Catalyst sites

An unstabilized high surface area alumina siaters severely upon exposure to temperatures over 900°C. Sintering is a process by which the small internal pores ia the particles coalesce and lose large fractions of the total surface area. This process is to be avoided because it occludes some of the precious metal catalyst sites. The network of small pores and passages for gas transfer collapses and restricts free gas exchange iato and out of the activated catalyst layer resulting ia thermal deactivation of the catalyst. 

A TWC catalyst must be able to partition enough CO present in the exhaust for each of these reactions and provide a surface that has preference for NO adsorption. Rhodium has a slight preference for NO adsorption rather than O2 adsorption Pt prefers O2. Rh also does not cataly2e the unwanted NH reaction as does Pt, and Rh is more sinter-resistant than Pt (6). However, the concentrations of O2 and NO have to be balanced for the preferred maximum reduction of NO and oxidation of CO. This occurs at approximately the stoichiometric point with just enough oxidants (O2 and NO ) and reductants (CO, HC, and H2). If the mixture is too rich there is not enough O2 and no matter how active the catalyst, some CO and HC is not converted. If the mixture is too lean, there is too much O2 and the NO caimot effectively compete for the catalyst sites (53—58). 

The main catalyst site poison for many years was tetraethyllead [78-00-2] even after use of unleaded gasoline. Not only is lead a catalyst... 

The mechanism of poisoning automobile exhaust catalysts has been identified (71). Upon combustion in the cylinder tetraethyllead (TEL) produces lead oxide which would accumulate in the combustion chamber except that ethylene dibromide [106-93-4] or other similar haUde compounds were added to the gasoline along with TEL to form volatile lead haUde compounds. Thus lead deposits in the cylinder and on the spark plugs are minimized. Volatile lead hahdes (bromides or chlorides) would then exit the combustion chamber, and such volatile compounds would diffuse to catalyst surfaces by the same mechanisms as do carbon monoxide compounds. When adsorbed on the precious metal catalyst site, lead haUde renders the catalytic site inactive. 

Lead compounds were not found on the surrounding activated coating layer, rather only associated with the precious metal. The Pt sites are less poisoned by lead than are Pd or Rh sites because the Pt sites are protected by the sulfur in the fuel. Fuel sulfur is converted to SO2 in the combustion process, and Pt easily oxidizes SO2 to SO on the catalyst site. The SO reacts with the lead compounds to form PbSO, which then moves off the catalyst site so that lead sulfate is not a severe catalyst poison. Neither Pd nor Rh is as active for the SO2 to SO reaction, and therefore do not enjoy the same protection as Pt. 

Fig. 6. Catalyst inhibition mechanisms where ( ) are active catalyst sites the catalyst carrier and the catalytic support (a) masking of catalyst (b) poisoning of catalyst (c) thermal aging of catalyst and (d) attrition of ceramic oxide metal substrate monolith system, which causes the loss of active catalytic material resulting in less catalyst in the reactor unit and eventual loss in performance.

Poisoning is operationally defined. Often catalysts beheved to be permanently poisoned can be regenerated (5) (see Catalysts, regeneration). A species may be a poison ia some reactions, but not ia others, depending on its adsorption strength relative to that of other species competing for catalytic sites (24), and the temperature of the system. Catalysis poisons have been classified according to chemical species, types of reactions poisoned, and selectivity for active catalyst sites (24). 

There is a complication in choosing a catalyst for selective reductions of bifunctional molecules, For a function to be reduced, it must undergo an activated adsorption on a catalytic site, and to be reduced selectively it must occupy preferentially most of the active catalyst sites. The rate at which a function is reduced is a product of the rate constant and the fraction of active sites occupied by the adsorbed function. Regardless of how easily a function can be reduced, no reduction of that function will occur if all of the sites are occupied by something else (a poison, solvent, or other function). 

Solvents influence rate as well as selectivity. The effect on rate can be very great, and a number of factors contribute to it. In closely related solvents, the rate may be directly proportional to the solubility of hydrogen in the solvent, as was shown to be the case for the hydrogenation of cyclohexene over platinum-on-alumina in cyclohexane, methylcyclohexane, and octane 48). Solvents can compete for catalyst sites with the reacting substrates, change viscosity and surface tension (108), and alter hydrogen availability at the catalyst surface. 

The amount of solvent relative to the amount of total catalyst is usually large, and the amount of solvent relative to the number of active catalyst sites larger still very small amounts of inhibitors or poisons can have, therefore, large adverse influences on the rate of reduction. Solvent purity per se is of little regard in this connection, for gross amounts of innocuous impurities can be present without untoward effect. 

Hydrogen is dissociatively adsorbed on two catalyst sites, indicated by an asterisk. Sites need not necessarily be on different atoms. ... 

Acetylenes are, in general, much more strongly adsorbed than the corresponding olefin, and as long as the acetylene is present, it will occupy most of the catalyst sites and be reduced preferentially, regardless of the relative rates of the acetylene and olefin hydrogenation when not in competition for sites. The reduction... 

The important property of ZSM-5 and similar zeolites is the intercrystalline catalyst sites, which allow one type of reactant molecule to diffuse, while denying diffusion to others. This property, which is based on the shape and size of the reactant molecules as well as the pore sizes of the catalyst, is called shape selectivity. Chen and Garwood document investigations regarding the various aspects of ZSM-5 shape selectivity in relation to its intercrystalline and pore structure. 

A porphinatoaluminum alkoxide is reported to be a superior initiator of c-caprolactone polymerization (44,45). A living polymer with a narrow molecular weight distribution (M /Mjj = 1.08) is ob-tmned under conditions of high conversion, in part because steric hindrance at the catalyst site reduces intra- and intermolecular transesterification. Treatment with alcohols does not quench the catalytic activity although methanol serves as a coinitiator in the presence of the aluminum species. The immortal nature of the system has been demonstrated by preparation of an AB block copolymer with ethylene oxide. The order of reactivity is e-lactone > p-lactone. 

In solid electrolyte fuel cells, the challenge is to engineer a large number of catalyst sites into the interface that are electrically and ionically connected to the electrode and the electrolyte, respectively, and that is efficiently exposed to the reactant gases. In most successful solid electrolyte fuel cells, a high-performance interface requires the use of an electrode which, in the zone near the catalyst, has mixed conductivity (i.e. it conducts both electrons and ions). Otherwise, some part of the electrolyte has to be contained in the pores of electrode [1]. 

GP 1[ [R 1[ A change from aluminum to platinum as construction material results in reduced micro-reactor performance concerning oxidation of ammonia, decreasing N2O selectivity by 20% [28]. This is explained by the lower thermal conductivity of platinum, which causes larger temperature differences (hot spots) within the micro channels, i.e. at the catalyst site, e.g. due to insufficient heat removal from the channels or also by non-uniform temperature spread of the furnace heating. 

This was explained by having only the contribution of surface reaction in the case of batch processing, whereas micro reactors profit, in addition, from processing inside the pores of the catalyst beads. The penetration of the reaction solution into the pores is achieved here by applying pressure [2]. By this means, the number of available catalyst sites is increased. 

The size of the cataly.st particle influences the observed rate of reaction the smaller the particle, the less time required for the reactants to move to the active catalyst sites and for the products to diffuse out of the particle. Furthermore, with relatively fast reactions in large particles the reactants may never reach the interior of the particle, thus decreasing the catalyst utilization. Catalyst utilization is expressed as the internal effectiveness factor //,. This factor is defined as follows ... 

Two characterization techniques will be discussed in this chapter, viz. physisorption and chemisorption. Physisorption mainly yields information on catalyst texture and morphology, whereas chemisorption studies potentially give information regarding the active catalyst sites. 

Active catalyst sites can consist of a wide variety of species. Major examples are coordination complexes of transition metals, proton acceptors or donors in a solution, and defects at the surface of a metallic, oxidic, or sulphidic catalyst. Chemisorption is one of the most important techniques in catalyst characterization (Overbury et al., 1975 Bartley et al, 1988 Scholten et at, 1985 Van Delft et al, 1985 Weast, 1973 and Bastein et al., 1987), and, as a consequence, it plays an essential role in catalyst design, production and process development. 

With regard to the s-BuNH2 results, it is likely that steric bulk, especially at the tertiary C-H alpha to the NH2 group, limits its ability to bind to the active catalyst site and therefore it cannot compete with EtgSiH, although it can still function as a reactant. 

The MO concentrations versus time profiles were fitted to second order polynomial equations and the parameters estimated by nonlinear regression analysis. The initial rates of reactions were obtained by taking the derivative at t=0. The reaction is first order with respect to hydrogen pressure changing to zero order dependence above about 3.45 MPa hydrogen pressure. This was attributed to saturation of the catalyst sites. Experiments were conducted in which HPLC grade MIBK was added to the initial reactant mixture, there was no evidence of product inhibition. 

Cleaning and sweeping of the Ti02 surface due to acoustic microstreaming allows for an access to more active catalyst sites at any given time. 

We should also point out that the adsorption equilibrium constants appearing in the Hougen-Watson models cannot be determined from adsorption equilibrium constants obtained from nonreacting systems if one expects the mathematical expression to yield accurate predictions of the reaction rate. One explanation of this fact is that probably only a small fraction of the catalyst sites are effective in promoting the reaction. 

Off = atomically adsorbed oxygen o = vacant catalyst site... 

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. 

The two limiting cases for the distribution of deactivated catalyst sites are representative of some of the situations that can be encountered in industrial practice. The formation of coke deposits on some relatively inactive cracking catalysts would be expected to occur uniformly throughout the catalyst pore structure. In other situations the coke may deposit as a peripheral shell that thickens with time on-stream. Poisoning by trace constituents of the feed stream often falls in the pore-mouth category. 

Several mechanisms for ring closure at a catalyst site consisting of a single metal atom have been suggested. Shephard and Rooney (186) pro-... 

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