Patent GB-591511-A (GB)
Title: Improvements in or relating to the production of antioxidants from vegetable meals
IPC: C11B5/00
Filed: 1945-04-05
Abstract: An antioxidant for fatty materials is extracted from a vegetable meal previously freed from its oil content, by treating the meal with a solvent in presence of ammonia, or with ammonia followed by solvent extraction.  Preferably, concentrated ammonia is used but gaseous and liquid ammonia and solutions of ammonia in solvents other than water are applicable.  The solvent may be almost any organic solvent for fatty or oily materials, specified solvents being hexane, heptane, octane, ethylene dichloride trichlorethylene, carbon tetrachloride, cyclohexane, methylcyclohexane, benzene, acetone and diacetone alcohol and advantageously a polar solvent such as any of the lower alcohols, e.g., methanol, ethanol or isopropanol may be used concurrently. Specified vegetable meals are cottonseed, soybean, sesame, corn, oat, corn germ, wheat germ, alfalforleaf, peanut, rice, bran, rye and barley meals.  The resultant antioxidant concentrate is applicable in stabilizing vitamin A-or D-containing materials such as cod, shark, swordfish, ling, cod or halibut liver oils and products obtained by high vacuum distillation of fish liver oils and menhaden or sardine oil; fatty vegetable or animal materials such as cottonseed, soybean, peanut, sesame and their edible products and lard are similarly stabilised.  Advantageously the antioxidant is added in proportions varying between 0.1 and 5 per cent. and it can be used together with other antioxidants such as tocopherols, hydroquinone or lecithin.  In examples: (1) a carbon-refined shark liver oil is stabilized by adding 2 per cent. of an antioxidant concentrate obtained by treating ether extracted wheat germ flour with methanolic acetone and concentrated ammonium hydroxide; (2) a carbon-refined shark liver oil is stabilized by adding 0.5 per cent. by weight of an acetone-soluble fraction obtained by treating oil-free soybean meal with a 50-50 acetone-methanol mixture containing glacial acetic acid; (3) the process of (2) is applied to oil-free linseed meal; (4) and (5) the oil of (1) is stabilized by adding an acetone-fraction obtained in the processes of (2) and (3) modified by neutralizing with concentrated ammonium hydroxide the respective acetone-methanol-acetic acid extracts before evaporation and subsequent fractionation; (6) and (7) the oil of (1) is stabilized by adding an acetone-fraction in acetone of an antioxidant obtained from soybean meal and linseed meal respectively.ALSO:An antioxidant is extracted from a vegetable meal by treating the meal with a solvent in presence of ammonia or with ammonia followed by solvent extraction.  Preferably, concentrated aqueous ammonia is used, but gaseous and liquid ammonia, and solutions of ammonia in solvents other than water are applicable, and in general, the amount of ammonia can be varied between 1 per cent and 20 per cent on the weight of meal.  The solvent may be almost any organic solvent for fatty or oily materials, specified solvents being hexane, heptane, octane, ethylene, dichloride, trichlorethylene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, acetone and diacetone alcohol and advantageously a polar solvent such as any of the lower alcohols, e.g. methanol, ethanol or isopropanol may be used concurrently. Specified vegetable meals are cottonseed, soybean, sesame, corn, oat, corn germ, wheat germ, alfalfa leaf, peanut, rice, bran, rye and barley meals, which are usually prepared either by cold pressing or by expelling oil from the vegetable and thereafter grinding.  The solvent is used in quantity equal to or in excess of the quantity of meal, i.e. up to five times the weight of meal. The resultant anti-oxidant concentrate is applicable in stabilizing vitamin A or D-containing materials, such as fish liver oils, or vegetable oils and edible or cosmetic products prepared therefrom; fatty animal products such as butter or lard, and rubber or petrol. The proportion of anti-oxidant added may vary between approximately 0.1 and 5 per cent, and it can be used together with other antioxidants such as tocophenols, hydroquinous or lecithin.  In examples: (1) wheat germ flour, previously ether-extracted, is refluxed with a mixture of methanol, acetone and concentrated ammonium hydroxide, and the filtrate and methanol washings evaporated in vacuo to dryness to obtain an antioxidant concentrate; (2) expeller soybean meal, substantially oil-free, is refluxed with acetone, methanol and glacial acetic acid, and the concentrate obtained by evaporating under nitrogen is fractionated by treating with acetone; (3) the procedure of (2) is applied to oil-free linseed meal; (4) and (5) the processes of (2) and (3) are modified by neutralizing with concentrated ammonium hydroxide the respective acetone-methanol-acetic acid extracts before evaporation and subsequent acetone-fractionation; (6) the process of (2) is applied, replacing the acetic acid by ammonium hydroxide; (7) the process of (6) is applied, replacing soybean meal by linseed meal.ALSO:Butter is preserved by means of an antioxidant concentrate made from a vegetable meal, exemplified by cotton-seed, soya bean, sesame, maize, oat, maize germ, wheat germ, alfalfa leaf, peanut, rice bran, rye, and barley meals, which has preferably been rendered substantially oil-free, by extraction, in the presence of ammonia with a solvent exemplified by hexane, heptane, octane, ethylene dichloride, trichlorethylene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, acetone and diacetone alcohol, together with, advantageously, a polar solvent, e.g. methanol, ethanol is isopropanol.ALSO:An antioxidant utilised for stabilising rubber is extracted from a vegetable meal by treatment with a solvent in presence of ammonia, or with ammonia followed by solvent extraction. Preferably concentrated aqueous ammonia is used, but gaseous and liquid ammonia, and solutions of ammonia in solvents other than water are applicable, and in general the amount of ammonia can be varied between 1 per cent. and 20 per cent. on the weight of meal. The solvent may be almost any organic solvent for fatty or oily materials, specified solvents being hexane, heptane, octane, ethylenedichloride, trichlorethylene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, acetone and diacetone alcohol, and advantageously a polar solvent such as any of the lower alcohols, e.g., methanol, ethanol or isopropanol may be used concurrently.  Specified vegetable meals are cottonseed, soybean, sesame, corn, oat, corn germ, wheat germ, alfalfa leaf, peanut, rice, bran, rye and barley meals.  The solvent is used in quantity equal to or in excess of the quantity of meal, i.e., up to five times the weight of meal.  The proportion of antioxidant added may vary between approximately 0.1 and 5 per cent., and it can be used together with other antioxidants such as tocopherols, hydroquinone or lecithin.  In examples: (1) wheat germ flour, previously ether-extracted, is refluxed with a mixture of methanol, acetone and concentrated ammonium hydroxide, and the filtrate and methanol washings are evaported in vacuo to dryness to obtain an antioxidant concentrate; (2) expeller soybean meal, substantially oil-free is refluxed with acetone methanol and glacial acetic acid, and the concentrate obtained by evaporating under nitrogen is fractionated by treating with acetone: (3) the process of (2) is applied to oil-free linseed meal; (4) and (5) the processes of (2) and (3) are modified by neutralizing with concentrated ammonium hydroxide the respective acetone-methanol-acetic acid extracts before evaporation and subsequent acetone-fractionation; (6) the process of (2) is applied, replacing acetic acid by ammonium hydroxide: (7) the process of (6) is applied, replacing soybean meal by linseed meal.ALSO:An antioxidant concentrate is extracted from a vegetable meal previously freed from its oil content by treatment with a solvent in presence of ammonia or with ammonia, followed by solvent extraction.  Preferably, concentrated aueous ammonia is used, but gaseous and liquid ammonia, and solutions of ammonia in solvents other than water, are applicable, and, in general, the amount of ammonia can be varied between 1 per cent. and 20 per cent. on the weight of meal.  The solvent may be almost any organic solvent for fatty or oily materials, specified solvents being hexane, heptane, octane, ethylenedichloride, trichlorethylene, carbon tetrachloride, cyclohexane, methyl cyclohexane, benzene, acetone and diacetone, alcohol, and advantageously a polar solvent such as any of the lower alcohols, e.g., methanol, ethanol or isopropanol may be used concurrently.  Specified vegetable meals are cottonseed, soybean, sesame, corn, oat, corn germ, wheat germ, alfalfa leaf, peanut rice, bran, rye and barley meals.  The solvent is used in quantity equal to or in excess of the quantity of meal, i.e., up to five times the weight of meal.  The resultant antioxidant concentrate is applicable in stabilising vitamin A or D-containing materials such as fish liver oils, or vegetable oils and edible products prepared therefrom and fatty animal products such as lard.  Cottonseed, soybean, peanut and sesame oils are specified.  The proportion of antioxidant added may vary between approximately 0.1 and 5 per cent., and it can be used together with other antioxidants such as tocopherols, hydroquinone or lecithin.  In examples: (1) wheat germ flour, previously ether-extracted, is refluxed with a mixture of methanol, acetone and concentrated ammonium hydroxide, and the filtrate and methanol washings are evaporated in vacuo to dryness to obtain an antioxidant concentrate; (2) expeller soybean meal, substantially oil-free, is refluxed with acetone, methanol and glacial acetic acid, and the concentrate obtained by evaporating under nitrogen is fractionated by treating with acetone; (