Raney nickel deactivation

Raney nickel deactivated with piperidine and zinc acetate has been used for semihydrogenation of acetylenic compounds. 

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 ... 

Reduction of oximes to ketones. Ketoximes can be converted to ketones by hydrogenation catalyzed by Raney nickel (deactivated with acetone) in THF/CH,OH/H,0 or in CHiOH/H,0 containing boric acid to facilitate hydrolysis of the intermediate imine... 

Two serious drawbacks of this method are the extensive deuterium scrambling around the reaction site and the occasional formation of olefinic side products, which are hard to separate by conventional means. The extent of olefin formation may depend on the nature of the Raney nickel since it is known that desulfurization with deactivated Raney nickel can yield olefins. Best results are obtained when the deuterated Raney nickel is prepared very rapidly and used immediately after preparation. 

The conventional desulfurization of thioketais by Raney nickel does not give olefins (for reviews see ref. 333, 334). However, aged or acetone-deactivated nickel used in ethanol gives considerable amounts of olefins. ... 

Four pilot plant experiments were conducted at 300 psig and up to 475°C maximum temperature in a 3.07-in. i.d. adiabatic hot gas recycle methanation reactor. Two catalysts were used parallel plates coated with Raney nickel and precipitated nickel pellets. Pressure drop across the parallel plates was about 1/15 that across the bed of pellets. Fresh feed gas containing 75% H2 and 24% CO was fed at up to 3000/hr space velocity. CO concentrations in the product gas ranged from less than 0.1% to 4%. Best performance was achieved with the Raney-nickel-coated plates which yielded 32 mscf CHh/lb Raney nickel during 2307 hrs of operation. Carbon and iron deposition and nickel carbide formation were suspected causes of catalyst deactivation. 

Flame-Sprayed Raney Nickel Plates vs. Pellets of Precipitated Catalyst in a Packed Bed. Experiments HGR-13 and HGR-14 demonstrated that the performance of the plates sprayed with Raney nickel catalyst was significantly better than that of the precipitated nickel catalyst pellets. The sprayed plates yielded higher production of methane per pound of catalyst, longer catalyst life or lower rate of deactivation, lower CO concentration in the product gas, and lower pressure drop across the catalyst bed. 

The initial reactivities of the catalyst beds in experiments HGR-13 and HGR-14 are considered satisfactorily high however, the overall rate of deactivation of the Raney nickel catalyst bed (0.029% /mscf/lb) was... 

Nickel carbide, detected on the catalyst in experiment HGR-14, is another compound suspected of deactivating Raney nickel catalyst. However, the shutdown involved purging with hydrogen while the catalyst... 

The metal surface area at the inlet end of the catalyst bed in experiment HGR-12 was smaller than that at the outlet end this indicates that a decrease in nickel metal sites is part of the deactivation process. Sintering of the nickel is one possible mechanism, but carbon and carbide formation are suspected major causes. Loss of active Raney nickel sites could also conceivably result from diffusion of residual free aluminum from unleached catalyst and subsequent alloying with the free nickel to form an inactive material. 

During water storage slow oxidation takes place. In particular the most active Raney catalysts show. severe deactivation (they should not be stored more than a few weeks). Other types of catalysts though less active are much more stable. In fine chemistry activity is often not the most important catalytic property. This certainly holds for Raney nickel. On a nickel... 

For desulfurization of compounds containing reducible functions the Raney nickel (20 g) is deactivated prior to the desulfurization by stirring and refluxing with 60 ml of acetone for 2 hours. This removes the hydrogen which is adsorbed in Raney nickel. 

Ring closure to an episulfide is a feasible reaction for thiocarbonyl ylides. In most cases, the sulfur is further extruded under the reaction conditions to afford an olefin as the final product. This cascade transformation has been utilized by Danishefsky and co-workers in their total synthesis of ( )-indolizomycin (Scheme 16)." In the Danishefsky s approach, diazo ketone 137 is treated with a catalytic amount of Rh2(OAc)4 to generate thiocarbonyl ylide 138, which cyclizes to give episulfide 139. This episulfide isomerizes to mercaptan 140, which is then desulfurized by partially deactivated W-2 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 ... 

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