Nickel dehydrogenation

Flydrodemetallization reduces the amount of nickel and, to a lesser extent, vanadium in FCC feeds. Nickel dehydrogenates feed to molecular hydrogen and aromatics. Removing these metals allows heavier gas oil cut points. 

Examples include hydrogenation of propanal over nickel, dehydrogenation of ethanol over copper-cobalt, dehydrogenation of methylcyclohexane to toluene over platinum, hydroformylation of olefins catalyzed by cobalt hydrocarbonyls on solid polymers, hydrogen-ion catalyzed hydration of olefins on ion exchangers, dehydrogenation of 1-butene to butadiene over chromia-alumina, and various hypothetical reactions. 

Nickel also is an important iadustrial catalyst. The most extensive use of nickel as a catalyst is ia the food iadustry ia connection with the hydrogenation or dehydrogenation of organic compounds to produce edible fats and oils (see Fats and FATTY oils). 

Another synthesis of pyrogaHol is hydrolysis of cyclohexane-l,2,3-trione-l,3-dioxime derived from cyclohexanone and sodium nitrite (16). The dehydrogenation of cyclohexane-1,2,3-triol over platinum-group metal catalysts has been reported (17) (see Platinum-GROUP metals). Other catalysts, such as nickel, rhenium, and silver, have also been claimed for this reaction (18). 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

The preparation of methyl 12-ketostearate from methyl ricinoleate has been accompHshed using copper chromite catalyst. The ketostearate can also be prepared from methyl ricinoleate in a two-step process using Raney nickel. The first step is a rapid hydrogenation to methyl 12-hydroxystearate, the hydrogen coming from the catalyst, followed by a slower dehydrogenation to product (50,51). 

Electroless reactions must be autocatalytic. Some metals are autocatalytic, such as iron, in electroless nickel. The initial deposition site on other surfaces serves as a catalyst, usually palladium on noncatalytic metals or a palladium—tin mixture on dielectrics, which is a good hydrogenation catalyst (20,21). The catalyst is quickly covered by a monolayer of electroless metal film which as a fresh, continuously renewed clean metal surface continues to function as a dehydrogenation catalyst. Silver is a borderline material, being so weakly catalytic that only very thin films form unless the surface is repeatedly cataly2ed newly developed baths are truly autocatalytic (22). In contrast, electroless copper is relatively easy to maintain in an active state commercial film thicknesses vary from <0.25 to 35 p.m or more. 

Dehydrogenation of A -imidazolines (294 Z = NR) gives imidazoles, but requires quite high temperatures and a catalyst such as nickel or platinum. Alternatively, hydrogen acceptors such as sulfur or selenium can be used (70AHC(12)103). 

It is not obvious how the adsorbed 2,2 -dihydro-2,2 -bipyridine (14) could leave the catalyst without undergoing dehydrogenation either simultaneously or before desorption. This second alternative could however be rationalized if it is assumed that in the preparation of 2,2 -bipyridine the two molecules of pyridine are bonded to one atom of nickel (15). The formation of the carbon-carbon bond could... 

Toluene is dealkylated to benzene over a hydrogenation-dehydrogenation catalyst such as nickel. The hydrodealkylation is essentially a hydrocracking reaction favored at higher temperatures and pressures. The reaction occurs at approximately 700°C and 40 atmospheres. A high benzene yield of about 96% or more can be achieved ... 

Metals are most active when they first deposit on the catalyst. With time, they lose their initial effectiveness through continuous oxidation-reduction cycles. On average, about one third of the nickel on the equilibrium catalyst will have the activity to promote dehydrogenation reactions. 

Catalyst composition and feed chloride have a noticeable impact on hydrogen yield. Catalysts with an active alumina matrix tend to increase the dehydrogenation reactions. Chlorides in the feed reactivate aged nickel, resulting in high hydrogen yield. 

The HVCH ratio is an indicator of dehydrogenation reactions. However, the ratio is sensitive to the reactor temperature and the type of catalyst. A better indicator of nickel activity is the volume of... 

Vanadium also promotes dehydrogenation reactions, but less than nickel. Vanadium s contribution to hydrogen yield is 20% to 50% of nickel s contribution, but vanadium is a more severe poison. Unlike nickel, vanadium does not stay on the surface of the catalyst. Instead, it migrates to the inner (zeolite) part of the catalyst and destroys the zeolite crystal structure. Catalyst surface area and activity are permanently lost. 

The effects of antimony passivation are usually immediate. By forming an alloy with nickel, the dehydrogenation reactions that are... 

Dehydrogenation. Under ideal conditions (i.e., a clean feedstock and a catalyst with no metals), cat cracking does not yield any appreciable amount of molecular hydrogen. Therefore, dehydrogenation reactions will proceed only if the catalyst is contaminated with metals such as nickel and vanadium. 

Nickel in the feed is deposited on the surface of the catalyst, promoting undesirable dehydrogenation and condensation reactions. These nonselective reactions increase gas and coke production at the expense of gasoline and other valuable liquid products. The deleterious effects of nickel poisoning can be reduced by the use of antimony passivation. 

The reaction scheme is rather complex also in the case of the oxidation of o-xylene (41a, 87a), of the oxidative dehydrogenation of n-butenes over bismuth-molybdenum catalyst (87b), or of ethylbenzene on aluminum oxide catalysts (87c), in the hydrogenolysis of glucose (87d) over Ni-kieselguhr or of n-butane on a nickel on silica catalyst (87e), and in the hydrogenation of succinimide in isopropyl alcohol on Ni-Al2Oa catalyst (87f) or of acetophenone on Rh-Al203 catalyst (87g). Decomposition of n-and sec-butyl acetates on synthetic zeolites accompanied by the isomerization of the formed butenes has also been the subject of a kinetic study (87h). 

Nickel metal successfully catalyzes the hydrogenation of double bonds in unsaturated hydrocarbons such as propylene and butene. Can this metal also catalyze the dehydrogenation of alkanes such as propane and butane ... 

In conclusion, hydrogenolysis processes and coke formation occur on large ensembles of surface platinum atoms [160], while dehydrogenation reactions would proceed on single (isolated) Pt atoms [169]. The presence of tin atoms regularly distributed on the metal surface diminishes the size of the ensemble [130,170-173], the same is observed for copper atoms on nickel surfaces [174] or tin atoms on rhodium and nickel surfaces [137,175-177], leading to site isolation and therefore to selectivity. 

The Raney nickel is a very efficient catalyst for the dehydrogenation of 2-butanol into butanone (Scheme 45) with a good selectivity (90%). But, for industrial applications selectivities as high as 99% are required. This can be achieved by poisoning some sites by reaction with Bu4Sn (the best results are obtained with a Sn/Ni ratio of 0.02), which probably occurs first on the sites responsible for the side reactions. The consequence is a slight decrease of the catalytic activity and an increase of the selectivity in 2-butanone which can reach 99%. This catalyst, developed by IFF, has been used commercially in Japan for several years [180]. 

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