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United States Patent (19) 11) 4,282,163 Suzuki Et Al

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United States Patent (19) 11) 4,282,163 Suzuki Et Al United States Patent (19) 11) 4,282,163 Suzuki et al. 45) Aug. 4, 1981 (54) METHOD OF PRODUCING (56) References Cited HYDROGENATED FATTY ACIDS U.S. PATENT DOCUMENTS 1,247,516 11/1917 Ellis ...................................... 260/409 75 Inventors: Masao Suzuki, Nishinomiya; Takeshi 1927,850 9/1933 Schellmann et al. ................ 260/409 Matsuo; Naomichi Yamada, both of 2,862,943 12/1958 Wheeler ............................... 260/419 Amagasaki, all of Japan 3,197,418 7/1965 Maebashi ... 260/409 3,896,053 7/1975 Broecker et al. 260/409 4,163,750 8/1979 Bird et al. ............................ 260/409 73) Assignee: Nippon Oil and Fats Co., Ltd., Japan 4,179,454 12/1979 Mehta et al. ......................... 260/409 Primary Examiner-John F. Niebling (21) Appl. No.: 102,533 Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher 22 Filed: Dec. 11, 1979 57 ABSTRACT Hydrogenated fatty acid having excellent color and 30 Foreign Application Priority Data stability can be obtained by hydrogenating fatty acid, oil or fat, and distilling the crude hydrogenated fatty Dec. 19, 1978 JP Japan ................................ 53-157101 acid; or splitting the hydrogenated oil or fat into crude hydrogenated fatty acid and distilling the crude 51) Int. Cl.............................. .................. C11C3/12 hydrogenated fatty acid. 52) U.S. Cl. ..................................... 260/409; 260/419 58 Field of Search ................................ 260/409, 419 10 Claims, No Drawings 4,282,163 2 and acid oils formed as a by-product in the purification METHOD OF PRODUCING HYDROGENATED of these oils and fats. FATTY ACDS The fatty acid to be applied to the present invention includes fatty acids obtained from the above described BACKGROUND OF THE INVENTION 5 oils and fats, and further includes oleic acid, linoleic (1) Field of the Invention acid, linolenic acid, lauric acid, palmitic acid, stearic The present invention relates to a method of produc acid, etc., which are obtained by the solvent or hydro ing hydrogenated fatty acids having excellent color and philization separation or by the fractional distillation of stability, the above described fatty acids obtained from oils and 10 fats. Further, synthetic fatty acids obtained by paraffin (2) Description of the Prior Art oxidation process, oxo process, oxidative cleavage pro Hydrogenated fatty acid can be obtained by splitting cess, skeletal isomerization process and th like can be oil or fat into fatty acid and hydrogenating the fatty applied to the present invention. acid; or hydrogenating oil or fat into hardened oil or fat As the hydrogenation catalyst, there can be used and splitting the hardened oil or fat. It is commonly 15 catalysts commonly used in the hydrogenation of or known that when fatty acid, oil or fat is hydrogenated, ganic compound. These catalysts include metals, such the hydrogenated fatty acid, oil or fat is less in the col as iron, cobalt, nickel, ruthenium, rhodium, palladium, oration and in the smell than the original fatty acid, oil osmium, iridium, platinum, chromium, molybdenum, or fat. However, the hydrogenated fatty acid, oil and fat tungsten, copper, rhenium, vanadium and the like; and are easily colored or oxidized when they are heated or 20 their alloys, oxides, hydroxides, sulfides and the like; used in a chemical reaction, and even when the hydro and are, for example, palladium black, palladium on genated fatty acid is distilled, the distilled hydrogenated carbon, platinum oxide, nickel on kieselguhr, Raney fatty acid is still insufficient in the stability. nickel, Raney iron, Raney copper, copper chromite, The inventors have made various investigations in molybdenum sulfide and the like. order to obtain hydrogenated fatty acid having excel 25 As the reducing metal, there are used magnesium, lent color and stability in the heating and chemical calcium, aluminum, zinc, tin and the like, and their reaction, and found out that the above described object alloys having no catalytic activity for hydrogenation. can be attained by hydrogenating fatty acid, oil or fat in As the boric acid compound, there are used orthobo the presence of a hydrogenation catalyst and a reducing ric acid, metaboric acid, tetraboric acid, boron oxide, metal, and distilling the crude hydrogenated fatty acid; 30 and esters and salts of the above described boric acids. or splitting the hydrogenated oil or fat into a crude As the phenolic compound to be used in the present hydrogenated fatty acid, and distilling the crude hydro invention, heavy phenolic compounds having a high genated fatty acid. thermal resistance and further having a boiling point The inventors have made further investigations and higher than that of hydrogenated fatty acid are prefera found out that, when the above described hydrogena 35 ble. The heavy phenolic compounds include, for exam tion is carried out in the presence of a hydrogenation ple, tetrakismethylene-(3,5-di-t-butyl-4-hydroxyhy catalyst, a reducing metal and at least one of boric acid drocinnamate)methane, (3,5-di-t-butyl-4-hydroxyhy compound and heavy phenolic compound, the hydro drocinnamate)methane, 4,4'-butylidenebis(3-methyl-6- genated fatty acid has lighter color and improved stabil t-butylphenol), octadecyl 3,5-di-t-butyl-4-hydroxyhy ity. drocinnamate, 4,4'-methylenebis(2,6-di-t-butylphenol), 2,6-bis(1-methylheptadecyl)-4-methylphenol, 1,3,5- SUMMARY OF THE INVENTION trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)ben Zene, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)bu One of the features of the present invention is to tane, 4,4'-cyclohexylidenebis(2-cyclohexylphenol), 2-t- provide a method of producing hydrogenated fatty 45 butyl-a-(3-t-butyl-4-hydroxyphenyl)-p-cumenylbis(p- acids, comprising hydrogenating a fatty acid, oil or fat nonylphenyl)phosphite, 2,2'-methylenebis6-(1-methyl in the presence of a hydrogenation catalyst and a reduc cyclohexyl)-p-cresol), 1,6-hexane diol-bis-3-(3,5-di-t- ing metal, and distilling the crude hydrogenated fatty butyl-4-hydroxyphenyl)propionate, 2,4-bis(n-octylthi acid, or splitting the hydrogenated oil or fat into a crude o)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, hydrogenated fatty acid, and distilling the crude hydro SO 2,2'-thiodiethylbis3-(3,5-di-t-butyl-4-hydroxyphenyl)- genated fatty acid. propionate), O,O-di-n-octadecyl 3,5-di-t-butyl-4- Another feature of the present invention is to provide hydroxybenzylphosphonate, N,N'-hexame a method of producing hydrogenated fatty acids, com thylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide) prising hydrogenating a fatty acid, oil or fat in the pres and the like. These heavy phenolic compounds are ones ence of a hydrogenation catalyst, a reducing metal and 55 generally used as an oxidation inhibitor. at least one of boric acid compound and heavy phenolic The use amount of the hydrogenation catalyst is not compound, and distilling the crude hydrogenated fatty particularly limited, but the hydrogenation catalyst is acid, or splitting the hydrogenated oil or fat into a crude preferably used in an amount of 0.01-5% by weight hydrogenated fatty acid, and distilling the crude hydro based on the amount of raw fatty acid, oil and fat. genated fatty acid. 60 The use amount of the reducing metal and boric acid DESCRIPTION OF THE PREFERRED compound also is not particularly limited due to the EMBODIMENT reason that the optimum amount varies depending upon the kind and quality of raw fatty acid, oil and fat. How The oils and fats to be applied to the present inven ever, each of the reducing metal and boric acid com tion include animal and vegetable oils and fats and fish 65 pound is preferably used in an amount of 0.01-2% by oils, Such as beef tallow, lard, mutton tallow, soybean weight based on the amount of raw fatty acid, oil and oil, rice bran oil, palm oil, tall oil, rapeseed oil, cotton fat. When the amount is less than 0.01%, the effect of Seed oil, coconut oil, whale oil, sardine oil and the like, the reducing metal and boric acid compound is poor, 4,282,163 3 4. while even when the amount exceeds 2% by weight, the hydrogenated fatty acid, and the crude hydrogenated effect does not so improve, and the distillation residue fatty acid is subjected to distillation. The splitting of rather increases. Particularly, when more than 2% by hydrogenated oil or fat into crude hydrogenated fatty weight of boric acid compound is used, the hydrogena acid can be carried out by any of thermal pressure split tion catalyst is poisoned. ting process or saponification process. The heavy phenolic compound is preferably used in The hydrogenation catalyst and reducing metal used an amount of 0.001-1.0% by weight based on the in the hydrogenation are removed by filtration or re amount of raw fatty acid, oil and fat. When the amount moved in the form of distillation residue. The boric acid of the heavy phenolic compound is less than 0.001% by compound and heavy phenolic compound used in the weight, the effect of the heavy phenolic compound is O hydrogenation are removed in the form of distillation poor, while even when the amount exceeds 1.0% by residue together with impurities formed into high boil weight, the effect does not so improve. The heavy phe ing point substances. Accordingly, a hydrogenated fatty nolic compound does not poison at all the hydrogena acid having excellent color and stability can be obtained tion catalyst in the use of 0.001-1.0% by weight. by hydrogenating a fatty acid, oil or fat in the presence The hydrogenation catalyst hydrogenates the double 5 of a hydrogenation catalyst and a reducing metal, and bond in the raw fatty acid, oil and fat, and further hy occasionally at least one of boric acid compound and drogenates colored or coloring impurities, such as car heavy phenolic compound, and distilling the crude bonyl compound, hydroxyl compound, epoxy com hydrogenated fatty acid; or splitting the hydrogenated pound, phenolic compound and the like, contained in oil or fat into a crude hydrogenated fatty acid, and the raw fatty acid, oil and fat.
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