Catalyst, alumina Raney nickel

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 ... 

The alkylation of pyridine [110-86-1] takes place through nucleophiUc or homolytic substitution because the TT-electron-deficient pyridine nucleus does not allow electrophiUc substitution, eg, Friedel-Crafts alkylation. NucleophiUc substitution, which occurs with alkah or alkaline metal compounds, and free-radical processes are not attractive for commercial appHcations. Commercially, catalytic alkylation processes via homolytic substitution of pyridine rings are important. The catalysts effective for this reaction include boron phosphate, alumina, siHca—alurnina, and Raney nickel (122). 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

Table II shows that, at least for the reactions with quinoline and with 4-methylquinoline (lepidine), nickel-alumina and degassed Raney nickel catalysts are of similar efficiency but better yields have been obtained with degassed Raney nickel, and only this catalyst produces the biaryl from 7-methyIquinoIine.

Several products other than 2,2 -biaryls have been isolated following reaction of pyridines with metal catalysts. From the reaction of a-picoline with nickel-alumina, Willink and Wibaut isolated three dimethylbipyridines in addition to the 6,6 -dimethyl-2,2 -bipyridine but their structures have not been elucidated. From the reaction of quinaldine with palladium-on-carbon, Rapoport and his co-workers " obtained a by-product which they regarded as l,2-di(2-quinolyl)-ethane. From the reactions of pyridines and quinolines with degassed Raney nickel several different types of by-product have been identified. The structures and modes of formation of these compounds are of interest as they lead to a better insight into the processes occurring when pyridines interact with metal catalysts. 

Supported Co, Ni, Ru, Rh, Pd and Pt as well as Raney Ni and Co catalysts were used for the hydrogenation of dodecanenitrile to amines in stirred SS autoclaves both in cyclohexane and without a solvent. The reaction temperature and the hydrogen pressure were varied between 90-140 °C and 10-80 bar, respectively. Over Ni catalysts NH3 and/or a base modifier suppressed the formation of secondary amine. High selectivity (93-98 %) to primary amine was obtained on Raney nickel, Ni/Al203 and Ru/A1203 catalysts at complete nitrile conversion. With respect to the effect of metal supported on alumina the selectivity of dodecylamine decreased in the order Co Ni Ru>Rh>Pd>Pt. The difference between Group VIII metals in selectivity can be explained by the electronic properties of d-band of metals. High selectivity to primary amine was achieved on base modified Raney Ni even in the absence of NH3. 

Catalysts - A commercial Raney nickel (RNi-C) and a laboratory Raney nickel (RNi-L) were used in this study. RNi-C was supplied in an aqueous suspension (pH < 10.5, A1 < 7 wt %, particle size 0.012-0.128 mm). Prior to the activity test, RNi-C catalyst (2 g wet, 1.4 g dry, aqueous suspension) was washed three times with ethanol (20 ml) and twice with cyclohexane (CH) (20 mL) in order to remove water from the catalyst. RCN was then exchanged for the cyclohexane and the catalyst sample was introduced into the reactor as a suspension in the substrate. RNi-L catalyst was prepared from a 50 % Ni-50 % A1 alloy (0.045-0.1 mm in size) by treatment with NaOH which dissolved most of the Al. This catalyst was stored in passivated and dried form. Prior to the activity test, the catalyst (0.3 g) was treated in H2 at 250 °C for 2 h and then introduced to the reactor under CH. Raney cobalt (RCo), a commercial product, was treated likewise. Alumina supported Ru, Rh, Pd and Pt catalysts (powder) containing 5 wt. % of metal were purchased from Engelhard in reduced form. Prior to the activity test, catalyst (1.5 g) was treated in H2 at 250 °C for 2 h and then introduced to the reactor under solvent. 10 % Ni and 10 % Co/y-Al203 (200 m2/g) catalysts were prepared by incipient wetness impregnation using nitrate precursors. After drying the samples were calcined and reduced at 500 °C for 2 h and were then introduced to the reactor under CH. 

Catalyst, alumina, 34, 79 35, 73 ammonium acetate, 31, 25, 27 copper chromite, 31, 32 36, 12 cuprous oxide-silver oxide, 36, 36, 37 ferric nitrate, hydrated, 31, 53 piperidine, 31, 35 piperidine acetate, 31, 57 Raney nickel, 36, 21 sulfuric acid, 34, 26 Catechol, 33, 74 Cetylmalonic acid, 34, 16 Cetylmalonic ester, 34,13 Chlorination, by sulfuryl chloride, 33, 45 ... 

In fact, there are only two heterogeneous catalysts that reliably give high enantioselectivities (e.s. s) (90% e.e. or above). These are Raney nickel (or Ni/Si02) system modified with tartaric acid (TA) or alanine for hydrogenation of /(-kctocstcrs [12-30], and platinum-on-charcoal or platinum-on-alumina modified with cinchona alkaloids for the hydrogenation of a-ketoesters [31-73],... 

Selective catalytic hydrogenation with chromium-promoted Raney nickel is reported (e.g. citral and citronellal to citronellol) NaHCr2(CO)io and KHFe(CO)4 reduction of a/3-unsaturated ketones (e.g. citral to citronellal) has been described (cf. Vol. 7, p. 7). The full paper on selective carbonyl reductions on alumina (Vol. 7, p. 7) has been published." Dehydrogenation of monoterpenoid alcohols over liquid-metal catalysts gives aldehydes and ketones in useful yields. ... 

Palladium on charcoal (Pd/C) is commonly used in the catalytic hydrogenation of pyrimidines in acidic media to form 1,2,4,5-tetrahydro derivatives which are stabilized as amidinium salts (62JOC2170, 65JCS1406). Platinum effects hydrogenation of the 5,6-double bond of uracils, for example, in the addition of deuterium to produce [5,6-2H2]5,6-dihydrouracil. The use of rhodium-on-charcoal and Raney nickel also gives good results. The addition of hydrogen to the 5,6-bond of thymidine and other 5-substituted uridines is stereospecific with rhodium-on-alumina as catalyst. 

Bipyridine has been prepared by the action of ferric chloride,8,9 iodine,10 or a nickel-alumina catalyst10 on pyridine at temperatures ranging from 300° to 400°. It has also been obtained from the reaction of 2-bromopyridine and copper.11 The present procedure is a modification of a previously published, general method.3 The W7-J nickel catalyst was developed from the description of the W7 Raney nickel catalyst of Billica and Adkins.12... 

HYDROGENATION, CATALYSTS Nickel on alumina. Nickel-Graphite. Palladium-Poly(ethylenimine). Palladium catalysts. Raney nickel. Rhodium catalysts. 

By means of this reaction Caldwell and Jones (103) obtained citronell-amide in 50% yield when 20 g. of citronellaldoxime and 3 g. of Raney nickel were heated at 100-105° for 2 hours, and, after dilution with ether, the catalyst was removed by filtration through activated alumina. The oxime of tetrahydrocitral, when heated for 2 hours at 110-120° with Raney nickel, gave a 70 % yield of the amide of 2,6-dimethyloctanoic acid. 

CATALYSTS Chlorotrisftriphenylphos-phine)rhodium(I). (S)-a-(R)-2-Di-phenylphosphinoferrocenyl ethyldl-methylamine. Hydridotrisftriisopropyl-phosphine)rhodium(I). Iridium black. 2,3-0-Isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane. Lindlar catalyst. Nickel-Alumina. Palladium catalysts. Raney nickel. Rhodium oxide-Platinum oxide. 

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