150 11. CHEMISTRY OF FATTY ACIDS AND GLYCEROL 



organic acids such as oxalic, hydroxy-acids, glucose and protein. In the 

 case of a mixed nickel-copper catalyst, it was found that the sodium and 

 potassium soaps exerted a pronounced deleterious action, while magnesium, 

 barium, calcium, lead, iron, magnanese, zinc, and cadmium, when present 

 as their soaps, had only a limited poisonous effect. ^"'^ Copper and silver 

 soaps actually caused an augmentative action. Copper salts are added to 

 nickel catalysts to prevent poisoning; they act as promoters, and will allow 

 hydrogenation to proceed at a lower temperature than would otherwise be 

 possible.*"^ Additional compounds which are reported to have a promoting 

 effect on nickel catalysts are the salts of beryllium, manganese, uranium, 

 and tungsten, as well as the chromate, phosphate, molybdate and tung- 

 state radicals. ^"^ 



The wide variety of catalysts in use can be realized from the list of nickel 

 compounds which have been employed. These include catalysts prepared 

 by reduction of nickel oleate,^"^-^"^ nickel salts of naphthenic acids, ^"^ 

 nickel oxalate, ^"^ nickel formate,^"'^-^"^ mixed nickel and copper formates,^"^ 

 and nickel carbonyl."" An active catalyst has been prepared by heating a 

 mixture of nickel nitrate and sucrose.^^^ The most effective of all the hy- 

 drogenating catalysts is that first used by Raney,^^- which is prepared by 

 treating a nickel aluminum alloy with sodium hydroxide.®^^'^^^ Still other 

 active nickel catalysts are nickel silicate and nickel borate, which are not 

 readily poisoned.^^^~®^^ However, it is believed that the latter salt de- 

 composes into the metal and boric acid on heating.^ ^^ It has been stated 



^ S. Uf-no, Y. Miyake, and R. Anzai, /. Soc. Chem. Ind. Japan, 43, suppl., 434-435 

 (1940); Chem. AbsL, 35, 3113 (1941). 



SOI J. Dewar and A. Liebmann, U. S. Patent No. 1,275,405 (Aug. 13, 1918). 



602 Badische Anilin und Soda Fabrik, Brit. Patent No. 2,306 (Jan. 28, 1914); Chem. 

 Abst., 10,287-288(1916). 



«" C. H. Hausamann, Canadian Patent No. 157,396 (Aug. 18, 1914). 



«>« C. Ellis, U. S. Patent No. 1,217,118 (Feb. 20, 1917). 



«« Deutsche Hydrierwerke, A.-G., Brit. Patent No. 396,311 (Feb. 10, 1933). 



806 E. C. Kayser, U. S. Patent No. 1,236,446 (Aug. 14, 1917). 



«" E. B. Higgins, Brit. Patent Nos. 4,665 (Feb. 23, 1914) and 23,377 (Oct. 12, 1912); 

 Chem. Abst., 8, 789 (1914); 10, 974 (1916); U. S. Patent No. 1,170,814 (Feb. 8, 1916). 



808 F. Wittka, Sudss Patent No. 151,9.55 (Nov. 15, 1930); Chem. .Ihst., 26, 4828 (1932). 



«09 C. Ellis, U. S. Patent No. 1,645,377 (Oct. 11, 1927). 



s") A. A. Shukoff, German Patent No. 241,823 (.Jan. 18, 1910). 



611 W. P. Schuck, Brit. Patent Xo. 122,192 (Jan. 6, 1919): Canadian Patent No. 200,591 

 (June 1, 1920); U. S. Patent No. 1,305,173 (Mav 27, 1919). 



612 M. Raney, U. S. Patents Nos. 1,628,190 (May 10, 1927) and 1,915,473 (June 27, 

 1933). 



613 R. Paul and G. Hilly, Bull. soc. chim. [5], 3, 2330-2332 (1936). 

 61* R. Mozingo, Org. Syntheses, 21, 15-17 (1941). 



616 H. Schonfeld, Seifensieder-Ztg., 41, 945-946 (1914); Chem. Abst., 8, 3868 (1914). 

 6>« Miiller Speisefettfabrik, A.-G., Brit. Patent Nos. 7G70 and 7671 (Mar. 26, 1914). 

 6" C. Ellis, U. S. Patent No. 1,255,590 (Feb. 5, 1918). 

 618 W. Normann, Seifensieder-Ztg., 42, 40-47 (1915); Chem. Abst., 9, 1552 (1915). 



