Poisoned catalysts, reaction rates

The temperature coeflScient of reaction on such poisoned catalysts will be markedly lower than on unpoisoned catalysts, as is discernible from the rate eq. (76). For large ho (greater than about 20) and for moderate amounts of poisoning (a = 0.2 to 0.9), then the hyperbolic tangent term in eq. (76) will always be about unity, and in the denominator 1.0 may be neglected as compared with aho. For such poisoned catalysts the rate becomes ... 

Conditions of hydrogenation also determine the composition of the product. The rate of reaction is increased by increases in temperature, pressure, agitation, and catalyst concentration. Selectivity is increased by increasing temperature and negatively affected by increases in pressure, agitation, and catalyst. Double-bond isomerization is enhanced by a temperature increase but decreased with increasing pressure, agitation, and catalyst. Trans isomers may also be favored by use of reused (deactivated) catalyst or sulfur-poisoned catalyst. 

Oxidation kinetics over platinum proceeds at a negative first order at high concentrations of CO, and reverts to a first-order dependency at very low concentrations. As the CO concentration falls towards the center of a porous catalyst, the rate of reaction increases in a reciprocal fashion, so that the effectiveness factor may be greater than one. This effectiveness factor has been discussed by Roberts and Satterfield (106), and in a paper to be published by Wei and Becker. A reversal of the conventional wisdom is sometimes warranted. When the reaction kinetics has a negative order, and when the catalyst poisons are deposited in a thin layer near the surface, the optimum distribution of active catalytic material is away from the surface to form an egg yolk catalyst. 

Figure 7.21 shows the results for the ammonia synthesis on real catalysts in a reactor. The surface is predominantly covered by atomic nitrogen and by NH intermediates. This actually limits the rate of the reaction as soon as an appreciable partial pressure of ammonia has built up. In fact, ammonia poisons the reaction. 

Figure 9. Relative rate of CO hydrogenation as a function of copper coverage on a Ru(OOOl) catalyst Reaction temperature 575K. Results for sulfur poisoning from Figure 7 have been replotted for comparison.

The reduction of this ester over Pd differed from the corresponding reaction over Pi in every important particular. Enantiomeric excess was low (high over Pt) and in the reverse sense (e g cinchonidine modification provided an S-excess in the product over Pd but an R-excess over Pt) Enantioselective reactions underwent self-poisoning over Pd (proceeded to completion over Pt), were of non-integral order (integral over Pt) and proceeded more slowly than reaction over unmodified catalyst (enhanced rate over Pt) Enantioselective reaction was solvent-specific over Pd (not over Pt) and was favoured by low catalyst reduction temperature (high reduction temperature for Pt)... 

Steady state measurements of NO decomposition in the absence of CO under potentiostatic conditions gave the expected result, namely rapid self-poisoning of the system by chemisorbed oxygen addition of CO resulted immediately in a finite reaction rate which varied reversibly and reproducibly with changes in catalyst potential (Vwr) and reactant partial pressures. Figure 1 shows steady state (potentiostatic) rate data for CO2, N2 and N2O production as a function of Vwr at 621 K for a constant inlet pressures (P no, P co) of NO and CO of 0.75 k Pa. Also shown is the Vwr dependence of N2 selectivity where the latter quantity is defined as... 

Such bimetallic alloys display higher tolerance to the presence of methanol, as shown in Fig. 11.12, where Pt-Cr/C is compared with Pt/C. However, an increase in alcohol concentration leads to a decrease in the tolerance of the catalyst [Koffi et al., 2005 Coutanceau et ah, 2006]. Low power densities are currently obtained in DMFCs working at low temperature [Hogarth and Ralph, 2002] because it is difficult to activate the oxidation reaction of the alcohol and the reduction reaction of molecular oxygen at room temperature. To counterbalance the loss of performance of the cell due to low reaction rates, the membrane thickness can be reduced in order to increase its conductance [Shen et al., 2004]. As a result, methanol crossover is strongly increased. This could be detrimental to the fuel cell s electrical performance, as methanol acts as a poison for conventional Pt-based catalysts present in fuel cell cathodes, especially in the case of mini or micro fuel cell applications, where high methanol concentrations are required (5-10 M). 

A few additional points have also been raised by specific surface-science work concerning the catalytic reduction of NO. For instance, it has been widely recognized that the reaction is sensitive to the structure of the catalytic surface. It was determined that rough surfaces such as (110), or even (100), planes enhance NO dissociation over flatter (111) surfaces, and also favor N2 desorption instead of N20 production. On the other hand, NO dissociation leads to poisoning by the resulting atomic species, hence the faster reaction rates seen with medium-size vs. larger particles on model rhodium supported catalyst (the opposite appears to be true on palladium). Also, at least in the case of palladium, the formation of an isocyanate (-NCO) intermediate was identified... 

Enantioselective hydrogenation of 2,3-butanedione and 3,4-hexanedione has been studied over cinchonidine - Pt/Al203 catalyst system in the presence or absence of achiral tertiary amines (quinuclidine, DABCO) using solvents such as toluene and ethanol. Kinetic results confirmed that (i) added achiral tertiary amines increase both the reaction rate and the enantioselectivity, (ii) both substrates have a strong poisoning effect, (iii) an accurate purification of the substrates is needed to get adequate kinetic data. The observed poisoning effect is attributed to the oligomers formed from diketones. 

Promoters may influence selectivity by poisoning undesired reactions or by increasing the rates of desired intermediate reactions so as to increase the yield of the desired product. If they act in the first sense, they are sometimes referred to as inhibitors. An example of this type of action involves the addition of halogen compounds to the catalyst used for oxidizing ethylene to ethylene oxide (silver supported on alumina). The halogens prevent complete oxidation of the ethylene to carbon dioxide and water, thus permitting the use of this catalyst for industrial purposes. 

In the design of commercial scale heterogeneous catalytic reactors, the activity of the catalyst will almost invariably change with time. We now wish to focus our attention on the implications of poisoning reactions for efficient use of catalyst surface areas. Since reactant molecules must interact with unpoisoned catalyst sites before reaction can occur, the poisoning process may have two effects on the reaction rate one observes. 

Now consider the other extreme condition where diffusion is rapid relative to chemical reaction [i.e., hT( 1 — a) is small]. In this situation the effectiveness factor will approach unity for both the poisoned and unpoisoned reactions, and we must retain the hyperbolic tangent terms in equation 12.3.124 to properly evaluate Curve C in Figure 12.11 is calculated for a value of hT = 5. It is apparent that in this instance the activity decline is not nearly as sharp at low values of a as it was at the other extreme, but it is obviously more than a linear effect. The reason for this result is that the regions of the catalyst pore exposed to the highest reactant concentrations do not contribute proportionately to the overall reaction rate because they have suffered a disproportionate loss of activity when pore-mouth poisoning takes place. 

For situations where the reaction is very slow relative to diffusion, the effectiveness factor for the poisoned catalyst will be unity, and the apparent activation energy of the reaction will be the true activation energy for the intrinsic chemical reaction. As the temperature increases, however, the reaction rate increases much faster than the diffusion rate and one may enter a regime where hT( 1 — a) is larger than 2, so the apparent activation energy will drop to that given by equation 12.3.85 (approximately half the value for the intrinsic reaction). As the temperature increases further, the Thiele modulus [hT( 1 — a)] continues to increase with a concomitant decrease in the effectiveness with which the catalyst surface area is used and in the depth to which the reactants are capable of... 

Catalysts are porous and highly adsorptive, and their performance is affected markedly by the method of preparation. Two catalysts that are chemically identical but have pores of different size and distribution may have different activity, selectivity, temperature coefficient of reaction rate, and response to poisons. The intrinsic chemistry and catalytic action of a surface may be independent of pore size, but small pores appear to produce different effects because of the manner and time in which hydrocarbon vapors are transported into and out of the interstices. 

The ideal performance of a fuel cell depends on the electrochemical reactions that occur with different fuels and oxygen as summarized in Table 2-1. Low-temperature fuel cells (PEFC, AFC, and PAFC) require noble metal electrocatalysts to achieve practical reaction rates at the anode and cathode, and H2 is the only acceptable fuel. With high-temperature fuel cells (MCFC, ITSOFC, and SOFC), the requirements for catalysis are relaxed, and the number of potential fuels expands. Carbon monoxide "poisons" a noble metal anode catalyst such as platinum (Pt) in low-temperature... 

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