the lengths momentum, and
developments
-2 (34)
d
No is unity, the the Schmidt velocity,
and and is the valuc
0.035 [95] to 0.0575 [96] momentum Skelland
[97] = 0.05 while [20] quoted = 0.04 all
of typical sizes of monoliths channels (d = 1.5 mm; = 7 h
mm) and typical conditions = 200), develop withiii
a distance of less than 20% of the total monolith length. the:
Schmidt liquids an of magnitude of up to lo',
229
which indicates that undeveloped the

channel. this case the of the mass coefficient along

the channel must be taken into account.
b. Drop. Johnson and Johnson [6] the data on
the in monoliths shown in Fig. 33. The values
slightly but in with the
equation:
32
= (35)
d2
The can be also by Weisbach equation:
The is valid only fully developed, steady flow of

media. With the length mean vaiue of the it
T
+
\3
z
Lu
CURVES
0 3ZPV
-
-I
33. of with gas flow unit of

6 by of the of Chemical En-
1961 All
230
also gives a of the with developins,

flows. The length mean values of the developing

flows calculated and fitted by [21], to give (3)
values of limiting channel
given in Table 7 (see Sec.
c. Heat Transfer. i. As indicatec!
in the discussion of the basic assumptions of the Young and
models, no significant within the washcoai
(catalytic in the to the wall; catalytic-
combustion in the estimated is aboul.
1
ii. Fluid/Solid As discussed in Sec. heat
between the gas and the channel walls can be by Eq. (4) and
the asymptotic values of the Nusselt given in Table 8.
[21] has the following
0.4s
1 + (37 1
The value of the constant B equals 0.078 smooth

[98], while catalytic monoliths the value found by
is 0.095. The limiting Nusselt value C depends on the
of the channel; the values shapes given in Table 8.
et al. [99] developed the following flowing
channels:
Nu = 0.571
( r7
et al. [lo01 studied mass oxidation of
(38 1
in
monolithic catalyst. They the following equation:
0.829
(39)
which gives values of heat coefficient than the

and The this et al.
[ 1011investigated of monoliths to stepwise changes
of the of the at the inlet. These Nu values
lengths (up to 7.6 cm) of channels up to 10% than those
calculated the smooth while
channels (up to 20.5 cm) they found Nu values at most 15%
The data discussed Nusselt which i n

along the channels. Young and Finlayson (231 solved balance
231
34. Nusselt (-) and (---) vs. dimensionless dis-

tance: CO oxidation, T,, = 615 Yf!A = 0.04, C = 0.0132 m/s; channels;
D , , = 0.61 mm, = 0.102 m (close to
23 by of the of Chemical
1976 All
equations models of flow and found that at the inlet

the Nusselt is much in spite of assuming that all
fully developed at the inlet. peaks Nu identified at the light-
off Nu to infinity model and to finite values
model 11-A, which includes axial heat in the solid. This situation
is in Fig. 34 [23]. ignition, the best Nusselt is that
constant wall
...
111. Axial Conduction. heat conductivities can be evalu-
ated using values and the of the Axial
heat conductivity in the fluid phase need not be taken into account
than 50, which is usually the case in monolithic
and [lo21 indicated that axial conduction in the
gas conditions may be neglected.
iv. Conduction. heat in mon-
oliths of low conductivity may be neglected. in metallic mon-
oliths heat has been found to be even effective than
in packed beds [ll, 121. Attempts have been made by Flytzani-Stephano-
poulos et al. [103], et al. [104, 1051, and Cybulski and
[lo61 to develop a model heat in metallic monoliths. The
model of the gives the best between calculated and
d. Transfer. i. and
232
[ 1071 the following the effectiveness

of a monolithic catalyst kinetics:
+ is Thiele modulus and is mass defined as =

These also the the
effectiveness any n:
1
q = (1 - exp
to the of effectiveness monolithic

catalysts with kinetics, of calculations oxi-
dation of monoxide in the catalytic of thickness of 0.0254 mm
shown in Fig. 35 [23]. Voltz et al. [lo81 on kinetics of this
used in these evaluations. is the that the
effectiveness significantly the light-off point the
jumps to 600-800C.
a of fact, evaluation of model in this does
not that catalysts and methods developed
pellets can be monolithic catalysts. who
in on this subject to books by
[lo91 and [110-1131.
ii. Fluid/Solid [21] has given the
analogous to that heat
0.4s
1 + (44)
constants B and C have the same values as B and C in

(37). et al. [99] data using the
following equation:
Sh = 0.705 g)"" (45)

233
35. Effectiveness CO oxidation

(in "C); D,,colD,~,, = 70. 23 by of the
of Chemical 1976 All
et al. [loo] the analogous to that heat
0.829
(46)
Ullah et al. [114] heat coefficients con-

ditions and of using the following equa-
tion:
0.483
Sh = 0.766 (47)
234
et al. [31, 851 evaluated mass coefficients ex-

also in a system (ethene combustion). data

located between those of and as shown in Fig. 36 and
in with the of Young and
Finlayson Shah and London (see Table 8). Like the data, the
values tend to an asymptotic value, to the mass
coefficient, which to when is no flow in the
channel.
iii. Axial flow in the applica-
tions of monoliths. this the axial coefficient can be
calculated using the equation [115]:
= -
192 Sc > 1
Sc
equivalently
(v)2d
= (49)
1920
flow (lo2 < < lo4), 11161 gives
0.28
= -
<f
f is the
typical conditions in = 2, and as a typical
monolith Lld = 70, amounts to 140, which is much
I' I
4 10 50
36. in monolithic Sc = 0.83)

235
than the limiting value of 50 above which axial in the gas

phase may be neglected. the liquid phase of much diffusivity, the

axial might become significant a single-phase flow;
that is beyond the scope of this
3.
The vast of modeling activities has been focused on
and combustion. These models in Table 11. A
amount of this only
of of pollutants and
[117] the simplest model with complete
mass limitations (i.e., the of the at the monolith
is essentially The simplified balance equations could be solved
analytically. also showed of
but no with calculations was made.
and [31, 851 used an extended model to also
account effects; the model was applied to cells. The
finite method using the scheme with a
size and a double collocation method was used to
solve the balance equations. The of the computations indicated that
effects can significantly affect the
et al. [lo21 calculations using one-dimensional and
two-dimensional models; evaluated using a
quasi-static the gas phase. They found that the light-off
point is closest to the inlet sinusoidal channels and that this distance
in the and cells. Nusselt
and small channel sizes lead to heat and, conse-
quently, to a delay in light-off. This disadvantage is compensated by
a mass and in the channel the ignition.
When the Lewis is than 1 (e.g., the wall
may jump above that to adiabatic This was
by [117]. The one-dimensional model with
asymptotic Nusselt gives which in good
with those of the two-dimensional model.
Young and Finlayson [ 1181 developed one- and two-dimensional models
channels. The method was used to solve equa-
tions of model and collocation model 11. was found that
the effectiveness is close to unity the ignition. This
to infinity at the light-off point and then to
due to mass limitations. The of the calculations sug-
gested that a cell with good mass and heat
may not always be to a with
in with the findings of et al. [102].
The at the light-off point implies that axial heat
11
of Catalytic
Flow in Axial cond.
Condition in solid kinet. method
Oxidation
S L No No No 1st Anal.
S L No No No n-th
S No No No n-th
s, T L, No No No Langm.
s, T L, No No No n-th OC
S L No Yes No n-th
S L No Yes No n-th Anal.
S L No Yes No n-th
S L No Yes No n-th
S No Yes No . Anal.
S Yes Yes No Langm. oc

S L, Yes Yes No Langm. OC
s, L Yes Yes No Langm. oc
S L No Yes Yes n-th
No Yes Yes
No Yes Yes
No Yes No
Yes Yes No .
No Yes No .
Yes Yes No . oc
Yes Yes No
S No No No
S No No No
S No Yes No
S No Yes No
S No No No
S No Yes Yes
T No No No
T No Yes No
T No Yes No
No Yes No
S, OC,
N
4
238
conduction might be of and should be included in model

et al. [121] used model in They found the

effect of longitudinal heat in the solid to be when =
(Lv,pC,/h,)(d(l - is less than 200. values of the
conductivity of the solid phase need not be taken into account and the
model to model steady states identified, which
to axial conduction in the walls.
Senkan and 11191 simulated monolithic catalysts by also
taking into account the effective heat conduction in a solid.
techniques used, depending on conditions. Effects
of changing conditions on the effectiveness and
maximum nth kinetics
and Sen [ 1201 asymptotic solutions model and
analyzed the of the of
conditions the asymptotic solutions
well.
Stevens and [122] used model while changes
in velocity due to systems, the
velocity model indicates a final and
than by the constant modei. was
found to have a small effect on the Thus monoliths, the
final given by the assumption of constant closely ap-
that by the full model in the individual channels.
Stock and Lowe [123] used model 11-A to equations the
kinetic analysis of in monolithic catalysts. These
[124] also applied the method the of data
CO oxidation, to aged poisoned catalysts. The most point in
the data is that axial wall
taken into
Finlayson [125] used model 11-A including diffusion in stud-
ied and multiplicity CO oxidation with
wood kinetics. found that the shape of the cell does not influence the
to axial conduction, which affects
significantly. Finlayson also studied the effect of an uneven velocity
bution at the inlet using model 11. he made the as-
sumption that the heat conduction in the walls is infinitely high.
this assumption he found that the 2 2 0 % of the velocity
the mean value does not change the monolith The
mances to those a single channel conditions.
Finlayson and Young [126] extended the study on to a
monoxide using model 11-A. They found that is enhanced
by high monoxide and low flow model
qualitatively with data, the
and axial conduction in the wafls have a effect on
to data, the simplest model is
239
in cases with multiple steady states, since it an extinction

essentially independent of flow in the catalytic

and axial conduction in the solid also taken into account in the model
of and [127]. The basic Finlayson conclusions
multiplicity of steady states but the of studies
was extended. They found that and oxidations have
a significant effect on the steady-state wall This should be
included in monolith calculations and The
effect of is especially since it was found that it can
significantly the multiplicity by the ex-
tinction also in wall than those
when only CO oxidation. these [125-
1271 modifications of collocation used to solve the
model equations.
and [128, 1461 studied the effect of on
the They used a simple model completed with a
et al. [ 1281 suggested into
the model. Sinkule and [146] found that: (1) the exit
is not affected by (2) the shape of in the
channel is dependent on the type of conditions, the
between and models is (3)
adiabatic conditions does not essentially influence
the ignition and extinction limits; and (4) the effect diminishes
five steady-state Studies on the in monoliths ex-
tended to a flow model by Lee and [129]. They an
design to evaluate the of monolith
lengths 99% of monoxide with and without
account being taken of
99 o/o
- 1 + O.~~~AO.~PP~O.IS~X-~.~~Y
-
A is of the
and is the solid
is channel is the of solid, and is

aspect Lld.
Oh and Cavendish [130] studied the of catalytic
taking into account oxidation of CO, methane, and
11-A was used calculations
240
monolith. typical conditions, ignition about 1 min,

while the steady state is 3 min. The maximum

was found to with both monolithic length and cell den-
sity. The position of the peak moves to the exit of the monolith
with exhaust flow The effect of axial conductivity of the
monolith was also investigated. As might be expected, the
mal conductivity the magnitude of the
the the magnitude and location of the tem-
peak found to be insensitive to the of the
solid conductivity. The initial does
not the essential of the except that the
location of the maximum wall is shifted
The most extensive studies on the state of
monolithic those by [ 1321. applied
a one-dimensional model accounting the heat exchange between neigh-
channels and with the CO oxidation was studied.
pinwheel, and even velocity assumed.
The model equations a complex system whose solution 48
min time on a to simulate the 240 s of the
found that flow may influence the
of the leading to of the light-off
The model showed that the heat losses to the
only slightly the ignition but may significantly the steady-
state flow can also influence the cat-
alyst deactivation. The of the simulations show that flow
and heat losses must be taken into account in any model
used to design catalysts optimal Catalysts poisoning also
has to be taken into
was the subject of many studies. Oh and Cavendish [131]
computed poison both the catalyst and along the length
of the time. They investigated the of the to the
time to poison. model was used by and
[147], who found that poisoning and had opposite effects on dif-
fusivities in the and Sekella [38] analyzed deactivated
monoliths and found the between the amount of poison de-
posited and the position within the monolith. The amount of poison was
found to be much dependent on the position, indicating
velocity the monolith. poisoning was found
to be the main of catalyst deactivation [ 148- 1511. Lee and [133]
assumed kinetics of poisoning to be and the poisoning
and emission uneven velocity
at the inlet.
oxidation was taken into in some studies
on the catalytic combustion of fuels. Tien [135] of inves-
tigations on the sensitivity of a one-dimensional model
241
design and A kinetic scheme was as-

sumed: of oxidation of ,
and oxidation of monoxide in the second step. Fuel and
lumped components.
and [136] used a model in computations
CO oxidation. They found that at inlet 650 to
1150 the homogeneous also A com-
(catalytic and homogeneous sections in was as a
of simulations.
Ablow and Wise [138] extended the above model to axial heat con-
duction in the solid phase. They the model simulations with
[117] and found ex-
tensive sensitivity studies, et al. [137] used a
model with velocities along the monolith. They found an excellent
between the of calculations and the data of
and [2]. The conclusion was that homogeneous combus-
tion must be when catalytic
and [ 1391 studied
cesses using a flow model. conclusions the
of the homogeneous to those of
who used models. means that at of 700-
1100 homogeneous gas-phase begin to significantly
to the pool. et al. [140] used a one-dimensional model
with a heat coefficient computed as functions of distance, wall
inlet gas and inlet flow conditions. The effect
of on was discussed. on
these the cell concept was developed. Subsequent ex-
testing this concept to be successful.
Tien [141, 1521 also simulated states of a using
the same as mentioned [135]. studied the
influence of and conditions on
time. Ahn et al. [143] also took into account the axial conduction
the heat balance in the solid when studying the of the
They found that fast to changes in
conditions is by monoliths with thin walls, low density, and low
heat capacity. cell density metallic in
to monoliths. Thus, channels
display a than sinusoidal
et al. [142] used a one-dimensional model accounting axial con-
ductivity in the solid and heat losses to the
oxidation was investigated using the mechanism. sen-
sitivity of the model followed the
et al. [144, 1451 studied the of com-
using a flow model. They investigated the of
oxidation both and by simulation. A good
242
ment was as as levels

the CO content in the gas flowing out the the

was The of two-dimensional effects within channels was
evidenced.
et al. [33,34] developed a two-dimensional model accounting
the axial heat conduction in the solid. They applied the model to
the of on ammonia oxidation in the monolith.
et al. [42] modeled the selective of N O with
ammonia using a one-dimensional model accounting diffusion in
The with the with both
unpoisoned and poison-doped V,OslTiO, catalysts. Effectiveness of
these catalysts 0.46 to 0.94 depending on the and
the catalyst
et al. [153] modeled a honeycomb
of naphtha. Silicon was chosen as
of the because of its high conductivity and its
to shocks. A detailed kinetic model including 1054
actions was used. convective and heat between a
wall and the fluid as well as and longitudinal conductive heat
exchange inside the wall taken into account. exchange with the
was also A good between
of simulations and was found. An simulated
of the feed was found to be in the monolithic (99.1%) than
in coils 91.3 to 92.4), with high ethylene yields.
B. GaslLiquid
1.
flow exist gadliquid small chan-
nels, as in Fig. 37 [154]. At low liquid velocities, small gas bubbles
the liquid. a slug flow, the continuous
flow of small bubbles/liquid is by a flow of
bubbles whose is with the of the channel
and whose length is even than the thin film of the
liquid between the bubbles and the wall gives to a significant
of mass as with a bubble flow. Axial
can only by this thin and, consequently, is much
limited. The flow can be as a case of slug flow
without small bubbles in the liquid. The film becomes
and pulsates at an flow. and time
then The between the flow
flowing a 2-mm tube is shown in Fig. 38 [155].
A mathematical model a slug flow has been out by
ziantoniou and [51] with to in a mono-
t
7.
......
...
. . '.
......
...... ..
.....
.........
.
.: :
..
..*. .
......
...
.*.:
:.. . :.
.:. ... .
*.
. ....
.
.
..
.
a
*
-
*.
243
t t
37. Flow in flow. 154

by of the of Chemical 1980
All
lithic catalyst such as that shown in Fig. 39 [53]. The gadliquid

flows sinusoidal channels, gas plugs as-
sumed to be as shown in Fig. 40 [53].
The following assumptions have been made: (1) the is
with to liquid component; (2) the channel can be
as a which is included in a system; (3) hy-
is to the catalyst the gas plugs and
the liquid plugs; (4) conditions within the
gas and liquid plugs; ( 5 ) gas and liquid plugs pass the
channels, giving conditions at the wall.
The balance equations to Fig. 41, the simplified slug flow
is The mass balance of in may be by
the usual a slab:
5 = XI61
= Dct/6t
=
244
200
1
I
150
<
c
-2
; 100
>
a
0
0 1 2 3
38. in a single with

155. 1977, Chemical Society.
39. The monolithic catalyst 53 with kind

Ltd. OX3
245
40. The gas plug in a sinusoidal monolith channel.

53 with kind Ltd.
ington OX3
41. model
into Eq. (54), one obtains:
The following steps in must be (a)

the gas plug into the liquid plug, ( b ) the liquid plug into the
wall, and ( c ) consumption of at the wall.
246
(a) the gas into the liquid is given by:

is constant.
(b) the liquid into the wall is given by:
= kcr(cHr- cw)n&d (60)
is used the low of
the solvent and of the solution at the wall when a gas plug is
passing
C, = C* = (61)
Since the conditions within the gas and the liquid plugs then
The conditions (58) as follows:

aclac = 0 5 = 0
c = c* 2; = 1 and 0 < 7 < 7 ,
6, is the thickness of the liquid film. Condition (64) is valid

the passage of the gas plug the channel, with a time constant
while condition (65) is valid the passage of liquid the channel,
with a time constant v2. Condition (63) must always be satisfied. Thus
c2
substituting u = and y = c/c*, ( 5 8 ) becomes:
4u-a *Y aY
+ 2 -au - +2y = -
aY
au2 a7
247
and conditions (65) and (65) become:

y = 1 u = l a n d O < ~ < ~ ~ (70)
y) u = 1 and <T <
Since the solution condition (70) is the initial condition

condition (71) and vice the solutions must be until they
The model equations solved using collocation.
2.
Drop. The two-phase flow in small
channels is the sum of the the static head, and
effects:
= - gPW - + (72)
and Ozel [155] suggested that the is of significance
only at high cell density, than 250 cpsi. to them, the
and static head et al. [54]found
that, in flow in the both
effects and effects. At low velocity and chan-
nels, the can be calculated the weighted sum
of the liquid- and gas-phase using the
equation:
b. Transfer. i. the Gas and the

Wall. The mass coefficient the liquid film
by the infinite plate) the gas plug is given by:
The following equation has been to the thickness

of the film, Sf, with conditions and of the
liquid:
Ca is [ 1561 evaluated the values of the

coefficients a = b = 2/3, while and Stubbs [157] found them
248
to be equal to 0.25 and 0.5, < 0.015.

and [53] data using the

a*
- = 0.18 [l exp( -3.1.Ca0.54)]
d
- (76 1
ii. the Liquid and the Wall. and
[158] studied mass in a slug flow. They
data using the following
0.44 -0.09
Sh = 3.51 (m)
Sc
(2) (77 1
and [53]
in
(68).
...
111. the Gas and the Liquid Clift et a1
[159] the following mass between the fluid
phases at the ends of the gas plugs:
I 5 400, and
Sh = 1 + (80)
400 < I2000. The equations
and [ 1601 have shown that the ends of thc
bubbles can be as These [53] also
the following equation:
Sh = 0.41 (81 )
et al. [161] found the best fit to data if
(80) was multiplied by a of 0.69, that is, using the following equation:
Sh = 0.69(1 + Sc1131 (82)
all the above equations, Sh is defined by (68).
iv. Axial Guedes de et al. [162] stucl-
ied axial mixing in slug flow. They found the following thc
coefficient:
the length equivalent to fully mixed wake, L,, is to channel

d
L, = (84)
249
-: 1.7818E-02
42. velocity in the liquid plug.

164 with kind Ltd.
and (Y 2.3 to 2.8 conditions. Axial

was also a subject of a study of and [163]. and
[ 1641 simulated the flow showing significant backflow
within bubbles (see Fig. 42). is, accepted that the
longitudinal mass can be neglected and plug flow assumed. This
is due to the small thickness of the liquid film gas bubbles and
little axial mass between these bubbles
3.
and [51] modeled the of ni-
acid to aminobenzoic acid in the of a monolithic pal-
ladium catalyst. Time constant and and plug lengths estimated
conductivity of these
shown in Fig..43. at the wall
conditions shown in Fig. 44. Effectiveness found
4-5 times than those in a the
of acid.
and [53] simulated of 2-ethyl-
hexenal using a simplified model. The model used the
well. The high of the monolith catalyst was suggested to
be mainly to two high gas-liquid and liquid-
wall and (2) thin liquid film the gas bubble the
wall.
et al. [52] studied of and
They found that the mass coefficient
250
43. Conduction the monolith of 427 channels of 2.0

mm2 (a) liquid 16.7 cm/s and gas 15.6 cmk; (b) liquid 16.7
cm3//sand gas 27.0 cm/s; (c) liquid 10.8 cm% and gas 15.6 cm/s. with
51. 1984, Chemical Society.
44. at the wall vs. time. with

mission 51. 1984, Chemical Society.
the the gas plugs to the liquid plugs is only 12% of that
the between the liquid plugs and the channel wall. The dom-
inating mechanism of mass is that the gas phase to
the wall, which than 70% of the total
This is insensitive to the gas holdup.
Cybulski et al. [ 1651modeled monolithic meth-
anol synthesis. They found that such might be an
native to conventional bubble column
251
V.
advantages of monolithic with both

walls have been
by simulations. No has been made with
of common use such as packed bed gas-phase
and gasiliquid
showed of monolith
of a oxidation and
genation Combustion is the main of applications of
monoliths. to the low heat conductivity of most monoliths, they
usually in an adiabatic mode. studies on the possible use of
monoliths in the chemical focused on
tions. These seem the most the application of
monoliths in the chemical because of as well as
some physical of the
Gas-
Some of typical monolithic and packed bed given

in Table 12. The most significant between the monolithic
and fixed-bed is that catalyst pellets packed and the
12
Typical and
bed
1.5 5.0
mm
Voidage, E 0.65 0.42
1900 1200
a(m2/m')
Volume of cat- 0.05-0.2 Up to 0.58
alyst
length (pm) 25-100 (washcoat thick- 100-2500 (depending on
ness) the catalyst
Flow = 50-600 = 50-500
and
= 2000-3000
0.1 at = 300 27 at = 150

m-')
252
flow of is while in monoliths the catalyst and f l o ~

evenly the whole packed beds, a

exists in local velocities and, consequently, in mass and heat
conditions. (e.g., at an of adjacent
the catalytic is much less accessible to
This can affect the yield and selectivity of complex 11
packed-bed is no in accessibility to the catalytic
in monoliths. The flow of is and so mass and
heat conditions. Thus, no unexpected events likely to
in monolithic like those
in packed beds.
The in also significant
monolithic catalysts is about 2 of magnitude
than beds of the same length and gas flow This is
in Fig. 45 [15] monoliths and a bed of small
Thus, depending on the it can be estimated that savingx
pumping up to 50% (e.g., in plants thL.
oxidation of
monoliths, coefficients heat and mass between the bulk
of the fluid and the of the catalyst (at the conditions of Table 12)
the in heat and mass coefficients i\
not as as that of the The Nusselt
channels at < 600 and Sc = 1 (gases) amount to 2.5-6.0.
beds, estimated using the hb
et al. [113], 10.7 to 29.6. The
(i.e., the mass and heat of monoliths) is than in packet 1
beds, as shown in Fig. 46. both types of the total amount
mass between the bulk and the catalytic unit volum:
1,000 10,000 100,000

(SCNCF
45. in monoliths and a packed bed vs. flow

with 14.
253
10 20 30 40 50 60 70 80
300 9
1 2 3 4 5 6 7 8
46. of monoliths and beds.
is although mass and heat coefficients mon-

oliths. The mass and heat can be enhanced in monolithic
by using monoliths. Velocity, and
developing in such monoliths. is well known that mass and heat
conditions then than in the case of fully developed flow.
to the the voidage in monoliths is
than in packed beds. This and the catalytic account
a significantly amount of catalytic species in monolithic catalysts
(see Table 12). when diffusion is not the step,
unit volume of monolithic catalyst will be less than
pellets. competitive monoliths
can good conditions optimization of the This is due to
the diffusion path.
The monoliths of thin catalytic can also be expected to give a
fast to changes in conditions. Thus, is
optimizing of complex kinetics, which
254
between of and ma!/

influence the selectivity. This is a why havt,

so much attention of scientists in the last decade (see, e.g.,
by of Lausanne Silveston of and co
No conclusion monoliths pellets

diffusion-limited can be A of thtb
monolith with the packed bed must be made
of
is significant in the use of monoliths, name]!
the heat exchange with the This implies an adiabatic,
which in a high gaseous systems nl
low heat capacity. The can be in many ways, example, b?
addition of steam to the if this does not affect
stability, activity, and selectivity of the catalyst. A monolith should not bt,
when the adiabatic the even
when is in the is
the the catalyst.
adiabatic can be when al-
flows coupling This can be done in thc
same in possibly monoliths. of
actions can then be easily, example, heating
up the out conjugated
with an by using the same monolith by al.
use of monoliths in with the hot monolith.
The the monolith in an adiabatic mode call
be eliminated by using a metallic monolith. effective conductivit;,
can be than that of packed beds. Such monoliths could be used
those sections of packed-bed the highest heat fluxes
expected to heat mechanisms in such monolith4
have not been sufficiently explained. studies need to be
to develop design methods metallic monoliths.
B. GaslLiquid
can be as an to and
Schoon [ 1661 monolithic
in a slug flow with and beds; see Table 13.
at liquid ve -
locities and much gas velocities than monoliths. The gas
velocities the by the flow
velocities a into flow would in
this to monolithic ones
by high consumption of gaseous this s u -
is at the cost of a much in
255
13
Typical and
Gas/Liquid
bed
~~~
(mm) 2.35 6.0 0.01

(1 96 catalyst)
Volume of catalyst 0.07-0.15 0.55-0.6 0.005-0.01
gas velocity (m =
Test 0.01-0.03 0.0001- 0.003 500-1000
Full scale 0.01-0.03 0.001-0.02
liquid velocity (m s-
Test 0.01-0.07 0.002-0.045
Full scale 0.01-0.07 0.15-3.0
m- 3.0 50.0 6.0
liquid/solid, 0.03-0.09 0.06 1-4
(s ')
gadliquid, 0.05-0.30 0.06 0.1-1
bed is almost 2 of magnitude than that in mon-

oliths, as by the data of both Table 13 and Fig. 47 [155]. should
be emphasized that of kinds, including flow
inside a packed bed, of
These can cause and sometimes hot spots
in such monoliths, the flow individual channels is stable
if designed installed the inlet to the monoliths.
mass in monoliths is slightly than that in
beds, in monoliths up to 70% of the total amount is
the gas to the wall a thin of the gas.
Thus mass monoliths could be fa-
a detailed
each has to be made. the diffusion path in monoliths
implies an manipulation of the selectivity than in beds.
changes in flow, can easily
influence and selectivity in monolithic
(an flow of gas and liquid plugs in the flow is an
of the monolithic pseudo-steady-state
Thus, monolithic can be competitive even
to at least of slow medium
as evidenced by discussed in Sec.
monoliths
as as the
and less sensitive to gas flow the
256
1 I
- 1 I I
4 2.80
4 5.22
-
0 6
6 -
= 2.80
5.22
i
-A = 2.63 7
V = 5.22
0 30 60 90 160
47. two-phase flow in monoliths and packed beds.

with 155. 1977, Chemical
Society.
ductivity unit volume is not because

of the low of catalyst in such is also no simple
to the selectivity and again each should be com-
in detail both a kinetic monoliths can be
advantageous due to The catalyst does not
due to the action, and catalyst is avoided.
Catalysts often handling of which is usually a
of monolithic can be achieved only
stable catalysts. quickly deactivating catalysts,
to since of decayed catalysts is
Scaling up of monolithic has to be simple: just
multiplication of the of channels in the full-scale This
scaling up was checked the of
nones in a plant. An adiabatic is not any
two-phase to the high heat capacity of the
liquid phase, the is much than that in gas-phase
monolithic have many advantages to

conventional fixed/fluidized-bed some of which listed
1. low catalyst volume, up to 2 of
magnitude than in packed beds.
2. of and mass/heat
257
all the channels in a monolith; this in

flow and heat/mass conditions the

whole of the monolith.
3. example, 1- to 2-mm
channels, the to an beds con-
sisting of pellets of 1.5-2.5 mm in
4. Thin catalyst and, diffusion length; thus
and access of to the catalyst can
be expected, which can speed up and modify the selec-
tivity of diffusion-limited
5. Good heat in metallic monoliths, even than
that in packed beds.
6. Low axial in the and low heat con-
duction of the walls of monoliths; this in less mul-
tiplicity of steady states.
7. Good gadliquid and gas/solid contact in slug and flow
gimes and, consequently, mass gadliquid
tions.
8. Easy of of example,
by a supply of along a with
walls.
9. Ease of scaleup.
monolithic some such as the fol-
lowing:
1. cost of monoliths.
2. of expensive monolith thus use
is to stable catalysts.
3. Low heat/mass coefficients between fluid and
catalytic wall gas-phase
4. heat single-passage mon-
oliths to the gaseous this in
adiabatic gadsolid hence, the
use of such monoliths is then to which the
maximum (which can exceed the adiabatic
does not significantly influence selectivity
catalyst stability.
5. sensitivity to initial velocity the
monolith section.
A balance of advantages and setbacks is positive. applications
of catalytic monoliths expected to include including man-
of chemicals. monoliths sys-
tems which can combine multiple functions such as
heat etc. of
258
monolithic in the chemical will changing attitudes

among the management of chemical companies. the use of mon-

oliths as and successfully
implemented in a full scale, is likely to be the main domain monoliths
in the
The wish to acknowledge Geleen, The Neth-

financial
a specific (m2 m ')

(m2)
(m')
limiting Eq. (3)
coefficient in Eq. (34)
in zone (m')
of of solid (m2)
coefficient in Eqs. (4), (37), and (44)
C (mol m-')
C constant in Eq. (37)
heat capacity
mean heat capacity of fluid (J
heat capacity of solid (J mol-'
of a channel (m)
D diffusion coefficient, diffusivity , Coefficient
(m2 s s l )
inside edge length (m)
bulk diffusivity (m' s-')
effective diffusivity (m' s - l )
(m)
Eq. (3)
flow (mol m-'
flow (m'
heat coefficient (W m-'
constant (m'
heat of (J mol-')
constant (mol(l-") m3("-')
mass coefficient in a liquid (m s
mass coefficient in a gas (m
(mol(1-")m3('"- S - 1 )
259
length of (m)
length of a gas plug (m)

length of a liquid plug (m)
length of a (m)
length equivalent to fully mixed wake (m)
mass (kg kmol-')
mean mass (kg kmol-')
cell density [cells (in.-2 cm-*)]
of moles
of
flux (mol m- 2 s-')
4
r of (mol m-' s-')
distance the axis (m)
gas constant (8.3144 J mol-l
(m)
of
time (s)
at adiabatic
conditions
of extinction
of fluid
mean of fluid
at the inlet
of ignition
initial
of solid
velocity (m
velocity of gas (m
velocity of liquid (m
volume (m3)
liquid volume in system (m')
mole (mol mol total-')
to flow
aspect = L/d
to flow
mole
mole in fluid
mole at the catalyst
length (m)
length of zone of developing (m)
260
channel (m)
constant in Eq. (12)
dimensionless adiabatic Eq. (42)
liquid film thickness (m)
washcoat thickness (m)
thickness (m)
thickness of the monolith wall (m)
dimensionless length, = &/D,
voidage (open of monolith
of solid
dimensionless distance, = x/8,
effectiveness
dimensionless =
dimensionless in zone, = TJT,
dimensionless in zone, = TJT,
conductivity (W
aidfuel
conductivity of fluid (W m-*
conductivity of solid (W m-2
dynamic viscosity s)
dynamic viscosity of gas s)
dynamic viscosity of liquid s)
coefficient of
dimensionless =
dimensionless length, =
dimensionless length, =
dimensionless distance, = r/d
density of fluid mW3)
density of solid m-3)
(m2
tension (kg
space time, time (s)
dimensionless time
of slugs
dimensionless distance, =
quantity
initial conditions
=
mass =
261
Ca = vlq/o
= (k&-
Le Lewis =
Nu Nusselt = hDH/Af
=
=
= C,pf/Af
= (
sc Schmidt =
=
=
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Monoliths in Heterogeneous Catalysis

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The use of catalysts in the chemical has been con-

to a monolithic that is, a which is

that met the high of combustion units. 1975

the equipped with catalytic became available. wab

have a advantage to conventional fixed catalyst beds,

0.01 0.1 1 10 100

is significantly as well. can affect the selectivity of

of available monoliths shown in Table

SSiO, The lowest

Silicon Sic Low-high not self-bond

100 300 500 700 900

2. Typical expansion monoliths.

9475 9482 9483 EX-68

monolith. instance, the heat conductivity of 30% is

size temp. limit

alumina is applied, possibly mixed with small amounts of oxides.

monoliths consist of of high open

1 10 1.0 0.10 0.010

when A of the of (10 pm) im-

4. Scanning of a silicate monolith

ezoidal, hexagonal (honeycomb monoliths), sinusoidal, etc. Sections of

5 . Scanning (a) A monolith made by

unit volume, u, to 6, and by the

Open 60% to 80%

6. monoliths of Camet. with of

metallic the wall thickness. Values of geo-

7. Typical cell of monoliths. 1 with

Values of the limiting channel

10. monolithic cell

[25]studied the influence of channel on the

is the best. The must be studied with to the specific

two basic kinds of monolithic catalysts: (1) coated-type

catalysts usually via an step

11. of monolithic catalysts.

called washcoating, which consists of depositing the of

Washcoating is usually by the monolith into contact

have been widely used emission and this is well

1. Control and Combustion

Shallow bed of the Ni Channel width 5 m m

of See above Gas-liquid

of See above Gas-liquid

although must also be used to the content of

some components oxides). this section with

conditions, the of the monolith

at the same conditions. The of the monolith

16. Flow of a catalytic of typical design: (a)

cone. A of devices flow equalization have been in the

17. Velocity a catalytic of the outlined

of the mentioned pollutants can only be achieved when

200 400 600 800 1000 1200

18. in metallic and monoliths. with

high to the of the

U.S., may emit no than 1.9 g NOz mile, 3.4 g CO mile,

olithic catalysts can be at as well. No

heating, except in the would be needed in flow

20. The simultaneous catalytic

1 of capacity. A typical station has the

c. Catalytic Combustion. The use of catalytic combustion