Nickel catalysts reduced

Ni-Gr I.1 This nickel catalyst reduces disubstituted alkynes to cis-alkenes the stereoselectivity is comparable to that observed with Lindlar catalyst or nickel boride (3, 208 -210 5,471-472). 

A/iPW-hydroxybenzaldehyde is available and hydrogenation of (38) with Raney nickel catalyst reduces the double bond and the aromatic ring, leaving only reoxidation for a short synthesis of (34). The overall yield is 25%. 

Draw the condensed structural formula, or skeletal formula if cyclic, for the organic product when hydrogen and a nickel catalyst reduce each of the followiug (12.4)... 

Undecomposed copper/nickel catalyst reduces very easily in hydrogen with two distinct reduction peaks. The first, between 180-280 C, corresponds to the reduction of free nickel and copper oxides. The second, between 240 50°C, corresponds to the single r uction peak of nickel catalyst. 

Insoluble in water, soluble in organic solvents b.p. — 15°C. Prepared by treating 1,4-dibromo-butane with metallic sodium. Reduced to n-butane by hydrogen at 200" C in presence of nickel catalysts. 

The sample is reduced in a hydrogen stream at 800°C in the presence of a nickel catalyst. The ammonia formed is detected by coulometry and the test sensitivity is on the order of one part per million. 

Nitro groups are efficiently reduced with hydrogen over Raney nickel catalyst (I. Fel-ner, 1967), with hydrides, or with metals. 

Tetrahydrofurfuryl alcohol reacts with ammonia to give a variety of nitrogen containing compounds depending on the conditions employed. Over a barium hydroxide-promoted skeletal nickel—aluminum catalyst, 2-tetrahydrofurfur5iarnine [4795-29-3] is produced (113—115). With paHadium on alumina catalyst in the vapor phase (250—300°C), pyridine [110-86-1] is the principal product (116—117) pyridine also is formed using Zn and Cr based catalysts (118,119). At low pressure and 200°C over a reduced nickel catalyst, piperidine is obtained in good yield (120,121). 

The first process utilizes a bed of nickel catalyst which has been regenerated with hydrogen to reduce the nickel content to metallic form. The finely divided metal then reacts with impurities and retains them in the bed, probably as nickel oxide in the case of oxygen or as physisorbed compounds for other impurities. Periodically, the bed is regenerated at elevated temperature using hydrogen to restore the metallic content. The nickel process can be used and regenerated indefinitely. 

Reduction. Acetaldehyde is readily reduced to ethanol (qv). Suitable catalysts for vapor-phase hydrogenation of acetaldehyde are supported nickel (42) and copper oxide (43). The kinetics of the hydrogenation of acetaldehyde over a commercial nickel catalyst have been studied (44). 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Uses ndReactions. Nerol (47) and geraniol (48) can be converted to citroneUol (27) by hydrogenation over a copper chromite catalyst (121). In the absence of hydrogen and under reduced pressure, citroneUal is produced (122). If a nickel catalyst is used, a mixture of nerol, geraniol, and citroneUol is obtained and such a mixture is also useful in perfumery. Hydrogenation of both double bonds gives dimethyl octanol, another useful product. 

Hydrogenation at lower temperature and ia the presence of catalysts yields organic sulfur compounds. With a reduced nickel catalyst at 180°C, methanedithiol [6725-64-0] is formed ... 

Dry reduced nickel catalyst protected by fat is the most common catalyst for the hydrogenation of fatty acids. The composition of this type of catalyst is about 25% nickel, 25% inert carrier, and 50% soHd fat. Manufacturers of this catalyst include Calsicat (Mallinckrodt), Harshaw (Engelhard), United Catalysts (Sud Chemie), and Unichema. Other catalysts that stiH have some place in fatty acid hydrogenation are so-called wet reduced nickel catalysts (formate catalysts), Raney nickel catalysts, and precious metal catalysts, primarily palladium on carbon. The spent nickel catalysts are usually sent to a broker who seUs them for recovery of nickel value. Spent palladium catalysts are usually returned to the catalyst suppHer for credit of palladium value. 

Reaction with hydrogen at 220°C in the presence of reduced nickel catalyst results in total decomposition to hydrogen chloride and carbon. An explosive reaction occurs with butylUthium in petroleum ether solution (4). Tetrachloroethylene also reacts explosively with metallic potassium at its melting point, however it does not react with sodium (5). 

Hydrogenation of Acetaldehyde. Acetaldehyde made from acetylene can be hydrogenated to ethanol with the aid of a supported nickel catalyst at 150°C (156). A large excess of hydrogen containing 0.3% of oxygen is recommended to reduce the formation of ethyl ether. Anhydrous ethanol has also been made by hydrogenating acetaldehyde over a copper-on-pumice catalyst (157). 

Effect of Catalyst The catalysts used in hydrotreating are molybdena on alumina, cobalt molybdate on alumina, nickel molybdate on alumina or nickel tungstate. Which catalyst is used depends on the particular application. Cobalt molybdate catalyst is generally used when sulfur removal is the primary interest. The nickel catalysts find application in the treating of cracked stocks for olefin or aromatic saturation. One preferred application for molybdena catalyst is sweetening, (removal of mercaptans). The molybdena on alumina catalyst is also preferred for reducing the carbon residue of heating oils. 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

According to Read and Smith i piperitone is, under natural conditions, optically inactive. By fractional distillation under reduced pressure, it is prepared, by means of its sodium bisulphite compound, in a laavo-rotatory form. The slight laevo-rotation is probably due to the presence of traces of cryptal. By fractional distillation alone, it is usually obtained in a laevo-rotatory form whether this is due to decomposition products or not is unknown. Piperitone has a considerable prospective economic value, as it forms thymol by treatment with formic chloride, inactive menthone by reduction when a nickel catalyst is employed, and inactive menthol by further reduction. Its char-Mters are as follows —... 

Pure piperitone was subjected to the action of purified hydrogen, in the presence of a nickel catalyst, for six hours, the temperature ranging between 175° to 180° C. The double bond in piperitone was readily opened out with the formation of menthone, but further action of the hydrogen under these conditions did not reduce the carbonyl group, even after continued treatment for two days. Under correct conditions, however, the reduction to menthol should take place. The ease with which menthone is formed in this way is of special interest, not only in connection with the production of this ketone, but also as a stage in the manufacture of menthol. 

A solution of 151 grams of 1-(3, 4 -dimethoxyphenyl)-2-propanone oxime in 200 cc of absolute ethanol is treated with 5 grams of Raney nickel catalyst and ammonia in an autoclave at about 25 atm of pressure and at 75 -100°C. The reduction is complete in about one-half hour and the reaction mixture is filtered and fractionated under reduced pressure to recover the a-methylhomoveratrylamine formed by the reduction. a-Methylhomoveratryl-amine thus prepared boiled at 163°-165°C at 18 mm pressure. 

Amines can be synthesized in a single step by treatment of an aldehyde or ketone with ammonia or an amine in the presence of a reducing agent, a process called reductive amination. For example, amphetamine, a central nervous system stimulant, is prepared commercially by reductive amination of phenyl-2-propanone with ammonia, using hydrogen gas over a nickel catalyst as the reducing agent. 

Kinetics. Extensive studies of the kinetics of methane synthesis were reported by White and co-workers (10,11, 12, 13, 14, 15). They studied the reaction between CO and hydrogen over a reduced nickel catalyst on kieselguhr at 1 atm and 300°-350°C (10). They correlated the rate of methane formation by the equation ... 

The synthesis of methane from C02 and hydrogen was studied by Binder and White (11) over a reduced nickel catalyst (Harshaw Ni-88). The surface reaction between the C02 and hydrogen appeared to be rate controlling. The rate of reaction can be correlated by either of the following rather awkward equations ... 

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. 

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