US2334850A - Refining of fatty acid esters and fatty acids - Google Patents
Refining of fatty acid esters and fatty acids Download PDFInfo
- Publication number
- US2334850A US2334850A US389174A US38917441A US2334850A US 2334850 A US2334850 A US 2334850A US 389174 A US389174 A US 389174A US 38917441 A US38917441 A US 38917441A US 2334850 A US2334850 A US 2334850A
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- US
- United States
- Prior art keywords
- acid esters
- fatty acids
- fatty acid
- fatty
- refining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 235000014113 dietary fatty acids Nutrition 0.000 title description 82
- 239000000194 fatty acid Substances 0.000 title description 82
- 229930195729 fatty acid Natural products 0.000 title description 82
- 150000004665 fatty acids Chemical class 0.000 title description 44
- -1 fatty acid esters Chemical class 0.000 title description 41
- 238000007670 refining Methods 0.000 title description 22
- 239000002253 acid Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 239000003921 oil Substances 0.000 description 22
- 235000019198 oils Nutrition 0.000 description 22
- 230000008569 process Effects 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 7
- 241000273930 Brevoortia tyrannus Species 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000000944 linseed oil Substances 0.000 description 5
- 235000021388 linseed oil Nutrition 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241001446467 Mama Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
Definitions
- This invention relates to fatty acid esters and fatty acids and more particularly to a process for refining such materials.
- Fatty acid esters and fatty acids have been refined by many methods in order to improve their However, such processes generally suffer volving a substantial loss of refined product or of changing desirable properties of the fatty materials treated, or of requiring excessive processing equipment and materials, or of improving the color to only a slight degree.
- .It is a further object of this invention'to provide an improved process for refining fatty acid esters and fatty acids in which the yield of refinedfatty acid esters or fattyacids based on the material treated is substantially quantitative.
- a still further objectof this invention is to provide a process which will effect a substantial improvement in the color of the treated fatty acid esters or fatty acids without substantially tion the treatment may be carried out on the fatty acid esters or fatty acids in the molten condition or on these materials dissolved in a suitable, solvent.
- the fatty acid esters or fatty acids or their solution may be washed to remove any water soluble material, and filtered to remove any suspended matter. If desired, the solution may be filtered prior to the water washing step. In the case of treatment of the fatty acid esters or fatty acids in solution, the fatty acid esters or fatty acids of improved color may then be recovered by evaporation of the solution.
- the fatty acid esters and fatty acids which may be refined according to the process of this invention are the fatty acid esters such as vegetable and animal oils, fats and waxes, and the fatty acids which may be derived'from them.
- examples of such materials are vegetable oils such astung oil, linseed oil, cottonseed oil, palm oil, etc., or animal oils such as bone oil, whale oil, beef tallow, etc., fish oils, such as menhaden oil,
- sardine oil etc.
- waxes such as sperm oil, beeswax
- the objects of the invention are accomplished broadly by treating the unrefined fatty acid esters or fatty acids under ionizing conditions with a metal above hydrogen in the electromotive series and an acid salt.
- the treatment is carried out under conditions which will provide intimate contact between the fatty acid esters. or fatty acids and the acid salt and the metal.
- the color of the fatty acidesters or'fatty acids is substantially lightened. with practically' no loss in yield and no perceptible effect on the" properties of the materials treated other than color.
- the process of this invention is especially valuable when applied to the unsaturated or drying type fatty acid esters'and fatty acids such as, for example tung oil, linseed oil, menhaden oil, oleic acid, linseed oil fatty acids, etc.
- unsaturated or drying type fatty acid esters'and fatty acids such as, for example tung oil, linseed oil, menhaden oil, oleic acid, linseed oil fatty acids, etc.
- the advantage of the'process of this invention of having no perceptible effect on the physical properties of the acid esters and fatty acids other than color is especially marked since other processes'of refining generally appreciably alterthose properties in lightening the color.
- any solvent for these materials may be employed which is itself inert in the treatment.
- monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, -etc.
- petroleum hydrocarbons such as gasoline, V. M. and P. naphtha, hexane, heptane, etc.
- hydrogenated petroleum hydrocarbons such as gasoline, V. M. and P. naphtha, hexane, heptane, etc.
- Solvesso solvents such as those known in the trade as Solvesso solvents: turpentine, terpenes, and solvents such as ethylene dichloride, carbon tetrachloride, cyclohexane, methyl cyclohexane, P menthane, tetrahydro and decahydronaphthalenes, isopropyl ether ,dichloroethyl ether, etc. Where sorted to.
- the treatment is carried out on' the fatty acid esters or fatty acids in solution
- the concentration of the fatty acid esters or fatty acids in solution is not critical and may be selected to provide adequate workability of the solution. In general, a concentration within the range of about to 75% by weight may be used, but
- the.concentration is' held within the range-of 30% to 60% by weight.
- the acid salts which may be used in the process of this invention are those which contain one or more replaceable hydrogen atoms, such as, for example, sodium acid sulfate, potassium acid sulfate, monosodium acid phosphate, disodium acid phosphate, monopotassium acid phosphate,
- the time of treatment of the fatty acid esters or fatty acids may be varied to produce the result desired.
- the time necessary to provide satisfactory refining will depend on such factors as the amount of color bodies present in the material refined. the temperature of the treatment, the amount of acid salt employed, and other factors. possible to state any definite time necessaryexcept in relation to a given set of conditions.
- the metal and acid salt should be contacted during the refining process under ionizing conditions.
- ionizing conditions conditions under which the acid salt and metal may dissociate, as in the presence of an ionizing solvent such as water. It is, therefore, desirable that at least a small amount of water or of some other ionizing solvent be present in order that such ionizing conditions are realized.
- the acid salt may be used in the form of a hydrate if it forms one, or in the form of an aqueous solution. Sodium acid sulfate in the form of its monohydrate is particularly desirable. Alternatively a small amount of water or other ionizing solvent may be added. An aqueous solution containing from about 20% of the acid salt to a saturated solution of the salt at the temperature employed may be used.
- The'speed with which the fatty acid esters or fatty acids become refined is also dependent on the temperature employed in the treatment. While the treatment may be carried out at room temperature, the rate of refining is slow for practical purposes. It is preferable to carry out the treatment at elevated temperatureaand temperatures as high as 200 C. have been found to be satisfactory, although even higher temperatures are possible. A temperature within the range of about 70 C. to about 125 C. is preferable.
- the amount of acid salt used may vary over a wide range depending on factors such as the particular acid salt used, the degree of refining desired, the particular conditions of treatment, as well as other factors.
- ratios of fatty acid esters or fatty acids to acid salt of as high as 40 to 1 on a weight basis are prac-' tical. In general, however, ratios varying between 10 of fatty acid esters or fatty acid to 1 of acid salt, down to 1 of fatty acid ester or fatty acid to 1 or more of acid salt are desirable.
- a preferred ratio is approximately 3 of fatty acid esters or fatty acids to 1 of acid salt.
- the amount of metal above hydrogen in the electromotive series used is not particularly critical. It will be desirable, however, to have an amount of such metal present which will be an excess over the theoretical amount required to react with the acid salt present.
- the process of refining fatty acid esters or fatty acids in accordance with this invention may also be carried out as a continuous process if desired.
- a solution of the fatty material may be treated with the metal above hydrogen in the electromotive series and an acid salt ina suitable vessel while additional fatty acid esters or fatty acid solution is fed
- additional fatty acid esters or fatty acid solution is fed
- the examples below are cited as typical of the various embodiments.
- the colors shown are the colors corresponding to grades of the Standard U. S. rosin type.
- Example 1 Seventy-five parts by weight of a, commercial Red Oil or oleic acid was dissolved in 310 parts by weight of benzene. This solution was refluxed for 1 hour with 15 parts by weight of zinc powder and 23 grams of sodium acid sulfate monohydrate. The treated solution was filtered to remove suspended matter, water washed, and the solvent removed from the refined oil by vacuum distillation. The color of the oil was improved from an 1+ to a WG grade.
- Example 2 The experiment of Example 1 was duplicated with tun'g oil of color grade N+. The oil was refined to a W grade.
- Example 3 Sixty parts by weight of menhaden oil was dissolved in 180 parts by weight of benzene and refluxed for one hour with 25 parts by weight of zinc powder and 40 parts by weight of sodium acid sulfate monohydrate. The benzene solution was decanted, water washed and the solvent removed from the refined oil by vacuum distillation. The color of the oil was-improved from a G+ to an M grade.
- Example 4- Sixty parts by weight of menhaden oil was heated to 95 C'. with 20 parts by weight of zinc and 60 parts by weight of a 50% aqueous monosodium acid phosphate solution. The mixture was maintained at this temperature for 45 minutes under constant agitation. The oil was sep-' arated from the treating solutiornfiltered and water washed. The color of the oil was improved from a (3+ to a K grade.
- Example 5 Example 5 .25 g. zinc powder and 40 g. NaI-ISOdhO was What I claim and desire to protect by Letters Patent is:
- vacuo distfllation left a substantially quantitative yield of bleached wax which was substantiallylighter in color than the, original (from dark brown to light brown).
- Example 6 A refining treatment was carried out exactly 7 as in Example 5, except the wax refined was montan wax.
- the refined material was substantially lighter than the original (from black gray to gray). Because of the opacity of the original and bleached waxes, an accurate color could not be obtained.
- tuna oil which consists or treating said tun: oil under ionizing conand zinc at a temperature within the range of about 70 to about 125 C.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
Description
. color.
from one or more of such disadvantages as in-,
Patented Nov. 23, 1943 REFINING OF FATTY ACID ESTERS AND FATTY ACIDS William N. Traylor, Hattiesburg, Miss., assignor V to Hercules Powder Company, 'Wilmington, Del., a corporation of Delaware No Drawing. Application April 18, [1941, Serial'No. 389,174
8 Claims. (01. 260-424) This invention relates to fatty acid esters and fatty acids and more particularly to a process for refining such materials.
Fatty acid esters and fatty acids have been refined by many methods in order to improve their However, such processes generally suffer volving a substantial loss of refined product or of changing desirable properties of the fatty materials treated, or of requiring excessive processing equipment and materials, or of improving the color to only a slight degree. Such disadvantages are encountered for example when treating fatty acid esters and fatty acids by adsorption or extraction methods whereby a considerable loss, of yield of refined material is obtained, or by=treating with strong reagents such as concentrated sulfuric acid, thereby destroying considerable fatty materials, or by hydrogenation, oxidation or chlorination which may-involve not only change in properties, but loss in yield or use of expensive equipment.
It is an object of this invention to provide an improved process for refining fatty acid esters and fatty acids.
It is a further object of this invention to provide an improved process for refining fatty acid esters and fatty acids, which is extremely simple and economical.
.It is a further object of this invention'to provide an improved process for refining fatty acid esters and fatty acids in which the yield of refinedfatty acid esters or fattyacids based on the material treated is substantially quantitative.
A still further objectof this invention is to provide a process which will effect a substantial improvement in the color of the treated fatty acid esters or fatty acids without substantially tion the treatment may be carried out on the fatty acid esters or fatty acids in the molten condition or on these materials dissolved in a suitable, solvent. After the treatment is completed, I
the fatty acid esters or fatty acids or their solution may be washed to remove any water soluble material, and filtered to remove any suspended matter. If desired, the solution may be filtered prior to the water washing step. In the case of treatment of the fatty acid esters or fatty acids in solution, the fatty acid esters or fatty acids of improved color may then be recovered by evaporation of the solution.
The fatty acid esters and fatty acids which may be refined according to the process of this invention are the fatty acid esters such as vegetable and animal oils, fats and waxes, and the fatty acids which may be derived'from them. Examples of such materials are vegetable oils such astung oil, linseed oil, cottonseed oil, palm oil, etc., or animal oils such as bone oil, whale oil, beef tallow, etc., fish oils, such as menhaden oil,
sardine oil, etc.,' waxes such as sperm oil, beeswax,
affecting the other properties of these substances.
Other objects of this invention will appear hereinafter.
The objects of the invention are accomplished broadly by treating the unrefined fatty acid esters or fatty acids under ionizing conditions with a metal above hydrogen in the electromotive series and an acid salt. The treatment is carried out under conditions which will provide intimate contact between the fatty acid esters. or fatty acids and the acid salt and the metal. As a result, the color of thefatty acidesters or'fatty acids is substantially lightened. with practically' no loss in yield and no perceptible effect on the" properties of the materials treated other than color.
In accordance with the process of thisinven carnauba wax, montan wax, etc.; and fatty acidssuchas commercial oleic acid, fatty acid soap stocks, and fatty acids derived from any of the above fats, oils and waxes.
The process of this invention is especially valuable when applied to the unsaturated or drying type fatty acid esters'and fatty acids such as, for example tung oil, linseed oil, menhaden oil, oleic acid, linseed oil fatty acids, etc. In the case of treating of such drying type fatty acid esters and fatty acids, the advantage of the'process of this invention, of having no perceptible effect on the physical properties of the acid esters and fatty acids other than color is especially marked since other processes'of refining generally appreciably alterthose properties in lightening the color.
As-solvents for the fatty acid esters and fatty acids when the treatment is carried out on the fatty acid esters and fatty acids in solution, any solvent for these materials may be employed which is itself inert in the treatment. Among such solvents are, for example, monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, -etc.; petroleum hydrocarbons such as gasoline, V. M. and P. naphtha, hexane, heptane, etc.; hydrogenated petroleum hydrocarbons. such as those known in the trade as Solvesso solvents: turpentine, terpenes, and solvents such as ethylene dichloride, carbon tetrachloride, cyclohexane, methyl cyclohexane, P menthane, tetrahydro and decahydronaphthalenes, isopropyl ether ,dichloroethyl ether, etc. Where sorted to.
the treatment is carried out on' the fatty acid esters or fatty acids in solution, the concentration of the fatty acid esters or fatty acids in solution is not critical and may be selected to provide adequate workability of the solution. In general, a concentration within the range of about to 75% by weight may be used, but
preferably the.concentration is' held within the range-of 30% to 60% by weight.
The acid salts which may be used in the process of this invention are those which contain one or more replaceable hydrogen atoms, such as, for example, sodium acid sulfate, potassium acid sulfate, monosodium acid phosphate, disodium acid phosphate, monopotassium acid phosphate,
7 dipotassium acid phosphate, calcium acid phosway limiting on the process, and the equipment employed will generally determine the maximum pressure which is practical.
The time of treatment of the fatty acid esters or fatty acids may be varied to produce the result desired. The time necessary to provide satisfactory refining will depend on such factors as the amount of color bodies present in the material refined. the temperature of the treatment, the amount of acid salt employed, and other factors. possible to state any definite time necessaryexcept in relation to a given set of conditions.
' Under usual conditions reaction time between In order to produce the necessary refining action, the metal and acid salt should be contacted during the refining process under ionizing conditions. By ionizing conditions is meant conditions under which the acid salt and metal may dissociate, as in the presence of an ionizing solvent such as water. It is, therefore, desirable that at least a small amount of water or of some other ionizing solvent be present in order that such ionizing conditions are realized. Thus, the acid salt. may be used in the form of a hydrate if it forms one, or in the form of an aqueous solution. Sodium acid sulfate in the form of its monohydrate is particularly desirable. Alternatively a small amount of water or other ionizing solvent may be added. An aqueous solution containing from about 20% of the acid salt to a saturated solution of the salt at the temperature employed may be used.
-It will be understood that the acid salt and the metal above hydrogen in the electromotive series are both in contact with the fatty acid esters or fatty acids during the treatment. To provide satisfactory contact of the acid salt and metal with the fatty acid esters or fatty acids, itwill be desirable to employ vigorous agitation,
I since the refining action will be appreciably accelerated thereby.
'The'speed with which the fatty acid esters or fatty acids become refined is also dependent on the temperature employed in the treatment. While the treatment may be carried out at room temperature, the rate of refining is slow for practical purposes. It is preferable to carry out the treatment at elevated temperatureaand temperatures as high as 200 C. have been found to be satisfactory, although even higher temperatures are possible. A temperature within the range of about 70 C. to about 125 C. is preferable.
When carrying out the treatment of the fatty acid esters or fatty acids in solution it is convenient to operate at the reflux temperature of the solvent. When the treatment is to be carried out above the normal boiling point of the solvent, use of superatmospheric pressure is re- The pressures employed are in no about 10 minutes and 5 hours may be satisfactory, although depending on specific conditions, longer or shorter contact times are entirely possible.
' The amount of acid salt used may vary over a wide range depending on factors such as the particular acid salt used, the degree of refining desired, the particular conditions of treatment, as well as other factors. Considering the acid salt on an anhydrous basis, for example, ratios of fatty acid esters or fatty acids to acid salt of as high as 40 to 1 on a weight basis are prac-' tical. In general, however, ratios varying between 10 of fatty acid esters or fatty acid to 1 of acid salt, down to 1 of fatty acid ester or fatty acid to 1 or more of acid salt are desirable. A preferred ratio is approximately 3 of fatty acid esters or fatty acids to 1 of acid salt.
The amount of metal above hydrogen in the electromotive series used is not particularly critical. It will be desirable, however, to have an amount of such metal present which will be an excess over the theoretical amount required to react with the acid salt present.
The process of refining fatty acid esters or fatty acids in accordance with this invention may also be carried out as a continuous process if desired. Thus, for example, a solution of the fatty material may be treated with the metal above hydrogen in the electromotive series and an acid salt ina suitable vessel while additional fatty acid esters or fatty acid solution is fed As illustrative of the improved process of refining fatty acid esters or fatty acids in accordance with this invention, the examples below are cited as typical of the various embodiments. The colors shown are the colors corresponding to grades of the Standard U. S. rosin type.
Example 1 Seventy-five parts by weight of a, commercial Red Oil or oleic acid was dissolved in 310 parts by weight of benzene. This solution was refluxed for 1 hour with 15 parts by weight of zinc powder and 23 grams of sodium acid sulfate monohydrate. The treated solution was filtered to remove suspended matter, water washed, and the solvent removed from the refined oil by vacuum distillation. The color of the oil was improved from an 1+ to a WG grade.
For this reason it is im- The iodine number of the on was substantially unchanged.
Example 2 The experiment of Example 1 was duplicated with tun'g oil of color grade N+. The oil was refined to a W grade.
Example 3 Sixty parts by weight of menhaden oil was dissolved in 180 parts by weight of benzene and refluxed for one hour with 25 parts by weight of zinc powder and 40 parts by weight of sodium acid sulfate monohydrate. The benzene solution was decanted, water washed and the solvent removed from the refined oil by vacuum distillation. The color of the oil was-improved from a G+ to an M grade.
Example 4- Sixty parts by weight of menhaden oil was heated to 95 C'. with 20 parts by weight of zinc and 60 parts by weight of a 50% aqueous monosodium acid phosphate solution. The mixture was maintained at this temperature for 45 minutes under constant agitation. The oil was sep-' arated from the treating solutiornfiltered and water washed. The color of the oil was improved from a (3+ to a K grade.
Example 5 .25 g. zinc powder and 40 g. NaI-ISOdhO was What I claim and desire to protect by Letters Patent is:
l. The process of refining a material selected from the group consisting of fatty acid esters and fatty acids which consists of treating said material under ionizing conditions with a metal above hydrogen in the an acid salt.
2. The process of refining a material selected from the group conslsting'of drying type fatty acid esters and drying type fatty acids which consists of treating said material under ionizing conditions with a metal above hydrogen in the electromotive series and an acid salt.
3. The process of refining a material selected from the group consisting of fatty acid esters and fatty acids which consists of treating said material under ionizing conditions with a metal added to a solution of 100 g. carnauba wax in V 400 g. ethylene dichloride, and the mixture refluxed for -1 hour with agitation. The solution was decanted from the bleaching agent while hot,
vacuo distfllation left a substantially quantitative yield of bleached wax which was substantiallylighter in color than the, original (from dark brown to light brown).
Example 6 A refining treatment was carried out exactly 7 as in Example 5, except the wax refined was montan wax. The refined material was substantially lighter than the original (from black gray to gray). Because of the opacity of the original and bleached waxes, an accurate color could not be obtained.
It will also be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.
.and water washed. Evaporation of solvent by i ditions with sodium acid sulfate monohydrate .perature within the range of about to about 6. The process of refining linseed oil which consists of treating said linseed oil under ionizing conditions with-sodium acid sulfate mono hydrateancf zinc at a temperature within the range of about 70 to about 125 C.
7. The process of.refining tuna oil which consists or treating said tun: oil under ionizing conand zinc at a temperature within the range of about 70 to about 125 C.
8. The process of refining menhaden oil which consists of treating said menhaden oil under ionizing'conditions with sodium acid sulfate monohydrate and aim: at a temperature within the range of about 70 to about 125' 0.
w. N. mama.
electromotive series and
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US389174A US2334850A (en) | 1941-04-18 | 1941-04-18 | Refining of fatty acid esters and fatty acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US389174A US2334850A (en) | 1941-04-18 | 1941-04-18 | Refining of fatty acid esters and fatty acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2334850A true US2334850A (en) | 1943-11-23 |
Family
ID=23537152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US389174A Expired - Lifetime US2334850A (en) | 1941-04-18 | 1941-04-18 | Refining of fatty acid esters and fatty acids |
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| Country | Link |
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| US (1) | US2334850A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428901A (en) * | 1947-10-14 | Polymerization nucleus fob | ||
| US2431357A (en) * | 1947-11-25 | Polymerization nucleus for | ||
| US2477116A (en) * | 1944-07-18 | 1949-07-26 | John C Cowan | Protective coating compositions and methods for producing the same |
| US2894939A (en) * | 1957-09-23 | 1959-07-14 | Glidden Co | Process for upgrading polymerized fatty acid mixtures |
| US3864370A (en) * | 1971-08-06 | 1975-02-04 | Ajinomoto Kk | Method of refining crude synthetic fatty acids |
| US4174409A (en) * | 1977-08-05 | 1979-11-13 | Minnesota Mining And Manufacturing Company | Depositing latent fingerprints and development thereof |
| US4258644A (en) * | 1977-08-05 | 1981-03-31 | Minnesota Mining And Manufacturing Company | Depositing latent fingerprints and development thereof |
-
1941
- 1941-04-18 US US389174A patent/US2334850A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428901A (en) * | 1947-10-14 | Polymerization nucleus fob | ||
| US2431357A (en) * | 1947-11-25 | Polymerization nucleus for | ||
| US2477116A (en) * | 1944-07-18 | 1949-07-26 | John C Cowan | Protective coating compositions and methods for producing the same |
| US2894939A (en) * | 1957-09-23 | 1959-07-14 | Glidden Co | Process for upgrading polymerized fatty acid mixtures |
| US3864370A (en) * | 1971-08-06 | 1975-02-04 | Ajinomoto Kk | Method of refining crude synthetic fatty acids |
| US4174409A (en) * | 1977-08-05 | 1979-11-13 | Minnesota Mining And Manufacturing Company | Depositing latent fingerprints and development thereof |
| US4258644A (en) * | 1977-08-05 | 1981-03-31 | Minnesota Mining And Manufacturing Company | Depositing latent fingerprints and development thereof |
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