Monolith Reactors

Catalysis Engineering June 2, 1999

1 Why monoliths
In the previous chapters we have used mass- and heat balances to describe mass and heat transport limitations in catalytic reactors. In this process we have derived dimensionless numbers, such as the Thiele modulus and the Carberry number Ca. All these numbers indicate that in most cases (i.e. when one doesnt want limitations) it would be best to have the highest possible specic surface area, i.e. the shortest diffusional lengths. In other words, it is often favorable to have small particles. On the other hand, many of our calculations have focussed on particles sizes where mass or heat transfer limitations did occur. The reason we often have such larger particles is that in reactor design also the momentum balance is considered. Solving the momentum balances for a packed bed lead to equations such as the Ergun equation for pressure drop in packed beds. These pressure drop correlations have in common that for increasing surface area the pressure drop will rise. In some applications high pressure drop is not a large issue. For instance, in a slow heterogeneously catalysed process a large residence time will be required. The resulting low supercial velocities are not likely to pose a large problem of pressure drop. On the other hand, fast reacting systems with high supercial velocities benet most from high surface areas. Here pressure drop may cause a problem. It can be argued that the high pressure drop is not only caused by the size of the particles, but also by the irregularity of the packing, i.e. the random way in which they are ordered geometrically in the column. For instance, the friction factor for a regular structure like a pipe is signicantly lower than for a packed bed. Moreover, there are more phenomena which are difcult in packed column design that are caused by this irregularity. Maldistribution and incomplete wetting. Maldistribution in three phase reactors occurs when some areas in the column have more liquid holdup (and thus less gas holdup) than other areas. In a severe case of maldistribution, some catalyst particles are not wetted (completely) by the liquid. These particles do not convert as much as completely wetted particles. Wall effects are also a form of maldistribution.

Fouling and Attrition. Erosion can occur when particles are moving with respect to each other.

All these considerations have led to the development of structured catalysts. There are several types of structured catalysts, such as the Sulzer packing, the Three Levels of Porosity Reactor and the Bead String Reactor. For more information on these types 1

(a) Sulzer Packing

(b) Cross ow Reactor

(c) Monolith

(d) Parallel Passage

(e) Three Levels of Porosity

(f) Bead-string Reactor

Figure 1: Structured catalytic reactors

Figure 2: monolith shapes

of reactors, as well as monolith reactors, the interested reader is referred to Moulijn and Cybulski (1998). All these catalytic reactor concepts have in common that a higher level of structuring is found relative to a packed bed to overcome some of the before-mentioned limitations. In some cases, the distinction between catalyst and reactor is lost, and the entire internal structure of the column is optimized to enhance mass and heat transfer and to lower energy consumption (pressure drop). The regular structure itself is made up entirely of catalytically active material or is coated on the surface with an active washcoat. One type of common structured reactor, the monolith reactor, will be treated in more detail in this chapter. The monolith reactor was developed for the cleaning of exhaust gases from combustion processes, both in cars and large power plants. For these processes, the monolith reactor offers an irresistible combination of low pressure drop (two to three orders of magnitude lower than in packed beds) and high surface area. Recently, an effort is made, amongst others by Delft University, to use the monolith concept in other areas, including three phase processes and counter current ow operations.

2 Geometry
The world monolith comes from Greek, and in interpreted here as made from one piece (of stone). Most monolith reactors consist of one piece of ceramic material. This ceramic block contains a large number of parallel channels extending over the entire length of the block, separated by thin walls. The channels usually have a small diameter, resulting in large specic surface areas, combined with the pressure drop of a (small) pipe. There are no open passages from one channel to neighboring ones, so the quality of distribution at the entrance of the block is maintained throughout the entire length of the block. The channels themselves can be square, hexagonal or triangular, etc. Another way of producing monoliths is to use corrugated plates of metals. Ceramic monoliths are extruded to a (currently) maximum length of one meter and a diameter of approximately 50 cm. Larger volumes of monolith structures are obtained by stacking smaller building blocks. Various channel geometries exist: square, hexagonal, triangular, nned channels, but also channel geometries produced by wrapping up at sheets with corrugated sheets in between. The monolith themselves have a square, oval, racetrack (cf. Indy 500), triangular or round geometry, depending on the application of the structure.

3 Engineering Correlations, single phase

Engineering correlations for pipes are readily available in the literature. These can be used for monoliths, assuming the feed of each channel is the same. The monolith can then be regarded as a large number of (parallel) tube reactors. For instance, the fanning equation for pressure drop in pipes (Bird et al., 1960)

is used successfully to model the pressure drop in monoliths. Off course this simple equation can be improved to cover some other phenomena. In the entrance region, the ow pattern develops from an initially at prole to a parabolic one. (A similar phenomenon will be observed with mass and heat transfer later). This consumes energy, and is accounted for by a term with a vanishing contribution for long channels. Also, the in- and outlet effects can be included in a fashion, similar to the modeling of pipes 64 1 Re d L
05

For mass and heat transfer, we can use the Chilton-Colburn analogies: for mass and heat transfer the equation will have the same form L d L Re Sc d

In Perry and Green (1984) we nd for heat transfer for round tubes Nu 3 66 0 17 Re Pr
L d 08 L d

which closely resembles the Sherwood correlation used for monoliths

The expressions for Sh and Nu contain a term for innitely long channels and a contribution for entrance effects. The length of the entrance effects depends on the ow properties (Re) and the uid properties (Re, Sc, Pr ). For a typical Re value of 100, a Sc value of 1 and 1000 for gases and liquids, respectively, and a channel diameter of 1 mm the entrance length is 0.1 and 10 m, respectively. (Since mass transfer is enhanced by the entrance effects, the fact that monoliths can only be extruded to a length of 1 m is less of a problem, if the entrance effects are repeated every once in a while.) So, we can conclude that well established solutions for the mass, heat and momentum balances can be used to create a reactor model for monolith reactors with single phase feed. And, indeed, these models have been applied successfully.

Sh

3 66 1

0 095ReSc

d L

0 117 Re Pr

0 45

Sh

Nu

Re Pr

05

4f

0 0445Re

16 laminar ow, round channels Re 14 9 laminar ow, square channels Re

L d

1 2

4f

(1) (2) (3)

d L

(4)

(5) (6)

(7)

(8)

4 Example: DeNOx
Today, worldwide legislation (with local deviations) require that the exhaust gases from power plants are cleaned, allowing a maximum of 100 ppm NOx. In order to comply with these requirements, one can distinguish primary measures, in which the combustion process itself is optimized for low NOx levels, and secondary measures, in which the efuent gas is cleaned. By primary measures alone, NOx levels of 1000 ppm are obtained, so the secondary measures are also necessary. In the so called DeNOx process, ammonium is fed to the efuent gas to reduce the oxides to nitrogen. In this process, SO2 is also oxidized to SO3 , which forms ammonium hydrates which damages process equipment and plugs the catalyst pores. The chemistry of the process can thus be written 4NO 4NH3 2O2 2SO2 O2 4N2 6H2 O 2SO3 desired unwanted

The reaction of NO is fast relative to the reaction of SO. Derive how the selectivity depends on the surface area and the catalyst volume The fact that selectivity is a linear function of specic surface area calls for small particles. Monoliths with thin channel wall are also suitable. A Major reason for choosing monoliths in this process is the low pressure drop. Throughputs are very high (u g s 3 m/s, even with very large cross sectional area), and the cost of a compressor is large. Another issue is that the feed contains many dust particles from the combustion stage. This dust would certainly plug a packed bed.

catalyst layers

Figure 3: Typical design of a monolith reactor for DeNOx The reactor shown in gure 3 is lled with monolithic modules that are stacked to ll the reactor. At the entrance of the reactor ammonia is fed. In this particular 5

 

 

distribution layer

module

honeycomb monolith

conguration, the position of the inlet at the side will lead to maldistribution. The ow rate and amount of dust will be highest at the side opposite of the entrance. This would cause ammonia to locally slip through and even using monoliths severe local erosion of the catalytic material. To counteract maldistribution, a special noncatalytic layer is mounted at the top to redistribute the gas. Pore-mouth poisoning, e.g. by arsenic oxide, and erosion by dust particles tends to favor fully active walls over washcoats.

5 Example: Car Converters

In 1970, the US Clean Air Act called for a reduction of polluting gases from car exhaust by 90% in 5 years. Today, the reduction of exhaust pollution still goes on. In the seventies, a catalytic system was introduced to convert gases like NOx and CO to less polluting gases was introduced in a packed bed like conguration. There are several reasons for preferring monoliths over packed beds in car converters. The most important ones are:

The fast heat up of monolith car converters has caused thermal stress problems. While the entrance of the monolith is already hot, the exit side is still rather cold. Due to thermal expansion the structure is likely to break. For this reason the ceramic material cordierite is used, which has a very small thermal expansion coefcient.

6 Three Phase Flow

Due to The succesfull application of monolith reactors for gas phase reactions, the use of the monolith reactor has been extended to three phase processes. Three phase processes require high surface-to-volume ratios, because diffusion through the liquid layer is often slower than reaction. Hydrodynamics play an important role in the contacting of the phases. Conventional three phase reactors are trickle bed reactors packed beds through which the gas and liquid move downwards and slurry reactors stirred liquid tanks, with gas and ne catalyst particles in suspension. The hydrodynamics of a gas and liquid, moving through a monolith channel closely resemble the hydrodynamics in two-phase pipe ow. The main difference is that due to the small channel sizes, surface tension forces play a large role, whereas they are 6

Pressure drop. At the very high temperature of the exhaust gas, the reaction is very fast, and high surface areas are needed to meet the pollution requirements. In a pecked bed, the pressure drop is so high that the engine performance drops considerably. Car manufacturers are very sensitive to reduction of engine power. Catalyst mass. An larger egg-shell catalyst could be used to have a reasonable pressure drop, but the reactor would have to become to long, and more importantly, too heavy. Weight reduction is a constant consideration in car design, but there is a more important reason for weight reduction. Cars do not in contrast to petrochemical reactors operate at steady states. During start-up, the catalyst is still cold and the system is inactive. Even today, using monoliths with very thin walls, most of the emissions occur during start-up of the car. Therefor, it is vital that the catalyst heats up fast.

usually ignored in pipe ow. The ow patterns found in monoliths are summarized in gure (add later) for increasing gas ow rates. At very low owrates, the bubbles are smaller than the channel diameter, and bubbly ow is observed. For higher gas owrates, the gas bubbles are larger than the channel diameter, and the two phase system moves through the reactor as a train of separate gas and liquid slugs. This ow pattern is called Taylor ow, and is of most interest to monoliths. For even higher ow rates, the pattern becomes less well dened an will eventually go to annular ow. In Taylor ow, the catalyst wall is separated from the gas bubble by a very thin lm. The thin lm gives rise to high concentration gradients in the case of a fast reaction at the wall, and thus high uxes. The Three phase monolith can be operated at even zero pressure drop. In this case, downow is the channel is driven by gravity alone.

Figure 4: Three phase monolith reactor In this case, the reactor design depicted in gure (4 can be used. Liquid is fed at the top of the reactor and enters the monolith blocks through a distributor. The gas is sucked in by the falling liquid plugs and recirculated inside the column, eliminating the need for a compressor. The liquid is collected at the bottom and can be recirculated.

7 Engineering correlations: three phase

The modeling of pressure drop (if any) in the monolith is very similar to the modeling of single phase pressure drop. Due to the capillary forces the gas bubbles are very rigid, and we can envision each liquid plugs as single phase entrance ow into a pipe. We safely ignore the contribution of the gas plug to the pressure drop, and recall the fanning equation with correction for entrance effects

A plot of experimentally obtained friction factors vs. Re, and assuming a constant plug length indeed gives a surprisingly good t (see gure 5.

f exp

0.10

L = 2 x 0.13 m L = 3 x 0.13 m

16 Re

Figure 5: three phase pressure drop The success of the pressure drop model invites us to apply the same principle to mass transfer: regard each liquid plug as an entrance region for developing mass transfer and use the single phase model, replacing channel length with liquid plug length. For mass transfer from the liquid plug to the catalytic wall (or vice versa), this model has indeed been successfully applied. This mass transfer model would also implicate that a higher conversion is obtained in a liquid-solid reaction, if inert gas is used in a monolith, which has indeed been experimentally demonstrated. For mass transfer from the gas plug through the lm to the wall we can make a rst estimation by assuming a at prole in the lm, zero concentration at the wall (fast reaction), and saturation at the liquid interface. In this case we only need the lm thickness as a function of ow and uid properties. Ca dchannel

Here the surface tension is expressed as the dimensionless ratio Ca of viscous forces to capillary forces. The mass transfer coefcient is now estimated by D

A complete model for mass transfer from gas phase to solid wall would also have to describe mass transfer from the gas plug to the liquid plug, and is beyond the scope of this introduction.

kG S

lm

0 18 1

exp

lm

' &

0.01

50

100

3 1Ca 0 54

1.00

4f

64 1 Re

0 0445Re

d L

05

600 cpsi

Re
1000

(9)

"

! (  

(10) (11)

(12)

8 Example: HDS
Desulfurization of vapor gas oil fractions is an important process in the petrochemical industry. One of the main problems is that this process is inhibited by its product H2 S. The lumped (all sulfur compounds treated as one) reaction equation and kinetics are given by:
2 cs cH2 1 K cH 2 S

In this case, it is favorable to operate the reactor in counter-current mode (For an in depth discussion of HDS and counter-current ow, the reader is referred to Krishna and Sie (1994)) A conventional packed bed cannot be operated in counter-current mode because the gas, owing upward, entrains the down owing liquid. This phenomenon is termed ooding. Several (structured) reactor concepts have been developed to allow countercurrent operation, amongst which a special type of monolith, the internally nned mnolith reactor (also see gure 2). The (relatively) small amount of liquid runs along the walls of the channel. This falling lm is stabilized by the nnes. The gas movews upward through the center of the channel. So, in essence, this is a falling lm reactor with a high area available for the falling lm. It has been shown that (using a specially designed outlet geometry) ooding limits are good and mass transfer is acceptable.

References
Bird, R. B., W.E.Stewart and Lightfoot, E., 1960, Transport Phenomena, John Wiley & sons. Krishna, R. and Sie, S., 1994, Strategies for Multiphase Reactor Selection, Chem. Eng. Sci. 49, 40294065. Moulijn, J. A. and Cybulski, A. (editors), 1998, Structured catalysts and reactors, Marcel Dekker. Perry, R. and Green, D., 1984, Perrys chemical engineers handbook, McGraw-Hill, New York, 6th ed.

0 1

org-S

4H2

org

H2 Sr

(13)