Nickel catalyst properties

C. It occurs in natural gas. May prepared by reduction of ethene or ethyne by hydrogen under pressure in the presence of a nickel catalyst, or by the electrolysis of a solution of potassium elhanoate. It has the general properties of the paraffins. Used in low-temperature refrigeration plant. 

An advantage of nickel catalysts over other metal systems is that the properties of the active species can easily be tuned by the addition of suitable ligands. For example, the presence of PPhj was shown to have a direct influence on the regiochem-istry of hydroalumination of 1,1-dimethylindene la [33]. While the reaction of BU2AIH with la gave a 4 1 mixture of regioisomeric products 13a/13b after deuterolytic workup, the same reaction carried out in the presence of PPh, yielded 13a and 13b in a ratio of >99 1 (Scheme 2-14). 

Scheme 6 displays the interplay of the two reaction channels for this type of nickel catalyst. The electronic and steric properties of the ancillary ligand are shown to have a pronounced influence on the kinetic and thermodynamic aspects of the VCH (via 2a 8a) and cis,cis-COD (via 4a 10a) generating routes (cf. Section 5.4) and will also affect the substitution process of the PR3/P(OR)3 ligand by incoming butadiene in the octadienediyl-Ni11 complex (vide infra). The species 2a and 2b are likely to... 

The isomer distribution of the nickel catalyst system in general is similar qualitatively to that of the Rh catalyst system described earlier. However, quantitatively it is quite different. In the Rh system the 1,2-adduct, i.e., 3-methyl-1,4-hexadiene is about 1-3% of the total C6 products formed, while in the Ni system it varies from 6 to 17% depending on the phosphine used. There is a distinct trend that the amount of this isomer increases with increasing donor property of the phosphine ligands (see Table X). The quantity of 3-methyl-1,4-pentadiene produced is not affected by butadiene conversion. On the other hand the formation of 2,4-hexadienes which consists of three geometric isomers—trans-trans, trans-cis, and cis-cis—is controlled by butadiene conversion. However, the double-bond isomerization reaction of 1,4-hexadiene to 2,4-hexadiene by the nickel catalyst is significantly slower than that by the Rh catalyst. Thus at the same level of butadiene conversion, the nickel catalyst produces significantly less 2,4-hexadiene (see Fig. 2). 

In the literature there are many reports of the formation of active catalyst for the 1 1 codimerization or synthesis of 1,4-hexadiene employing a large variety of Co or Fe salts, in conjunction with different kinds of ligands and organometallic cocatalysts. There must have been many structures, all of which are active for the codimerization reaction to one degree or another. The scope of the catalyst compositions claimed to be active as the codimerization catalysts is shown in Table XV (69-82). As with the nickel catalyst system discussed earlier, the preferred Co or Fe catalyst system requires the presence of phosphine ligands and an alkylaluminum cocatalyst. The catalytic property can be optimized by structural control of these two components. 

Nickel catalysts, 77 94, 99, 109 precipitated, 77 121-122 Nickel-catalyzed dinitrotoluene hydrogenation, 25 194 Nickel chelates, 77 117 Nickel chloride hexahydrate, 77 109, 110 Nickel chromate, molecular formula, properties, and uses, 6 562t Nickel-chromium alloy 600, in galvanic series, 7 805t... 

As work began on the process, it quickly became apparent that the extraordinary catalyst properties required for the process were not then available, and even with a superior catalyst, consumption would undoubtedly be severe. Figure 3 shows how Ramsbottom Carbon and nickel plus vanadium vary in the same reduced crude oils. All levels are very high far beyond anything normally encountered in a gas oil feedstock. 

In addition to the activity, other important requirements for the catalyst are the capability to start the reaction rapidly without the necessity for previous reduction with hydrogen and to perform effectively with intermittent operation these are essential properties for the catalyst in reformers, especially for portable and small-scale stationary fuel cell applications. In this respect, Dias and Assaf [61] focused on the potential of Pd, Pt and Ir to promote fast and intermittent ignition of methane ATR in Ni/y-Al203. They concluded that the three metals are very good promoters of the reduction of the nickel catalyst with methane, but the lower cost of palladium makes this metal more suitable than Pt and Ir for small fuel cells. 

Oxiranes react with a wide variety of nucleophilic reagents, under neutral or base- or acid-catalyzed conditions, and this property has led to their extensive exploitation in synthesis. They also undergo hydrogenation in the presence of Raney nickel catalyst, which,... 

It is clear that the influence of surface geometry upon catalytic activity is extremely complex and many more studies are required before any definitive relationship between catalytic activity and metal particle size can be established. Such studies will require to take cognisance of such factors as the perturbation of surface structure due to the formation of carbidic residues, as noted by Boudart [289] and by Thomson and Webb [95], and by the modification of catalytic properties on adsorption, as noted by Izumi et al. [296—298] and by Groenewegen and Sachtler [299] in studies of the modification of nickel catalysts for enantioselective hydrogenation. Possible effects of the support, as will be discussed in Sect. 6.3, must also be taken into account. 

The benzaldehyde was 99.5% pure, as measured by GC and HPLC. Its contact with air was avoided so as to eliminate the possibility of oxidation. The purity of hydrogen was better than 99.7%. Two nickel catalysts were used, both provided by Engelhard, de Meem B.V. Their properties are given in Table 1. 

The introduction of further alloying components into a Ni2A1 alloy had a substantial effect on the properties of the Raney nickel catalyst. 

The modification of the Ni Al alloy by addition of molybdenum or chromium has a significant effect on the properties of the Raney nickel catalyst in the reaction of hydrogenation of valeronitrile. In the case of molybdenum, the catalytic properties may be correlated to the physico-chemical characteristics of the catalysts. Chromium is an effective promoter for initial activity and for selectivity. The mechanism for promotion of chromium in Raney nickel is not known exactly. 

Liquid-phase hydrogenation of 1,4 butynediol to cis-1,4-butenediol and 1,4-butanediol has been carried out on nickel catalysts supported on thirteen different supports. Some commercial nickel catalysts were used as references. Furthermore, metal loading and Ni-Cu alloying have also been studied. The results obtained indicates that catalytic activity, selectivity and metal surface area of catalysts are closely correlated to some textural and/or acid-base properties of the corresponding support. Similarly, the influence of Cu as a second metal in catalyst behaviour is also related to the nature of the support. 

TABLE 6 General expression of the correlation y = ax + b obtained between some surface properties of the supports in Table 1 and the corresponding catalytic properties of supported nickel catalysts in Table 2. ... 

In Section IV, the kinetics and mechanisms of catalytic HDM reactions are presented. Reaction pathways and the interplay of kinetic rate processes and molecular diffusion processes are discussed and compared for demetallation of nickel and vanadium species. Model compound HDM studies are reviewed first to provide fundamental insight into the complex processes occurring with petroleum residua. The effects of feed composition, competitive reactions, and reaction conditions are discussed. Since development of an understanding of the kinetics of metal removal is important from the standpoint of catalyst lifetime, the effect of catalyst properties on reaction kinetics and on the resulting metal deposition profiles in hydroprocessing catalysts are discussed. 

Most investigations have revealed that vanadium removal rates exceed those of nickel in petroleum residua. Results are summarized in Table XXVI. Cases of V/Ni activity ratios of less than one have been reported less frequently (Inoguchi et al., 1971 Galiasso et al., 1985). These have generally been due to a temperature phenomenon but may also result from unique feedstock or catalyst properties. 

Secondary amines can be prepared from the primary amine and carbonyl compounds by way of the reduction of the derived Schiff bases, with or without the isolation of these intermediates. This procedure represents one aspect of the general method of reductive alkylation discussed in Section 5.16.3, p. 776. With aromatic primary amines and aromatic aldehydes the Schiff bases are usually readily isolable in the crystalline state and can then be subsequently subjected to a suitable reduction procedure, often by hydrogenation over a Raney nickel catalyst at moderate temperatures and pressures. A convenient procedure, which is illustrated in Expt 6.58, uses sodium borohydride in methanol, a reagent which owing to its selective reducing properties (Section 5.4.1, p. 519) does not affect other reducible functional groups (particularly the nitro group) which may be present in the Schiff base contrast the use of sodium borohydride in the presence of palladium-on-carbon, p. 894. 

There have been a considerable number of papers reporting the properties of sulphur-resistant methanation catalysts, i.e., catalysts which can operate successfully in significant partial pressures of H2S. Most of these report work using catalysts containing vanadium, molybdenum, and such metals. However, attempts have been made to find nickel-based catalysts containing suitable additives to allow them to operate in such atmospheres. For example, Bartholomew and Uken115 have compared the deactivation behaviour of a range of nickel catalysts in 10 p.p.m. H2S. They found that nickel boride catalysts and Raney nickel materials deactivated more slowly than did unsupported nickel and alumina-supported nickel. They attributed this improvement to two factors ... 

Surface area, pore size, and pore volume are among the most fundamentally important properties in catalysis because the active sites are present or dispersed throughout the internal surface through which reactants and products are transported. The pores are usually formed by drying or calcining precipitates of hydrous oxides however, some materials possess porosity naturally, as in the case of carbons, natural zeolites, and others. Raney nickel catalysts... 

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