Catalytic beds

Catalytic Incinerators. Catalytic incinerators, often used to remove hydrocarbons from exhaust gas streams, are more compact than direct-flame incinerators, operate at lower temperatures, often require Htfle fuel, and produce Httle or no NO from atmospheric fixation. However, the catalytic bed must be preheated and carefliUy temperature controlled. Thus these are generally unsuited to intermittent and highly variable gas flows. 

ActivatedL yer Loss. Loss of the catalytic layer is the third method of deactivation. Attrition, erosion, or loss of adhesion and exfoHation of the active catalytic layer aU. result in loss of catalyst performance. The monolithic honeycomb catalyst is designed to be resistant to aU. of these mechanisms. There is some erosion of the inlet edge of the cells at the entrance to the monolithic honeycomb, but this loss is minor. The peUetted catalyst is more susceptible to attrition losses because the pellets in the catalytic bed mb against each other. Improvements in the design of the peUetted converter, the surface hardness of the peUets, and the depth of the active layer of the peUets also minimise loss of catalyst performance from attrition in that converter. 

Several other changes that are supposed to slow down the reaction can cause runaway. In the case of ethylene oxidation, chlorinated hydrocarbons are used as inhibitors. These slow down both the total and the epoxidation, although the latter somewhat less. When the reaction is running too high and the inhibitor feed is suddenly increased in an attempt to control it, a runaway may occur. The reason is similar to that for the feed temperature cut situation. Here the inhibitor that is in the ppm region reacts with the front of the catalytic bed and slowly moves down stream. The unconverted reactants reach the hotter zone before the increased inhibitor concentration does. 

Other variations of the dual-bed scheme exist as a combination of thermal oxidizing reactors and catalytic reducing reactors. The Questor company has developed a reactor with three zones the first zone is a thermal reactor with limited air to raise the temperature of the exhaust gas, the second zone is a catalytic bed of metallic screens to reduce NO, and the third zone is another thermal reactor where secondary air is injected to complete the oxidation of CO and hydrocarbons (45). 

Simultaneous oxidation and reduction can take place in a single catalytic bed, provided that the air-to-fuel ratio is adjusted precisely at the stoichiometric 14.7 =t 0.1. This precise metering is required for the redox or three-way catalyst as shown in Fig. 8. A narrow window exists for some catalysts where more than 80% conversion efficiency can be obtained on all three pollutants (46). This precise metering cannot be attained by... 

Fig. 9. Principle of single catalytic bed for simultaneous reduction and oxidation with oxygen sensor and feedback control on air-to-fuel ratio.

Another important constraint comes from the pressure drop across the catalytic bed, which must be kept to a minimum to avoid a loss in engine power and performance. This requirement is satisfied by a very shallow pellet bed of no more than ten pellets deep, a monolithic structure with many open parallel channels, or a pile of metallic screens and saddles. 

The rates of catalytic bed warm-up from a cold start and of destructive overheating are governed by the rate of heat transfer from the gas phase to the solid surfaces. In the highest flow rate of gases, the rate of mass transfer of pollutant molecules to the catalytic walls is inadequate in the monolith. 

In a catalytic bed, lead tends to deposit more heavily at the front rows of pellets or at the front end of a monolith, and at the outside of a catalyst pellet (132). 

Many elements of a mathematical model of the catalytic converter are available in the classical chemical reactor engineering literature. There are also many novel features in the automotive catalytic converter that need further analysis or even new formulations the transient analysis of catalytic beds, the shallow pellet bed, the monolith and the stacked and rolled screens, the negative order kinetics of CO oxidation over platinum,... 

A comprehensive mathematical model of the pellet bed was developed in the IIEC program, and described by Wei 127) and by Kuo ei al. 21, H0). This model seeks to replace the catalytic bed by a series of cells with uniform temperatures and concentrations. The heat balance of the solid in cell i is given by... 

The IIEC model was also used to study the importance of various design parameters. Variations in gas flow rates and channeling in the bed are not the important variables in a set of first-order kinetics. The location of the catalytic bed from the exhaust manifold is a very important variable when the bed is moved from the exhaust manifold location to a position below the passenger compartment, the CO emission averaged over the cycle rose from 0.14% to 0.29% while the maximum temperature encountered dropped from 1350 to 808°F. The other important variables discovered are the activation energy of the reactions, the density and heat... 

The cracking of diphenylmethane (DPM) was carried out in a continuous-flow tubular reactor. The liquid feed contained 29.5 wt.% of DPM (Fluka, >99%), 70% of n-dodecane (Aldrich, >99% solvent) and 0.5% of benzothiophene (Aldrich, 95% source of H2S, to keep the catalyst sulfided during the reaction). The temperature was 673 K and the total pressure 50 bar. The liquid feed flow rate was 16.5 ml.h and the H2 flow rate 24 l.h (STP). The catalytic bed consisted of 1.0 g of catalyst diluted with enough carborundum (Prolabo, 0.34 mm) to reach a final volume of 4 cm. The effluent of the reactor was condensed at high pressure. Liquid samples were taken at regular intervals and analyzed by gas chromatography, using an Intersmat IGC 120 FL, equipped with a flame ionization detector and a capillary column (Alltech CP-Sil-SCB). 

After 24 h of reaction, the catalytic bed was retrieved and sieved to separate the catalyst from the diluent. The used catalyst particles were placed in a Soxhlet apparatus, washed with n-hexane for 8 hours and then dried overnight at 393 K. Their carbon content was determined by automatic titration of the CO2 formed by burning the washed sample, in a Strohlein Coulomat 702 apparatus. 

Figure 4.15. Schematic representation of the progressive adsorption of NO on a catalytic bed in a reactor flow [182].

Discontinuous (batch) processes are carried out in pressure vessels (autoclaves) where DMC is maintained as liquid by autogenous pressure. Instead, CF reactions at atmospheric pressure require that both DMC and the reagent(s) in the vapor phase come into contact with a catalytic bed a constraint that has spurred the development of new applications and alternative reaction engineering, namely, GL-PTC and the continuously fed stirred-tank reactor (CSTR). 

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