Nickel catalysts stability

Ethylene has been reported to copolymerize with butadiene using bisfylide)-stabilized nickel catalysts. Ostoja Starzewski, K. A. DE 3916211 to Bayer A. G., Fed. Rep. Ger., priority date May 18, 1989. Similar catalysts also provide styrene terminated oligomers of ethylene. Ostoja Starzewski, K. A. DE 4018068 to Bayer A. G., Fed. Rep. Ger., priority date June 6, 1990. 

Unfortunately, investigations with ionic liquids containing high amounts of AlEtCl2 showed several limitations, including the reductive effect of the alkylaluminium affecting the temperature stability of the nickel catalyst. At very high alkylaluminium concentrations, precipitation of black metallic nickel was observed even at room temperature. 

Intimate mixing of the components can lead to the formation of compounds or of solid solutions of the components which are difficult to reduce at 300°C but which, when reduced, contain well dispersed and well stabilized nickel. Methanation catalysts in practice therefore are compromises which combine optimum reducibility with activity and stability. As an example of compound formation, alumina readily forms with nickel... 

In experiment HGR-13, the commercial grade precipitated nickel catalyst was in a reduced and stabilized condition when it was charged into the reactor. No special activation treatment was needed. It was, however, kept under hydrogen at all times until the temperature and pressure of the system were brought to synthesis conditions, at which time the synthesis feed gas was gradually fed into the system to start the run. 

Fig. 3 showed the catalyst stability of Ni-Mg/HY, Ni-Mn/HY, and Ni/HY catalysts in the methme reforming with carbon dioxide at 700°C. Nickel and promoter contents were fixed at 13 wt.% and 5 wt.%, respectively. Initial activities over M/HY and metal-promoted Ni/HY catalysts were almost the same. It is noticeable that the addition of Mn and Mg to the Ni/HY catalyst remarkably stabilized the catalyst praformance and retarded the catalyst deactivation. Especially, the Ni-Mg/HY catalyst showed methane and carbon dioxide conversions more thrm ca. 85% and 80%, respectively, without significant deactivation even after the 72 h catalytic reaction. 

A. Cyclo-Oligomerization with Zerovalent PR3/P(0R)3-Stabilized Nickel Complexes as the Catalyst... 

Scheme 6. Interplay of the C8- and C -production channels for the cyclo-oligomerization of 1,3-butadiene with zero valent PR3/P(OR)3-stabilized nickel complexes as the catalyst. Free energies (AG, AGJ in kcalmol-1) are given relative to the favorable rf-synrfiC A-cis isomer of 2a for catalysts bearing strong a-donor ligands namely I (L = PMe3), III (L = PPrj), VI (L = PBU3), and -acceptor ligands namely V (L = P(OMe)3), IV...

For PR3/P(OR)3-stabilized nickel complexes, there are two borderline cases known from the experimental investigation of Heimbach et al. 1 which, unlike the usual behavior, redirect the cyclo-oligomerization reaction into the Ci2-cyclo-oligomer production channel. Catalysts bearing either strong a-donor ligands that must also introduce severe steric pressure (e.g., PBu Pr2) or sterically compact n-acceptors (like P(OMe)3) are known to yield CDT as the predominant product. From a statistical analysis it was concluded,8a,8c that the C8 Ci2-cyclo-oligomer product ratio is mainly determined by steric factors (75%) with electronic factors are less important. 

The following conclusions can be drawn (a) ir-Allylnickel compounds are probably not involved in the catalytic dimerization of cyclooctene, because the highest reaction rate occurs when only traces of these compounds can be detected further, the concentration of the new 7r-allyl-nickel compound (19) becomes significant only after the catalytic reaction has ceased, (b) The complex formed between the original 7r-allylnickel compound (11) and the Lewis acid is transformed immediately upon addition of cyclooctene to the catalytically active nickel complex or complexes. In contrast to 7r-allylnickel compounds, this species decomposes to give metallic nickel on treatment of the catalyst solution with ammonia, (c) The transformation of the catalytically active nickel complex to the more stable 7r-allylnickel complex occurs parallel with the catalytic dimerization reaction. This process is obviously of importance in stabilizing the catalyst system in the absence of reactive olefins. In... 

The effect of tin compounds, especially tetra-alkyl and tetra-aryl tin compounds, is similar to that of phosphine, though lower temperature and pressure are required for the catalyst s optimum activity. Tin can promote the activity of the nickel catalyst to a level that matches that of rhodium under mild conditions of system pressure and temperature e.g. 400 psig at 160 C. The tin-nickel complex is less stable than the phosphine containing catalyst. In the absence of carbon monoxide and at high temperature, as in carbonyl-ation effluent processing, the tin catalyst did not demonstrate the high stability of the phosphine complex. As in the case of phosphine, addition of tin in amounts larger than required to maintain catalyst stability has no effect on reaction activity. 

The activity of the nickel catalyst is affected by major variations in carbon monoxide partial pressure. With very low carbon monoxide partial pressure, nickel precipitates as a metal powder and occasionally as nickel iodide. Stability of the catalyst is improved with higher CO partial pressure up to a point above which the catalyst activity drops linearly. The optimum level of carbon monoxide is different from one catalyst mixture to another. This behavior is characteristic of all the nickel catalyzed carbonylation reactions we studied. In the Li-P system, optimum carbon monoxide partial pressure is in the range of 700 to 800 psi (Table V). On the other hand, the optimum carbon monoxide partial pressure for the Li-Sn system is in the range of 220 to 250 psi, at 160 C, and 450 psi at 180 C (Table VI). It is presumed that the retarding effect of higher carbon monoxide partial pressure is associated with stabilizing an inactive carbonyl species. 

Amination of i-butanol to diisobutylamine was investigated on vanadium modified granulated Raney nickel catalyst in a fixed bed reactor. The addition of 0.5 wt.% V to Raney nickel improved the yield of amines and the stability of catalyst. Factorial experimental design was used to describe the conversion of alcohol, the yield and the selectivity of secondary amine as a function of strong parameters, i.e. the reaction temperature, space velocity and NHs/i-butanol molar ratio. Diisobutylamine was obtained with 72% yield at 92% conversion and reaction parameters P=13 bar, T=240°C, WHSV=1 g/g h, and molar ratios NH3/iBuOH= 1.7, H2/NH3= 1.9. 

The V-modified Raney nickel catalyst showed noticeable stability in time-on-stream experiment for 55 h, and tolerated several heating-cooling cycles. It is... 

ACTIVITY AND STABILITY OF PROMOTED RANEY-NICKEL CATALYSTS IN GLUCOSE HYDROGENATION... 

It is well known, even from old literature data (ref. 1) that the presence of metal promotors like molybdenum and chromium in Raney-nickel catalysts increases their activity in hydrogenation reactions. Recently Court et al (ref. 2) reported that Mo, Or and Fe-promoted Raney-nickel catalysts are more active for glucose hydrogenation than unpromoted catalysts. However the effects of metal promotors on the catalytic activity after repeated recycling of the catalyst have not been studied so far. Indeed, catalysts used in industrial operation are recycled many times, stability is then an essential criterion for their selection. From a more fundamental standpoint, the various causes of Raney-nickel deactivation have not been established. This work was intended to address two essential questions pertinent to the stability of Raney-nickel in glucose hydrogenation namely what are the respective activity losses experienced by unpromoted or by molybdenum, chromium and iron-promoted catalysts after recycling and what are the causes for their deactivation ... 

Considering the reductive elimination mechanism that takes place within the coordination sphere of the palladium, one might expect the nucleophilic addition of unstabilized nucleophiles to be more enantioselective than that of stabilized nucleophiles because the nucleophile can directly interact with the chiral ligand. However, there are only a few examples in the literature that give high enantioselectivity. In the case of the alkylation with unstabilized carbanions, nickel catalysts have been more frequently used (see next section). 

A model manure solution was prepared based on 10% glucose (as a carbohydrate hydrolysate model) with the various mineral components. The model solution was processed with three different catalyst formulations for comparison. The two nickel catalysts, ruthenium stabilized and copper stabilized (4), exhibited no effects from the contaminants, while the ruthenium showed reduced activity similar to that already noted. 

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