Catalyst deactivation selective poisoning

The importance of catalyst stability is often underestimated not only in academia but also in many sectors of industry, notably in the fine chemicals industry, where high selectivities are the main objective (1). Catalyst deactivation is inevitable, but it can be retarded and some of its consequences avoided (2). Deactivation itself is a complex phenomenon. For instance, active sites might be poisoned by feed impurities, reactants, intermediates and products (3). Other causes of catalyst deactivation are particle sintering, metal and support leaching, attrition and deposition of inactive materials on the catalyst surface (4). Catalyst poisons are usually substances, whose interaction with the active surface sites is very strong and irreversible, whereas inhibitors generally weakly and reversibly adsorb on the catalyst surface. Selective poisons are sometimes used intentionally to adjust the selectivity of a particular reaction (2). 

Trace metal concentrations in herbaceous biomass materials are the final area of concern, particularly with the emphasis on mercury emissions management and the possible concern for selective catalytic reduction catalyst deactivation or poisoning as a result of cofiring straws and other herbaceous biomass fuels [1,17]. The database ftM" herbaceous materials is not extensive. Table 5.10 presents a general range of values. 

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. 

The selectivity in a system of parallel reactions does not depend much on the catalyst size if effective diffusivities of reactants, intermediates, and products are similar. The same applies to consecutive reactions with the product desired being the final product in the series. In contrast with this, for consecutive reactions in which the intermediate is the desired product, the selectivity much depends on the catalyst size. This was proven by Edvinsson and Cybulski (1994, 1995) for. selective hydrogenations and also by Colen et al. (1988) for the hydrogenation of unsaturated fats. Diffusion limitations can also affect catalyst deactivation. Poisoning by deposition of impurities in the feed is usually slower for larger particles. However, if carbonaceous depositions are formed on the catalyst internal surface, ageing might not depend very much on the catalyst size. 

Catalyst deactivation refers to the loss of catalytic activity and/or product selectivity over time and is a result of a number of unwanted chemical and physical changes to the catalyst leading to a decrease in number of active sites on the catalyst surface. It is usually an inevitable and slow phenomenon, and occurs in almost all the heterogeneous catalytic systems.111 Three major categories of deactivation mechanisms are known and they are catalyst sintering, poisoning, and coke formation or catalyst fouling. They can occur either individually or in combination, but the net effect is always the removal of active sites from the catalyst surface. 

Studies of the deactivation of ATR catalysts show that the sulfur present in conventional fuels is responsible for rapid deactivation of both Ni-based and noble metal catalysts. At some conditions, sulfur appears to selectively poison the sites responsible for the SR reaction(s). 

The authors believe that sulfur selectively poisons the SR reaction (Reaction (2)), rather than the oxidation reactions (Reactions (1) and (4)). However, because the catalyst is neither described nor analyzed before or after the reaction, the cause(s) and extent of the deactivation are not clear. 

Allowing for some spread in the data it seems as if little deactivation is caused by the first 4-5% wt carbon deposited, after which there is an exponential activity decline. This deactivation behaviour is of course indicative of the way in which coke is deposited on the catalyst surface, The initial deposition of coke mainly takes place on the bare A1203 surface, i,e. does not interfere with the active phase as demonstrated in a previous paper [6], At higher coke levels we observe an exponential activity decline indicative of a fouling type of deactivation rather than selective poisoning. 

FTIR model experiments were performed to reveal the nature of catalyst deactivation in C02. The spectrum taken at 15 bar in a C02/H2 mixture is shown in Fig. 1. The bands at 2060 and 1870 cm 1 indicate considerable coverage of Pt by linearly and bridge-bonded CO [12], formed by the reduction of C02 on Pt (reverse water gas shift reaction). The three characteristic bands at 1660, 1440 and 1235 cm 1 are attributed to C02 adsorption on A1203, likely as carbonate species [13, 14], It is well known [15] that CO is a strong poison for the hydrogenation of carbonyl compounds on Pt, but can improve the selectivity of the acetylene — olefin type transformations. Based on the above FTIR experiments it cannot be excluded that there are other strongly adsorbed species on Pt formed in small amounts. It is possible that the reduction of C02 provides also -COOH and triply bonded COH, as proposed earlier [16]. 

The catalyst is rapidly poisoned by vanadium and nickel, which deactivate the catalyst permanently and lower reaction selectivity. 

In the second step, the triple bond in 63 is selectively reduced to the cz -alkene using the Lindlar catalyst to form 64. In this case, the Lindlar catalyst is a poisoned heterogeneous palladium catalyst on barium sulfate. The deactivation of the catalyst with quinoline is responsible for the selective hydrogenation to the alkene and not through to the alkane. The reason for the highly stereoselective reduction with syn-addition to the cw-alkene is that one face of the triple bond is shielded by the catalyst surface. 

J. Barbier, P. Marecot, N. Martin, C. Elasah, and R. Maurel, Selective Poisoning by Coke Formation, in B. Delmon and G.R. Froment (Eds.), Catalyst Deactivation, Elsevier, Amsterdam, 1980, p. 53. 

Rather than increasing the operating S/C ratio, it is more desirable to develop reforming catalysts that are inherently more carbon-tolerant than Ni [19, 35, 37-43], For example, it has been suggested that Ru and Rh do not facilitate the formation of carbon deposits because of poor carbon solubility in these metals [30, 44]. However, Ru and Rh are prohibitively expensive. It has also been shown that the promotion of Ni with alkaline earth metals such as Mg suppresses carbon-induced catalyst deactivation [18, 36]. There have also been reports that by selectively poisoning the low-coordinated Ni sites with small amounts of sulfur, the carbon-induced deactivation of Ni can be suppressed [9, 45]. In addition, the patent literature is rich with multiple examples where numerous additives, including those mentioned below in this text (e.g., Sn and Au), have been suggested to promote the stability of Ni catalysts [46]. 

Besides activity and selectivity, stability is crucial in catalysis applications. Catalyst deactivation can have a kinetic origin. For instance, deactivation might occur by a serial reaction mechanism in which an intermediate can undergo a reaction to form a substance that is a poison for the active catalyst sites. Frequently encountered examples are oligomerization and coke formation. 

A Pt-Rh three way catalyst used in natural gas-fueled engine systems for 21,000 h showed specific deactivation characteristics, including a decrease in the selectivity of NO reduction, which can neither be reproduced by heat treatment nor explained by physical poisoning such as the blockage of micropores. Through chemieal analyses, EPMA, and activity tests of the used catalyst and model-poisoned catalysts, it was found that the activities of Rh on the used eatalyst were decreased by chemical poisoning due to Pb, causing a decrease in the NO reduction selectivity, and that the absolute rates of NO reduction and other reactions are considerably reduced by a decrease in the effective surface area of the catalyst due to accumulated compounds on the wash coat surface, in addition to thermal effects. 

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