Documente Academic
Documente Profesional
Documente Cultură
CATAL REV.-SCI.
E N G . , 3 0 ( 3 ) . 341-392 (1988)
BENGT ANDERSSON*
Reaction Engineering
Technology
Sweden
..................
MODELING . . . . . . . . . . . . . . . . . . . . .
A . Single-Phase Flow . . . . . . . . . . . . . . .
B . Cross Flow . . . . . . . . . . . . . . . . . .
C . Two-Phase Flow . . . . . . . . . . . . . . . .
111. COMMERCIAL MONOLITHS . . . . . . . . . . . . .
A . Material . . . . . . . . . . . . . . . . . . . .
B . Geometric Shape of Monolith Channels . . . . .
C . Selection of Monolith Substrate . . . . . . . .
IV . APPLICATIONS . . . . . . . . . . . . . . . . . .
A . Methanation . . . . . . . . . . . . . . . . . .
B . Hydrogenation and Dehydrogenation . . . . . .
C . Hydrotreatment . . . . . . . . . . . . . . . .
D . Biochemical Reactions . . . . . . . . . . . . .
E . Electrochemical Reactions . . . . . . . . . . .
F . Oxidation . . . . . . . . . . . . . . . . . . .
G . Catalytic Combustion . . . . . . . . . . . . .
.
I1 .
I
INTRODUCTION
342
343
343
355
358
365
365
372
372
374
374
375
377
378
379
380
381
342
......
..............
CONCLUSION. . . . . . . . . . . . . . . . . . . .
SYMBOLS. . . . . . . . . . . . . . . . . . . . . .
ACKNOWLEDGMENT. . . . . . . . . . . . . . . . .
REFERENCES. . . . . . . . . . . . . . . . . . . .
Stationary-Source Emission Control
Other Applications.
H.
I.
V.
I.
383
385
385
386
387
388
INTRODUCTION
0
0
0
0
0
MONOLITHIC CATALYSTS
343
TABLE 1
Comparison Between a Monolithic Catalyst Reactor
and a Fixed-Bed Reactor
Fixed bed
(d,=1.5 mm)
Ceramic Monolith
(d = 1.5 mm)
2.8
10-3
1.8
10-4
0.23
5.1
Solid fraction, %
60
30
2400
1900
0.75
(0.15
11.
10-
MODELING
A.
Single-Phase Flow
Most work on monoliths has been performed with singlephase flow. The flow is usually laminar with a developing velocity profile. Only at very high velocity in gas turbines is the
flow turbulent. The typical flow regimes for different reactions
are given in Table 2 .
1. Pressure Drop
It is chiefly the low pressure drop that has given the monoliths their applications. In one of the first articles on ceramic
honeycomb structures, Johnson et al. 101 measured the pressure
344
TABLE 2
Application
Velocity,
m Is
Re
Ref.
Car exhaust
1- 3
900- 1200
14
200
171
Gas turbine
3-25
400-2000
23-34
2000- 3000
[ 71
Methanation
60
670
21
100
181
Hydrogenation
500-600
10-3-0.05
0.1-10
91
3 2 LV
~
-
d2
(All symbols used are defined in the list at the end of the text.)
Other studies by Pratt and Cairns [ 111 and Howitt 1121 confirm
these results. Metallic monoliths exhibit lower pressure drops
than ceramic types with similar cell densities, because of larger
open area resulting from low wall thickness 1111.
In Figure 1 is also plotted the pressure drop, calculated
from the Ergun equation [ 131, of a corresponding packed bed
with the same fluid-solid contact area as the monolith. The pressure drop is about two orders of magnitude higher in the packed
bed than in the monolith. Moreover, the pressure drop in packed
beds is often increased further due to deposition of small particles from the feed o r from crushing of the catalyst particles.
2.
Entrance Effects
MONOLITHIC CATALYSTS
345
--,
LAW:
---
FLOW,SCFM/IN'
F I G . 1. Variation of pressure drop with gas flow per unit
of cross section (D: channel diameter). Reprinted with permission
from Ref. 10. Copyright 1961, American Institute of Chemical
Engineers.
-Z =
0.05 Re
(2)
0.05 Re Sc
(3)
346
and the corresponding thermal entry length is obtained by replacing Sc with Pr:
Z
0.05 Re P r
(4)
Axial Dispersion
Packed beds are often used when high conversion is required, due to their low axial dispersion. In monoliths the axial
dispersion is much more dependent on channel diameter and flow
rate. In laminar flow the axial dispersion can be calculated from
the following equation given by Taylor [ 171 :
Pe
a =
v d
D=
192
D
v
d,
ea
Re Sc
>
(5)
MONOLITHIC CATALYSTS
347
1.09
1 : Da = 1.28, Sc = 1.09
L / ( P e r R)
- v2d2
EE
Dea -
-- -0 . 2 8
10'
Jf
<
Re
<
lo4
(7)
(8)
=-
= 2,
'ea
Re
<
500
348
and
v d
-2
Dea - 2
A condition for Eqs. (9) and (10) is that dt/dp > l o . In a typical case of air at room temperature with v = 0 . 1 m / s and dt =
m , the dispersion coefficient will be 2
m2/s
dp =
for the monolith and 5
l o w 5m2/s for the packed bed. For gasphase flow the axial dispersion is much less in the monolith than
in the packed bed. In liquid phase, however, the diffusivity
is four orders of magnitude smaller, and the axial dispersion
will be significant in the monolith; while in packed beds where
the dispersion is independent of the diffusivity, the flow pattern
is close to ideal plug flow.
Dispersion in liquid flow can be decreased substantially by
introducing a gas or a nonmiscible liquid into the flow. In twophase slug flow the residence time distribution is close to ideal
plug flow. The flow patterns of two-phase flow are discussed
further in a later section.
4.
(:
Nu = B - Re Pr
y3
MONOLITHIC CATALYSTS
349
TABLE 3
Constant B
in Eq. ( 11)
Geometry
Nusselt ,
constant
wall temp.
Circular
4.364
3.608
Square :
b/a = 1
1.16
2.976
2.967
Rectangle :
b/a = 0 . 5
b/a = 0 . 2 5
1.23
1.38
3.392
4.441
3.391
4.439
Equilateral triangle
2.491
2.470
3.111
Trapezoid :
b = l
c = 0.5
b = 0.75 c = 0.25
2.744
2.120
2.617
Sinusoidal
1 + 0.095 Re Pr
1 + 0.095 Re Sc
(
(
r3
q3
Re -
Re -
ScoeS6
350
<
Re
<
480
0.57
<
Sc
<
3.3
Pr = 0.74
They used air in all their experiments, and no heat transfer dependence on the Prantl number could be calculated.
Both Boersma et al. [251 and Heck et al. [ 2 6 ] found that
their data correlated slightly better with Hawthorn's model.
Figure 3 shows the two models and some experimental data. The
main difference between the models is at low Reynolds number,
where Votruba's model predicts a continuous decrease in Sherwood number with decreasing Reynolds number while Hawthorn's
model reaches an asymptotic value.
The observed mass transfer coefficients are within a factor
of 2 of the theoretical calculations presented by Young and
Finlayson [ 201. The reason for this deviation of experiments
from theory is not yet established. Possible causes are experimental errors, errors in the values of diffusivities and Viscosities used in the calculations, or that the theoretical models are
too simple.
In Figure 3 the Sherwood number is also plotted for a packed
bed with the same surface area per volume of reactor a s the
monolith. The Sherwood number for the packed bed is the same
at low flow rates, but at high flow values it becomes more than
one order of magnitude higher. However, the lower Sherwood
number can be compensated by using a monolith with a higher cell
density. Decreasing the channel diameter by a factor of 3 increases the mass transfer coefficient kLa by a factor of 9. The
lower limit of channel diameter is determined by manufacturing
methods and is at present about 1 m m .
An enhanced mass transfer in liquid phase can be obtained
by introducing plugs of a nonmiscible liquid or a gas into the
flow. This disturbs the laminar flow and increases the radial mass
transfer. This effect is more thoroughly discussed later in connection w i t h two-phase flow.
5.
Mathematical Modeling
MONOLITHIC CATALYSTS
351
Sh
30 -
25-
--_
20 -
___.-.--.+*+$
_ _
o--0
.-. -.
._ .-.
-. -. -.-.
- ----------------
-. -.-.
_ _ _ _ _ _
+^ _ _ _ _ _ _ _
200
400
600
800
1000
1200
1400
1600
1800
Re ;Rep
a. Distributed-Parameter Models
All published distributed-parameter models have approximated
the monolith with an adiabatic cylinder. The mass and heat transfer in a circular tube with fully developed incompressible laminar
flow can be written
a
at
Ia
and
=D. i -(ra
1 r ar
+ Di-
az2
IIa
IIIa
IVa
x)
a if
(16)
352
TABLE 4
Ref.
Model
Condition
Heat
conduction
in
solid
Lumped
Steady
No
No
No
Distributed
Steady
Yes
No
No
Distributed
Steady
No
No
No
Lumped
Distributed
Transient
Steady
No
No
No
No
No
No
Lumped
Steady
No
No
No
Distributed
Transient
Yes
No
Yes
Lumped
Transient
Yes
No
No
Lumped
Steady
Yes
No
No
Lumped
Steady
Yes
No
Yes
Lumped
Steady
Yes
No
No
Distributed
Steady
Yes
No
No
Lumped
Steady
Yes
No
No
Distributed
Steady
Yes
Yes
No
I : lumped
11: distr.
111: distr.
Transient
Transient
Transient
Yes
Yes
Yes
No
No
No
No
Yes
N0
2)
Internal
mass
transfer
in solid
Radiation
-
aTf +
at
a 2Tf
+ 2v(l
hf-
az2
IIb
Ib
5)
IIIb
aaTf
=
z
Xf
a r (r
IVb
acif
-=-
ar
aTf
ar
= o
(17)
MONOLITHIC CATALYSTS
353
3
at
7
a2cis= D
+D
ei
1a ( r 7
a is )
+
e. r ar
1
Va
VIa
Vb
VIIa
VIb
VIIb
vijrj
(19)
VIIIa
VIIIb
ar
a TS = O
ar
a t r = R + S
At the boundary between t h e fluid and solid ( r = R ) , the balances are written
a is
-De
i
xs
ar
a TS
ar
--
a if
D. 1 ar
a Tf
ar
(23)
354
b. Lumped-Parameter Model
Most calculations have been done with lumped-parameter
models. In these models only the average concentration and
temperature in the phases are considered. The lumped-parameter models are sufficient in many applications where t h e gradients in the fluid and the solid are small.
-a '-if
at
-a T- f
at
-., a a'ifz
"
- - kfi(Cif
- Cis)
a Tf
-v az
- Cis) =
wijrj
~,'ps
aTS
a 2TS
at
az
- + A-
r. ( - A H . )
+
j
(27)
MONOLITHIC CATALYSTS
7.0-
355
II
11
B.
Cross Flow
Heat Transfer
356
860
G = 10 Ib/hr Np-l
S.V. = 17.000 hr
805
PACKED BED
1/8" x 1/8" alumina pellets
750
Y
I-
*, ,a
695
3
l-
a
w
640
I-
0
UI
m
-I
5
a
585
---
530
475
-/
420
0.0
CENTER
0.33
0.67
1 .o
WALL
MONOLITHIC CATALYSTS
357
ar
- 0
-a T
-s at
aTm
ar
a t r = R + S
358
In a series of articles, de Vos et al. [39, 42, 431 have described a monolith reactor in which the reactants were separated
by a catalytic wall. The diffusion and reaction are described by
Eq. (19) but the diffusion is from opposite sides, which gives
the concentration profiles shown in Fig. 7. These concentration
profiles will give very different selectively conditions compared
to catalysts where the reactants diffuse from the same side [43].
The thick porous walls (>0.1 mm) give severe mass transfer
resistance for fast reactions. In order to improve the mass
transfer, Hatziantoniou et al. [44] developed a catalytic wall for
gas-liquid reactions in which most of the wall is not wetted by
the liquid. Only a narrow reaction zone, in which the gas and
liquid have to be in contact, is wetted. Since the gas-phase
diffusivity is about four orders of magnitude higher than the
liquid-phase diffusivity , the effectiveness factor is increased
substantially (Fig. 8).
In this improved catalytic wall the mass transfer resistance
in the liquid channel becomes the rate-determining step. Static
mixers in the liquid channel were installed to increase the mass
transfer.
C.
Two-Phase Flow
In bubble flow the bubbles are much smaller than the channel
diameter. The bubbles disturb the laminar flow and increase the
-0
1
-0
1
360
C" x 10
FIG. 8. Concentration profiles for hydrogen ( H ) and nitrobenzoic acid ( A ) in hydrogenation with a thin and active plate.
( b : bulk, z: dimensionless length coordinate in the plate).
Reprinted with permission from Ref. 44. Copyright 1986, American Chemical Society.
MONOLITHIC CATALYSTS
361
.. .. ... ...
..
. ...
.. ..
....
., ... ..
. ... .' .. ..
....
.....
.. .......
....
a.
0
Bubble
flow
FIG. 9.
Slug
flow
Taylor
flow
:a.
.. .. .. .. .
. . .. .. ..
....
......
.. . .. .. .
.. .. . .
:. . .
. *. . .'
*
Annular
flow
Both bubble flow and slug flow are desirable in monolith reactors. Slug flow gives better mass transfer and residence time
but requires a higher gas hold-up.
The transition between the flow regimes is difficult to predict.
Most experiments are done with channel diameters larger than
1 cm.
Taitel et al. [ 4 5 ] give a qualitative discussion of the phenomena involved in the transition between flow patterns, which can
give some guidelines about where to expect the transition. The
bubble-slug transition requires an agglomeration of bubbles.
When the gaslliquid flow ratio is increased, the bubbles come
closer to each other and the coalescence rate increases. A theoretical upper limit of the gas hold-up is 0.52, which is the maximum allowable packing of spherical gas bubbles. However, the
gas bubbles move and collide randomly, and published data [ 4 5 1
indicate that at hold-up above 30% the bubble flow will irreversibly transform into slug flow. For void fractions less than 0.20,
coalescence is rarely observed. Only at high velocities are the
forces large enough to break the large bubbles into smaller ones.
Transition to annular flow occurs at high gas velocities.
Turner et al. [ 4 9 ] suggested that annular flow cannot exist un-
362
less the gas velocity in the gas core is sufficient to lift the entrained droplets. When the gas rate is insufficient, the droplets
fall back, accumulate, and form a bridge, and slug flow takes
place.
Figure 10 shows the annular and slug transition regimes for
the system air-water in a 2-mm capillary tube. There is a wide
area in which the flow pattern is dependent on how the gas is
introduced into the fluid.
1.
Pressure Drop
200
Transition
Transition
1 50
.
5
VI
>
k
Slug Flow
100
>
7
4
/%
50
Depends on
Method of
Liquid introduction
7
/
&
&
0
0
MONOLITHIC CATALYSTS
363
Satterfield and &el [50] measured the pressure drop in monoliths and separated it into its components. They concluded that
only at high cell density (greater than 250 cells/in. 2 , did the
orifices have any effects. The frictional pressure drop and
static head accounted for more than 70% of the total pressure
drop in all monoliths tested.
At low velocity and narrow channels, the frictional pressure
drop is viscosity-dominant and can be calculated from the weighted sum of the liquid- and gas-phase pressure drops [ 131 :
Monoliths
Wp = 2.63 cmls
Vp = 5.22 cmls
~~
30
60
90
120
150
180
cm/s
FIG. 11. Comparison of pressure drop in monoliths (200cell, 15.2-cm blocks) with that in packed beds. Reprinted with
permission from Ref. 50. Copyright 1977, American Chemical
Society.
364
2.
Film Thickness
(33)
Ti6
= 0.18
1-
exp ( - 3 . 1
(~y-~~)],
lJV < 2
U
(34)
to their data.
3.
Mass Transfer
(7)
Sh = 3 . 5 1 Re Sc
o-44 B-OSo9
(35)
MONOLITHIC CATALYSTS
4.
365
Axial Dispersion
COMMERCIAL MONOLITHS
A.
Material
Monolithic support material is mainly used for emission control. Most of the development of monolithic material has been
directed toward high-temperature applications required in that
area. However, there is a growing interest from the chemical
industry to find applications for monoliths a s catalysts in chemical processes. These applications often require a high-surfacearea support.
Today monoliths are made of many different materials. Table
5 gives a list of monolithic materials that are available or under
development.
1.
0
Thermal shock and thermal stress resistance, involving
a very low coefficeint of thermal expansion
0
Refractoriness
0
Porosity and pore size distribution for catalyst coating
application, that is, 30-40% open porosity and 5-15 p m medium
pore size
0
Axial crushing strength > 20 MN/m2
Cordierite meets these demands for standard automotive applications ; but in some applications, for example, heavy-duty
trucks and gas turbines, the low melting point (1735 K) limits
its application. However, refractory oxide materials have high
366
Name
Composition
a- and y-Alumina
A1 2
C or dierite
Cordierite - mullite
MgO-MgO *A12
Mullite
3A1 2O 4 i O
Silica
SiO
Silicon carbide
Sic
Silicon nitride
Si 3N ,,
Spinel
MgO .A1 2
Titania
Ti0
Zeolites
A1 2O3-
Zirconia
ZrO
Zirconia- spinel
Metallic
Fe- C r -Al- Y t
03
03
03
SiO
MONOLITHIC CATALYSTS
2.
367
Metallic Monoliths
Manufacturing
Ceramic monoliths have been manufactured by different techniques IS]. The two most frequently used methods are corrugation and extrusion.
In the corrugation method, a slurry of inorganic oxides and
salts with particles 1-5 p m in diameter is mixed w i t h organic
binders and plasticizers and impregnated onto a fabric or paper.
The sheet is often enforced with glass fibers or other inorganic
fibers. These sheets are then stacked or rolled together, with
every other sheet corrugated. The corrugated sheets are put
parallel to form conventional monoliths, or criss-crossed to form
cross-flow monoliths. The monolith is then fired at high temperature. Monoliths of almost any shape or size can be made by
the corrugation method. Heat exchangers with a diameter of
more than 5 m have been manufactured by this method.
++
++
+
+
Mullite
MulliteC
Cordierite
+++
++
+++
Cor dierite
Cordierite
++
++
++
++
++
++
++
Strength
+++
Shack
resistance
Cordieriteb
Alumina
Alumina
Alumina
Substrate
composition
1950
DuPont
Amer. Lava
Torvex
Thermacomb MD- 3
1430
Gen. Refr.
Ver sagrid
1400
1350
W. R . Grace
corning
Poramic
Celcor 9475
Amer. Lava
1200
1200
Thermacomb 795
1200
Amer. Lava
Thermacomb 614
1540
Coors
Dupont
Manufacturer
Torvex
Trade
name
1500
Upper temp.
limit, C
Thermal characteristics
TABLE 6
++
++
++
++
++
++*
+++
++
++
+
+
++
+
++
++
++
+++
+++
Zirconia- spinel
Zircon - mullite
Silicon carbide
Metallic
Metallic
Silicon nitride
Zirconia
Mullite
Mullite
Fecralloy
Kanthal
~~
SpectramicRX 384
SpectramicR X 3 8 7
Thermacomb 784
Celcor
Versagrid
1250
1400
1540
1650
1480
1700
2200
1700
1650
Johnson Matth.
K Y Metal
Norton
Norton
Amer. Lava
Corning
Corning
Cwrs
Gen. Refr.
370
TABLE 7
High-Surface-Area Monolithic Material
Heat treat.
temp.,
Surface
area,
m /g
Porosity,
%
Median
pore
size,
Composition
y - Alumina
800
200
63
35
1300
80
59
140
1300
155
800
155
47
1300
60
60
800
50
63
1300
30
46
Transition alumina
93%Alumina + 7 %
silica
Silica
Bimodal
Magnesium
Aluminate spinel
Titania
Titania- silica
4 10
310
MONOLITHIC CATALYSTS
37 1
TABLE 8
Comparison of Ceramic and Metal Substrate Parameters I: 111
Ceramic cell
density, cell /in.
Cell area,
Metal cell
density, cell/in
200
300
400
400
500
600
2.30
1.43
1.21
1.50
1.10
0.97
1890
2205
2790
3230
3580
3940
70
60
76
89
86
83
0.28
0.30
0.15
0.05
0.05
0.05
m2.1O6
Surface to volume
ratio, m-
Open area, %
Wall thickness,
m -103
5.
Washcoatin g
372
MONOLITHIC CATALYSTS
373
374
1V.
APPLICATIONS
Methanation
T h e methanation of carbon oxides is a rapid, exothermic reaction which makes the temperture control of the reactor difficult.
In such a case the use of metallic monoliths is very suitable,
especially when high reactant gas flow is desired.
Tucci and Thomson [65] have compared metal monolith and
pellet methanation catalysts based on equivalent metal loading.
The catalyst used was Ru in both cases. Pelleted catalyst showed
high initial activity which decreased slightly and finally regained
its original high activity. Monolith catalyst held a constant,
lower activity. Selectivity for converting CO to CHI,was about
97% for ruthenized monolith and about 83%for pelletized catalyst.
Jarvi et al. [661 have investigated the catalytic activity and
selectivity of nickel supported on washcoated ceramic monoliths
and pellets. The reactions were performed over a wide range of
temperture, pressure, and space velocity. It was shown that
washcoated monoliths provide less pore diffusional resistance
than pellet catalysts. This makes monolithic catalysts ideal for
intrinsic kinetic studies. The experimental results also showed
that, due to smaller pore diffusional resistance and consequently
high mass transfer rates, the monolithic catalyst used was 20100% more active than commercial catalyst pellets. The monolithic
catalysts were more active and selective under any given pressure and temperature conditions. Thus, the authors concluded
that monolithic nickel is the ideal catalyst for application in highthroughput recycle methanators.
MONOLITHIC CATALYSTS
375
De Bruijn et al. [671 have also investigated the use of monolith reactors for the methanation of carbon dioxide in hydrogen
at atmospheric pressure. The reaction temperature was between
473 K and 523 K . It was concluded that monolithic reactor systems have better temperature control and are very suitable for
large quantities of gas, which makes them appropriate within
SNG production.
Another study on this subject has been carried out by
Sughrue and Bartholomew [ 681 , who investigated the kinetics of
carbon monoxide methanation on nickel monolithic catalysts. It
was emphasized that the use of the coated monolithic catalysts
made it possible to determine kinetic data at higher temperatures
than was possible for a supported metal.
B . Hydrogenation and Dehydrogenation
1.
Liquid-Phase Reactions
376
MONOLITHIC CATALYSTS
377
Gas-Phase Reactions
Hydrotreatment
Hydrodesulfurization and hydrodenitrogenation are slow reactions and not suitable for standard monolith reactors. The stand-
378
ard washcoated cordierite monolith has less than 5% porous support in the washcoat layer per volume reactor, while the usual
hydrotreatment in a trickle-bed reactor has more than 10 t i m e s
as much porous support per volume reactor.
Soni and Crynes [75] have performed these reactions on pure
y-alumina monoliths. These monoliths had 92 m2/g surface area
and were impregnated with 3.37% COO and 7.25% MOO3 . The
reactions were performed at 100 bar and 644 K. The activity
of the catalysts for hydrodesulfurization and hydrodenitrification
was about the same a s a commercial hydrotreatment catalyst
The catalyst was tested both on
(Nalcomo 747 from Katalco)
a high-boiling stock and on a low-boiling coal-derived liquid.
The authors conclude that the mass transfer , liquid distribution ,
and catalyst wetting are better in the monolith than in a trickle
bed. The monolith also minimizes bed plugging when fine solid
particles are present.
D.
Biochemical Reactions
The application of monolithic geometry is biochemical reactions, such as immobilization and precision separations , has
recently attracted attention from many authors. The honeycomb
support is in many applications superior to conventional supports. Advantages gained by the former are high surface-areato-volume ratio, low pressure drop , and even flow of liquid
medium as well as adequate oxygen diffusion. For systems w i t h
viscous liquid flow and high oxygen demand, this novel reactor
has proved to be very efficient.
In general packed-bed columns, fluidized-bed reactors, and
monolith reactors can be used as bioreactors. For fermentation
systems with gas evolution, the use of honeycomb monolith a s
a bioreactor is the most appropriate choice. The packed-bed
columns and fluidized-bed reactors are not recommended due to
channeling and plugging of liquid flow in the former and lower
conversion due to backmixing in the latter.
Ariga et al. [76] have recently studied the immobilization of
microorganisms on honeycomb monolith supports for biochemical
reactions with and without gas evolution. The effects of mass
transfer resistance and axial dispersion on the conversion of
substrates were studied. They found that the monolithic reactor had characteristics close to plug flow, that i s , minimum reactor volume for a given conversion of substrate, even for systems
w i t h gas evolution. The residence time distribution of the monolithic reactor was comparable to four completely mixed tanks in
MONOLITHIC CATALYSTS
379
Electrochemical Reactions
380
Oxidation
Strongly exothermic catalytic reactions involving large quantities of gas such as oxidation reactions can take advantage of
certain properties of the monolithic catalyst such as low pressure
drop. The cross-flow monolith reactor can ideally be used for
oxidation reactions providing facile temperature control of the
catalytic surface. Furthermore, simple flow pattern and structure of the monolithic reactor make the scale-up process of this
reactor more reliable. Finally, better mechanical properties of
catalysts are of great value for this kind of reactions. One
limitation for monolithic reactors is observed for operations in
the laminar flow regime where mass transfer to the tube wall
limits the conversion.
The oxidation of ammonia to nitrogen was studied by Bernauer
et al. [ 2 8 1 , who found a monolithic reactor suitable for kinetic
investigation. The kinetics of this reaction were obtained by
use of data from a tubular wall reactor. They derived dimensionless equations which permit evaluation of temperature and
concentration profiles in the catalyst.
Boersma et al. [25] have compared the behavior of the empty
and packed tubular wall reactor both theoretically and experimentally using the air oxidation of ethene catalyzed by platinum.
Their experiments were applied to three different hydrodynamic
conditions: : laminar flow, turbulent flow, and the transition
region between.
Zabar and Sheintuch [811 have studied a monolithic reactor
for oxidation of SO, over platinum catalyst. The application of
cross-flow design was compared to two monolith blocks w i t h interstage cooling. They optimized the operating conditions for
MONOLITHIC CATALYSTS
381
Catalytic Combustion
382
MONOLITHIC CATALYSTS
383
The emission of volatile organic compounds and carbon monoxide from fossil fuel combustion, gas turbine exhaust, petroleum,
and petrochemical processes results in grave environmental destruction.
These emissions are significant sources of energy and power.
Thus, combustion of flue gases results not only in pollution control, but also in enhancing energy recovery. The control of
environmental pollution has received much attention for well over
a decade.
The existing emisison control systems are generally based on
0
0
0
Incineration
Selective catalytic reduction (SRC)
Non-selective catalytic reduction (NSCR)
384
MONOLITHIC CATALYSTS
385
the SCR method. Further, the removal of No increases with increasing temperature up to about 720 K , above which the r e moval rate of NO is decreased with increasing temperature. This
is probably due to oxidation of NH, by oxygen that occurs at
high temperatures.
Bartholomew 1911 has studied reduction of nitric oxides by
use of monolithic supported palladium-nickel and palladiumruthenium alloys. The effect of reaction parameters such as
temperature, space velocity, and C O / O p ratio on the reduction
of NO are reported.
Becker and Zygourakis [ 921 have recently considered the
design parameters for a catalytic monolithic reactor. The authors
developed a mathematical model which clarifies the effect of various design parameters on reactor light -off characteristics. The
parameters con sidered were nonuniform velocity distribution in
the honeycomb channels, thermal mass of the reactor, geometric
surface area of monolith, and stoichiometry of the exhaust gases.
It was found that reducing the thermal mass of the reactor, and
increasing exhaust gas temperature and the geometric surface
area, improved the light -off performance of the reactor. Moreover, the authors emphasized that a radially nonuniform velocity
profile may drastically increase the reactor light-off temperature.
The most important effect of heat losses proved to be a decrease
of steady-state conversion.
To sum up, the special performance of the catalyst system
depends on the type of contaminants in exhaust gases, desired
level of pollutant removal, exhaust temperature, and flow rates.
I.
Other Applications
CONCLUSION
386
3
d
Da
De
DP
dt
f
g
(-AH)
h
kLa
L
L1
Nu
P
Pe
Pr
R
r
r
Re
sc
Sh
MONOLITHIC CATALYSTS
t
T
V
387
time, s
temperature, K
linear fluid velocity, m / s
axial coordinate, m
Greek Letters
B
Y
6
5
E
x
!J
V
P
U
Subscripts
a
axial
benzene
cooling fluid
effective
fluid phase
frictional
gas phase
hydrogen
component number
reaction number
liquid phase
monolith
orifice
particle
solid phase
tube
wall
Bz
C
e
f
fr
H2
i
j
1
m
Or
P
S
ACKNOWLEDGMENT
We acknowledge useful discussions concerning this work with
D r . I . M. Lachman, Corning Glass Works.
388
REFERENCES
MONOLITHIC CATALYSTS
1211
389
1223
. .
390
345 (1980).
t 461
[ 471
29,
481
[ 491
501
981 (1983).
[ 511
( 1935).
1521
[ 531
[ 541
20,
181 (1981).
[ 591
(1981).
[ 631
18,
[ 641
487 (1973).
S. T. Gulati, Paper 750171 Presented at SAE Automotive
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[ 651
E. R
. Tucci and- W .
MONOLITHIC CATALYSTS
391
392
[ 901
[911
[ 921
931