US2510379A - Preparation of break-free glyceride oils - Google Patents
Preparation of break-free glyceride oils Download PDFInfo
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- US2510379A US2510379A US47130A US4713048A US2510379A US 2510379 A US2510379 A US 2510379A US 47130 A US47130 A US 47130A US 4713048 A US4713048 A US 4713048A US 2510379 A US2510379 A US 2510379A
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- oil
- break
- alkali
- acid
- constituents
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- Expired - Lifetime
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- 239000003921 oil Substances 0.000 title description 96
- 125000005456 glyceride group Chemical group 0.000 title description 12
- 239000002253 acid Substances 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000470 constituent Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 description 93
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 238000004061 bleaching Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 235000021588 free fatty acids Nutrition 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 239000000944 linseed oil Substances 0.000 description 4
- 235000021388 linseed oil Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000005687 corn oil Nutrition 0.000 description 3
- 235000012343 cottonseed oil Nutrition 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 210000002683 foot Anatomy 0.000 description 3
- 229910000286 fullers earth Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000000787 lecithin Substances 0.000 description 3
- 229940067606 lecithin Drugs 0.000 description 3
- 235000010445 lecithin Nutrition 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 101150091111 ACAN gene Proteins 0.000 description 1
- 244000182067 Fraxinus ornus Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001620634 Roger Species 0.000 description 1
- -1 acetic Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
Classifications
-
- 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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
Definitions
- the present'inveition relates vto therlning of crudezor but partially rened glyceri'de ko'ils Such as soybeanboil, lin'seed oil, cottonsee'fd oil, corn oil or the'l'ike and it has particular relation to the refining ofsuch'oils for purposes of removing the break constituents thererom.
- One object of the invention is to provide a process of treating 'glyceride'oils of the foregoing types gior purposes of .removing or transforming break. constituents-which. process ⁇ is..accompanied '-1 by ybut.. s1ight losses. of the. constituents desirable in the oil.
- 1A 4fourth :oloioot .of fhoinvonion .I is to 1 provido a. process- .of .treating .orrido oil oon-taining .break oonstituoots lsu/ch lecithin ,or .Similar .phosohatdos and .oolorinemattor ⁇ to:providelvvfho,.1.1t substantial loss of glycerides, .aiproduct which .can thonroasilvbo bleached :forpurlooses offromoving or otherwiseeliminating the color constituents i therefrom.
- Glyceride oils such assoybean oil,.1inseedoil, cottonseed; oil, corn ⁇ oil and the like as obtained by conventional methods of removal. from the seeds .constituting the source thereofVinclude various4 constituentsf-such as.. .gums or breakt constituents Whichflhave ia tendency .-toseparate fout andrsform .a .iT-lock, .especially .Whensthe ⁇ aoil heated. Y'The Aoil ⁇ also usually.
- V vIt comprises adding Aa few frirops 'of aqueoushydrochloric acifd and heating the ⁇ 'il1to ⁇ 550WF. "Formation of a precipitatefis a positivr'eV test. The precipitatemaybeltered o, :washed free 4ofoil with carbon tetrachloride and ⁇ weighed to ldeterrnine ipercent of Gardner break. Tnemetnqd isignownas A. 0.o.-
- V'The'preseritiirnention is basedupon thel "discoverythat Whenjglyceride' foils 'aratreatednrith an alkalsuh'as'odiurn hydroxide'sodium carbonate, sodium bicarbonate or ⁇ the corresponding potassium coinp'oundsijgin lorderrpartially" to ⁇ decornjpose ⁇ such l*break forming constituents as lecithin "or "other phosphatide'sf/ occurring- “in “the natural4 or crude oil,”theyormmproducts ⁇ Whicl'l ean”"the'n be successfully neutralized with an 'ajc'id j'such as "sulfuric jac'id, hydrochloric acid, phosphoric 'acidpr organic acids suchas ⁇ acetic a'crd,-rnaleic acidor the-dike 4tolprovide ai'break lfr'eeoil.
- the salts if filtered out, may further be washed with a solvent such as naphtha designed to extract out the glycerides which may be absorbed in or cling to the salts.
- a solvent such as naphtha designed to extract out the glycerides which may be absorbed in or cling to the salts.
- an oil containing gum or break constituents such as a whole soybean oil, corn oil, linseed oil or cottonseed oil, or a raffinate oil obtained by furfural extraction of a glyceride oil as described in U. S. Patent 2,200,391, is treated with alkaline material preferably in the form of a water solution.
- the amount should be comparatively low, and may, for example, be within a range of from .01 to 1.00% solid alkali added as a solution per pound of oil.
- the mixture of oil and alkali solution preferably, are agitated together for sufficient time to permit adequate reaction of the constituents therein.
- This reaction may be promoted by heating the mixture moderately during the ag1tation, for example, to a temperature of 50 to 100 .0. Agitation may be continued as long as desired but, of course, there is no point in continuing it excessively long, since such operation merely ties up the apparatus, occupies the time of the operator and is power consuming. Usually, a period of twenty minutes to one hour is sufficient.
- acids should be added to neutralize the alkali.
- phosphoric acid, sulfuric acid, hydrochloric acid or organic acids such as acetic, maleic or fumaric or other acid capable of decomposing fatty acid soaps may be employed.
- the amount should be sumcient, or slightly in excess of the amount required approximately to neutralize any free alkali and to decompose the alkali salts in the solution.
- the correct amount can easily be calculated from the amount of alkali added or, if preferred, by titration of samples of the oil from time to time as acid is added.
- removal of the alkali salt can be effected either by drying the oil and thus precipitating the salts so that they can be ltered out, or by washing the oil with water in order to extract out the salts.
- the oil should be dried after acidification or after washing with water, for example, by bubbling inert gas such as carbon dioxide or nitrogen therethrough at an appropriate temperature, e. g. 100 to 200 C. Lower temperatures can be employed but the removal of the water is then slower. Also vacuum could be applied to hasten the drying operation at a moderate temperature.
- the oil product as obtained is only slightly higher in acid value than the original oil. Doubtless, it contains nearly all of the fatty acids and glycerides with which it started so that rening losses are no more than a few tenths of a percent, yet it is perfectly satisfactory for most uses to which the oils are conventionally applied, e. g. as modifiers of, or raw materials for alkyd resins for use in 2,510,379 f -Y A coating compositions. 1n the latter, it does not poison the catalyst.
- the oil may also be subjected to further treatment as, vfor example, solvent fractionation as above described.
- the coloring of the oil will be about the same as that of the original oil. If lighter products are desired, the break free product as obtained by the application of the foregoing technique, is excellently adapted for simple bleaching operations.
- the treated oil can be admixed with l to 5% of fullers earth or acid activated bleaching clay, e. g. acid treated bentonite, or with activated charcoal such as bone char or other bleaching ⁇ agents and the decolorizing agents filtered out to obtain oil of very light color.
- the bleaching agent of course, will carry out a certain amount of oil absorbed or adherent thereto. This oil can easily be recovered by extraction with naphtha and, evaporation of the naphtha therefrom.
- the oil recovered from the bleaching agent in this manner is notl of excessively dark color and can be added to the next batch or the parent batch if desired.
- Example 1 One hundred parts of partially degummed soybean oil (-24% free fatty acids, 10.5 Gardner color, 133.5 I. V.) was treated with 1.7 parts of 8% sodium hydroxide solution at 25 C. for 30 minutes and at 65 C. for 30 minutes. Enough phosphoric acid (0.136 part) was added to neutralize the alkali used and the mixture heated to 110 C. and dried by bubbling inert gas. Two parts of an acid activated bleaching earth was added and agitation continued for 30 minutes. The filtered oil had a free fatty acid content of 0.36, a negative Gardner break test, and a Gardner color of 4.
- the oil readily underwent an alcoholysis with glycerol with litharge as a catalyst, indicating that the break had been transformed to an innocuous form.
- the oil loss including that on the spent clay was 1.50%, but if the oil on the clay were recovered with naphtha. the loss was only 0.177%.
- Example 2 One hundred parts of crude linseed oil (0.88% free fatty acids, l1 Gardner color, 177.0 I. V.) and giving a positive break test, was stirred with 5.9 parts of 8% alkali for 30 minutes, then heated to 65 C. A 15% solution of sulfuric acid, 5.46 parts, was added and the mixture stirred and heated to 110 C. Four parts of bleaching earth was added and the temperature allowed to fall to C. ⁇ where it was held until 30 minutes from the addition of earth had elapsed. The oil was then ltered to yield a product having a fatty acid content of 1.90%, a negative Gardner break test, and a Gardner color 'of 4. The loss after the spent earth had been freed of oil by a naphtha wash was 0.31%.
- the oil recovered from the spent cake with naphtha contained no break and was not excessively dark and could be Iadded to the next batch or the main body of oil if desired.
- the product underwent ⁇ an alcoholysis with glycerol in the presence of litharge with no poisoning effects.
- Example 4 One hundred parts of crude soybean oil (0.63% Ifree'fa-ttyacids, l13rGardner-color, 131.9 iodine va-lue) 'andz giving'a positive break that was treated with 8.4 parts of 8% alkali solution at 65 1C.for 30 minutes and then acidied with 10.32 parts of 15% sulfuric acid. The temperature was raised to 110 C. and held there until .the mixture was dry. The oil was allowed to cool and the inorganic salts filtered. The loss of material remaining on the cake was 1.51% of the oil after entrained oil was removed as a naphtha wash. As bleaching earth was not used, the color gof -oil was only .sl1ghtly improved, -but it was( break-free and underwent an alcoholysis readily. The final. free fattyvacid content was 3.20%.
- Example One hundred parts of solvent extracted partially degummed soybean oil (0.30% free fatty acids, 10 Gardner color, 136.8 I. V. and a positive Gardner break test) was treated with 1.8 parts of 8% alkali for 30 minutes at room temperature. The temperature was raised to 65 C. and 1.66 parts of sulfuric acid solution was added. The mixture was dried by heating to 110 C. and filtered. The resultant oil was break-free and had a free fatty acid content of 0.55%, but as no bleaching earth was used was the same color as the original oil.
- Example 6 A sample of crude cottonseed oil (I. V. 110.2, F. F. A. 1.03%, 13 Gardner color, and a positive Gardner break test) was treated with 8.3% by Weight of a 12 B. caustic soda solution. The mixture was stirred at 25 C. for 30 minutes and then heated to 65 C. and stirred for 30minutes. 'Inhe mixture was then acidiiied with 7.66% of 15% sulfuric acid solution and allowed to settle.
- ExampleI 7 One hundred parts of a crude hydraulic pressed linseed oil (1.05% F. F. A., a positive Gardner break test, and 10 Gardner color) was treated @wiwi-,6.2 parts ef 8%ralka-li solution at.' 25 .G1-,fof 30 minutes. The mixture was heated .to 1652.36. and 5.1711 parts-of- 15.%sulfuric acid was ,added .with stirring. The Ymixture was then dried'by .heating to C. and three parts of an acid-.acftivated bleaching earth was added and steamV introduced. The mixture was stirred 30 minutes .with steam ⁇ and 15 minutes to dry the mixture and then filtered.
- a crude hydraulic pressed linseed oil 1.05% F. F. A., a positive Gardner break test, and 10 Gardner color
- the gross oil loss was 2.27%, but if theoil on the earth were recovered, the net losswas only 0.31%.
- the oil recovered from the earth could .be added to the major fraction ortothevnext batch.
- the final 'oil had a Gardner'colorzof v6, a free fatty acid content of 1.875%, and a negative break test.
- Example 8 One hundred parts of crudeexpeller. ylinseed oil-1 was treated with 5.8 parts of 8% alkali, ,5.36 parts of 15% sulfuric acid, and .three parts of bleaching earth as described above in Example 7.
- the original oil had a Gardner color :.of 12,-a F. F. A. content of 0.80% and a positives-break test.
- the nal oil has a Gardner color of ,5, 1.49% F.v F. A., and a negative break test.
- the loss',y ifmechanically held oilon the Yspent earth was :removed .with naphtha, was 0.48%.
- the .steps of decolorizing the oil is not yrequired where Vtheoil .isinherently of light color or ifa lightl colored ⁇ product is .not demanded. Any surface :active adsorbentmay be employed in decolorizing. Acid activated clays such asareemployednin the mineral'oil and other industries, fullers earth and the .likeare examples.
- Theioils of the examples could be admixedwith drliers,ve. g. .1 to l5% lead cobalt or manganese oleates or naphthenates to make paints and varnishes. They could be fractionated by the technique of Freeman Patent 2,200,391 to obtain high iodine value and low iodine fractions. They could be cooked with phthalic acid and glycerinek in place of conventionally alkali rened oils to provide alkyds of any desired oil length and were not poisonous to the catalysts.
- a method of treating oil containing break constituents for purposes of overcoming a tendency to produce break which process comprises treating the oil with an alkali, then further treating the oil with a strong acid in an amount approximately equivalent to the total alkali with which the oil was treated and subsequently removing the resultant salt of the alkali and the acid.
- a method of forming a break negative oil from oil containing break constituents comprises adding to the oil approximately .0l to 1% of alkali as a Water solution, then adding a strong mineral acid in an amount equivalent to the alkali added and removing the salts of the mineral acid and the alkali from the oil.
- a method of treating soya bean oil containing break constituents for purposes of overcoming the tendency of the oil to produce break when heated comprises adding to the oil .01 to 1% of caustic soda as a water solution, agitating the mixture to effect thorough contact between the oil and the caustic soda, then adding a strong mineral acid in an amount equivalent to all of the caustic soda added, and removing the 8 resultant salts of the strong mineral acid and sodium.
- a method of treating soya bean oil containing break constituents for purposes of overcoming the tendency to produce break when the oil is heated comprises agitating the oil with .0l to 1% of caustic soda at a temperature of to 100 C. until the oil is thoroughly contacted with the caustic soda, then adding a strong mineral acid in an amount equivalent to all of the caustic soda added, drying the oil and removing the salts of sodium and the strong mineral acid therefrom.
Description
Patented June 6,.,1950
PREPARAIHQN oFL-BREA-KFREE GLXGERIDEDILS Aloger'l Christensen, Milwaukeefwis., assigner toPttslugliPl'ate' Glass Company, Allegheny "'Couiity,'Pa.,a corporationfof Pennsylvania "13 Claims.
. '1 LThe present'inveitionrelates vto therlning of crudezor but partially rened glyceri'de ko'ils Such as soybeanboil, lin'seed oil, cottonsee'fd oil, corn oil or the'l'ike and it has particular relation to the refining ofsuch'oils for purposes of removing the break constituents thererom.
One object of the invention is to provide a process of treating 'glyceride'oils of the foregoing types gior purposes of .removing or transforming break. constituents-which. process `is..accompanied '-1 by ybut.. s1ight losses. of the. constituents desirable in the oil.
u .Asecond object of,the,invention`.is .tolprovidera process .=.of .treating .glyoeride oils `containing fbreak` constituents, or other ,objectionable con- -stituents 1in. order to ieliminatasuch constituents for. renderv themoinnocuous, .which .cansbeieffected inea` minimum. of `time .Witha g minimum of...ap vparatus and. in which .there but llittle -ormo degradationof..the.oil.treated. 1
-A.. 4.third obj ect e. of .ftheiinvention to provide a process of .treating glyceride .oils containing breakl or-:gum `constituents -to obtain .a product which Withoutisubstantial .losslofi glycerides, Acan he; employed for` such purposelas .the 4formation ofoalkydstyp e` resins on fortfnrthenextraction Iwith selected polar solvents in. order. -toiractionate the oil into highly unsaturatedwand highly saturated portions of light color.
1A 4fourth :oloioot .of fhoinvonion .I is to 1 provido a. process- .of .treating .orrido oil oon-taining .break oonstituoots lsu/ch lecithin ,or .Similar .phosohatdos and .oolorinemattor `to:providelvvfho,.1.1t substantial loss of glycerides, .aiproduct which .can thonroasilvbo bleached :forpurlooses offromoving or otherwiseeliminating the color constituents i therefrom.
. vvThese and other A objects of thel invention will be xapparent from consideration of; the following specification and the .appendedclaims. Glyceride oils such assoybean oil,.1inseedoil, cottonseed; oil, corn `oil and the like as obtained by conventional methods of removal. from the seeds .constituting the source thereofVinclude various4 constituentsf-such as.. .gums or breakt constituents Whichflhave ia tendency .-toseparate fout andrsform .a .iT-lock, .especially .Whensthe `aoil heated. Y'The Aoil ^also usually. includes .other :objectionable :materials such cas .fcoloring `matter. For some purposes and with some gradespffol, these latter constituents :maynot be particularly objectionable. However, if anoil of light color isirequired, theyjmayjreguire treatment inzorder to geffect;removartnereof.
I"The convent na1"^test 'for break is known as ApplicationAugust 31, 194s, Serial No- 47,130
the yGardner test.V vIt comprises adding Aa few frirops 'of aqueoushydrochloric acifd and heating the`'il1to`550WF. "Formation of a precipitatefis a positivr'eV test. The precipitatemaybeltered o, :washed free 4ofoil with carbon tetrachloride and `weighed to ldeterrnine ipercent of Gardner break. Tnemetnqd isignownas A. 0.o.-
'The'ccnventionalymethod oftreating glyceride oils in..order tof/remove: break and` to improve the coloring linvolved, most usuallytreatment" with a strong'aljkaii such assodiu'rnl hydroxide 4in Vconsjderahierquantities; or vby.tdegurmning 'unitari/atar. The alkali reacts With the "free `fatty '-acids; the
1 break Yc'oristiti'ie,ntsaridto's'orne'extentvvitli the 'glycerdes, producingsoaps 'which' loyA appropriate cooling ,andsettling technique can' be collected as jan Aunder layer called roots. *Tvheefoots and the oiljin"conventionalipracticeA areseparated by jdecaritati'on,'jcentrifugationor otherappropriate technique. With Nthe i'foots, vis entrapped #consilderable'uam'ounts'o'f' gooclo'il. The foots orby- 'product can jbe jsol'rl *only-ata greatly wreduced price.
Simple degunirning, i or treatment with 'Water 'may `also be' employed* torenne the "oil, butit results" 'in lossesarijd fdoes not'\fcompletely"remove the break. "Thefbreak is'apoison for leadcatalysts ernpioyed in` formation fof alkydw-resins. V'The'preseritiirnention is basedupon thel "discoverythat Whenjglyceride' foils 'aratreatednrith an alkalsuh'as'odiurn hydroxide'sodium carbonate, sodium bicarbonate or` the corresponding potassium coinp'oundsijgin lorderrpartially" to `decornjpose `such l*break forming constituents as lecithin "or "other phosphatide'sf/ occurring- "in "the natural4 or crude oil,"theyormmproducts `Whicl'l ean""the'n be successfully neutralized with an 'ajc'id j'such as "sulfuric jac'id, hydrochloric acid, phosphoric 'acidpr organic acids suchas` acetic a'crd,-rnaleic acidor the-dike 4tolprovide ai'break lfr'eeoil.
i The' behavior of' the #break Aconstituents man b e explained 'up'onirthe"theory"'that phosphatides such as" lecithin "spliteither-betweentheglycjerol nucleus `and the Aphosphori'cacid'radicalfortbetween i the A'latter' raplifoalfand' thebasic group; e. gchoflinej orjtljianolarnine. t Vrn'ay he" 'that the split iny jsoine'instanc'es will ib'e n atj'one @position and 'in'` otherfiiistanceshit Willfbe' k.at'fth'ej'othenso thaihere vorbeiamanreofetheztwotypes/of Products'ihttho ^foilfsbsoquontlynt ve noilrcan bofdriodl to. eliminato-Water. andto. precipitato tho the alkali and perhaps choline and the acid may be washed out by treating the oil with water and nally drying the oil by blowing it with inert gas, e. g. CO2.
The salts, if filtered out, may further be washed with a solvent such as naphtha designed to extract out the glycerides which may be absorbed in or cling to the salts. By such treatment, practically all of the oil is recovered. The recovered portion may be returned to the oil or may be added to the next batch as desired. The usual separation of degraded products from the main body of the oil is thus avoided and rening losses are cut to a minimum.
In the practice of the invention, an oil containing gum or break constituents, such as a whole soybean oil, corn oil, linseed oil or cottonseed oil, or a raffinate oil obtained by furfural extraction of a glyceride oil as described in U. S. Patent 2,200,391, is treated with alkaline material preferably in the form of a water solution. The amount should be comparatively low, and may, for example, be within a range of from .01 to 1.00% solid alkali added as a solution per pound of oil.
The mixture of oil and alkali solution preferably, are agitated together for sufficient time to permit adequate reaction of the constituents therein. This reaction may be promoted by heating the mixture moderately during the ag1tation, for example, to a temperature of 50 to 100 .0. Agitation may be continued as long as desired but, of course, there is no point in continuing it excessively long, since such operation merely ties up the apparatus, occupies the time of the operator and is power consuming. Usually, a period of twenty minutes to one hour is sufficient.
After the mixture has been sufficiently agitated to obtain adequate reaction between the alkaline material and the break constituents of the oil, acids should be added to neutralize the alkali. For this purpose, phosphoric acid, sulfuric acid, hydrochloric acid or organic acids such as acetic, maleic or fumaric or other acid capable of decomposing fatty acid soaps may be employed.
The amount should be sumcient, or slightly in excess of the amount required approximately to neutralize any free alkali and to decompose the alkali salts in the solution. The correct amount, of course, can easily be calculated from the amount of alkali added or, if preferred, by titration of samples of the oil from time to time as acid is added.
As previously stated, removal of the alkali salt can be effected either by drying the oil and thus precipitating the salts so that they can be ltered out, or by washing the oil with water in order to extract out the salts. The oil should be dried after acidification or after washing with water, for example, by bubbling inert gas such as carbon dioxide or nitrogen therethrough at an appropriate temperature, e. g. 100 to 200 C. Lower temperatures can be employed but the removal of the water is then slower. Also vacuum could be applied to hasten the drying operation at a moderate temperature.
After the salts have been removed, the oil product as obtained, is only slightly higher in acid value than the original oil. Doubtless, it contains nearly all of the fatty acids and glycerides with which it started so that rening losses are no more than a few tenths of a percent, yet it is perfectly satisfactory for most uses to which the oils are conventionally applied, e. g. as modifiers of, or raw materials for alkyd resins for use in 2,510,379 f -Y A coating compositions. 1n the latter, it does not poison the catalyst. The oil may also be subjected to further treatment as, vfor example, solvent fractionation as above described. If treatment with alkali then with acid, without further treatment is employed, the coloring of the oil will be about the same as that of the original oil. If lighter products are desired, the break free product as obtained by the application of the foregoing technique, is excellently adapted for simple bleaching operations. For example, the treated oil can be admixed with l to 5% of fullers earth or acid activated bleaching clay, e. g. acid treated bentonite, or with activated charcoal such as bone char or other bleaching `agents and the decolorizing agents filtered out to obtain oil of very light color. The bleaching agent, of course, will carry out a certain amount of oil absorbed or adherent thereto. This oil can easily be recovered by extraction with naphtha and, evaporation of the naphtha therefrom. The oil recovered from the bleaching agent in this manner is notl of excessively dark color and can be added to the next batch or the parent batch if desired.
The following examples are illustrative of specific applications of the principles of the invention.
Example 1 One hundred parts of partially degummed soybean oil (-24% free fatty acids, 10.5 Gardner color, 133.5 I. V.) Was treated with 1.7 parts of 8% sodium hydroxide solution at 25 C. for 30 minutes and at 65 C. for 30 minutes. Enough phosphoric acid (0.136 part) was added to neutralize the alkali used and the mixture heated to 110 C. and dried by bubbling inert gas. Two parts of an acid activated bleaching earth was added and agitation continued for 30 minutes. The filtered oil had a free fatty acid content of 0.36, a negative Gardner break test, and a Gardner color of 4. The oil readily underwent an alcoholysis with glycerol with litharge as a catalyst, indicating that the break had been transformed to an innocuous form. The oil loss including that on the spent clay was 1.50%, but if the oil on the clay were recovered with naphtha. the loss was only 0.177%.
Example 2 One hundred parts of crude linseed oil (0.88% free fatty acids, l1 Gardner color, 177.0 I. V.) and giving a positive break test, was stirred with 5.9 parts of 8% alkali for 30 minutes, then heated to 65 C. A 15% solution of sulfuric acid, 5.46 parts, was added and the mixture stirred and heated to 110 C. Four parts of bleaching earth was added and the temperature allowed to fall to C. `where it was held until 30 minutes from the addition of earth had elapsed. The oil was then ltered to yield a product having a fatty acid content of 1.90%, a negative Gardner break test, and a Gardner color 'of 4. The loss after the spent earth had been freed of oil by a naphtha wash was 0.31%. The oil recovered from the spent cake with naphtha contained no break and was not excessively dark and could be Iadded to the next batch or the main body of oil if desired. The product underwent `an alcoholysis with glycerol in the presence of litharge with no poisoning effects.
Example 3 One hundred parts of crude soybean oil (0.38%
free fatty acids, 10.5 Gardner color, 135.0 I. V.) and giving a positive break test was treated with i75l7r-1212l15 0f 8% alkali solutionf for 30 -min-utesrlai. room temperature and heated to 65 C. Then k12-parts of r15-.% sulfuric-.acid solution was added mld-inertgas (CO2) was bubbled into the mixtureia-nd the temperature raised to 110 C. Two ,parts-by 'weight of an acid activated bleaching earth lwas `.added and agitation continued for 30 minutes. The mixture was iilteredand a breakfree oilfwith 1.90% free fatty acids, la Gardner .color-fof 4.5 resulted. A loss of 0.28%` resulted if the iiltercakewas washed free ofoil with naph- .tha. The oil washed from the cake-was of good color and break-free. The product reacted .prop- .erly :.withvglycerol in the 4presence of litharge showing that the catalyst poisons had been eliminated or rendered innocuous.
Example 4 One hundred parts of crude soybean oil (0.63% Ifree'fa-ttyacids, l13rGardner-color, 131.9 iodine va-lue) 'andz giving'a positive break that was treated with 8.4 parts of 8% alkali solution at 65 1C.for 30 minutes and then acidied with 10.32 parts of 15% sulfuric acid. The temperature was raised to 110 C. and held there until .the mixture was dry. The oil was allowed to cool and the inorganic salts filtered. The loss of material remaining on the cake was 1.51% of the oil after entrained oil was removed as a naphtha wash. As bleaching earth was not used, the color gof -oil was only .sl1ghtly improved, -but it was( break-free and underwent an alcoholysis readily. The final. free fattyvacid content was 3.20%.
Example One hundred parts of solvent extracted partially degummed soybean oil (0.30% free fatty acids, 10 Gardner color, 136.8 I. V. and a positive Gardner break test) was treated with 1.8 parts of 8% alkali for 30 minutes at room temperature. The temperature was raised to 65 C. and 1.66 parts of sulfuric acid solution was added. The mixture was dried by heating to 110 C. and filtered. The resultant oil was break-free and had a free fatty acid content of 0.55%, but as no bleaching earth was used was the same color as the original oil.
Eample 6 A sample of crude cottonseed oil (I. V. 110.2, F. F. A. 1.03%, 13 Gardner color, and a positive Gardner break test) was treated with 8.3% by Weight of a 12 B. caustic soda solution. The mixture was stirred at 25 C. for 30 minutes and then heated to 65 C. and stirred for 30minutes. 'Inhe mixture was then acidiiied with 7.66% of 15% sulfuric acid solution and allowed to settle.
The lower aqueous layer was withdrawn and the ExampleI 7 One hundred parts of a crude hydraulic pressed linseed oil (1.05% F. F. A., a positive Gardner break test, and 10 Gardner color) was treated @wiwi-,6.2 parts ef 8%ralka-li solution at.' 25 .G1-,fof 30 minutes. The mixture was heated .to 1652.36. and 5.1711 parts-of- 15.%sulfuric acid was ,added .with stirring. The Ymixture was then dried'by .heating to C. and three parts of an acid-.acftivated bleaching earth was added and steamV introduced. The mixture was stirred 30 minutes .with steam `and 15 minutes to dry the mixture and then filtered. The gross oil loss was 2.27%, but if theoil on the earth were recovered, the net losswas only 0.31%. The oil recovered from the earth could .be added to the major fraction ortothevnext batch. The final 'oilhad a Gardner'colorzof v6, a free fatty acid content of 1.875%, and a negative break test.
Example 8 One hundred parts of crudeexpeller. ylinseed oil-1 Was treated with 5.8 parts of 8% alkali, ,5.36 parts of 15% sulfuric acid, and .three parts of bleaching earth as described above in Example 7. The original oil had a Gardner color :.of 12,-a F. F. A. content of 0.80% and a positives-break test. The nal oil has a Gardner color of ,5, 1.49% F.v F. A., and a negative break test. The loss',y ifmechanically held oilon the Yspent earth was :removed .with naphtha, was 0.48%.
The .steps of decolorizing the oil is not yrequired where Vtheoil .isinherently of light color or ifa lightl colored `product is .not demanded. Any surface :active adsorbentmay be employed in decolorizing. Acid activated clays such asareemployednin the mineral'oil and other industries, fullers earth and the .likeare examples.
Theioils of the examples could be admixedwith drliers,ve. g. .1 to l5% lead cobalt or manganese oleates or naphthenates to make paints and varnishes. They could be fractionated by the technique of Freeman Patent 2,200,391 to obtain high iodine value and low iodine fractions. They could be cooked with phthalic acid and glycerinek in place of conventionally alkali rened oils to provide alkyds of any desired oil length and were not poisonous to the catalysts.
It is a feature of the invention that the gum and break constituents of the oil are removed or converted by the combination of steps to an innocuous form in which they will not separate when the oil is heated to break temperature and they Will not poison such catalysts as litharge. The advantages of alkali refining are thus secured with little or no loss of valuable oil as foots or soapstock.
The forms of the invention herein shown and described are to be regarded merely as exemplary, and it will be apparent to those skilled in the art, that numerous modifications may be made therein, without departure from the spirit of the invention or the scope of the appended claims.
I claim:
1. A method of treating oil containing break constituents for purposes of overcoming a tendency to produce break, which process comprises treating the oil with an alkali, then further treating the oil with a strong acid in an amount approximately equivalent to the total alkali with which the oil was treated and subsequently removing the resultant salt of the alkali and the acid.
2. In a process of treating a glyceride oil containing break constituents, the steps which comprise treating the oil, rst with a small amount of caustic soda in solution in water, then with a strong acid equivalent in amount to the total caustic soda introduced, drying the oil and lter- :lng off the saltsv of the caustic soda andthe strong acid.
3. In a process of treating a glyceride oil containing break constituents, the steps which comprise treating the oil with a small amount of an alkali adapted to react with the break constituents of the oil, then subsequently adding a strong acid in an amount equivalent to the total alkali added and removing the resultant salts of the alkali and the acid, and drying the oil.
4. A process as dened in claim 3 in which the amount of alkali is in excess of .01%.
5. A process as defined in claim 4 in which the v-oil after addition of the acid is treated With an adsorbent as a bleaching agent.
6. The steps as defined in claim 3, in which the removal of the salts is eiected by water- Washing the oil.
7. The steps as defined in claim 6, in which the oil treated is linseed oil.
8. A method of forming a break negative oil from oil containing break constituents, which process comprises adding to the oil approximately .0l to 1% of alkali as a Water solution, then adding a strong mineral acid in an amount equivalent to the alkali added and removing the salts of the mineral acid and the alkali from the oil.
9. A method of treating soya bean oil containing break constituents for purposes of overcoming the tendency of the oil to produce break when heated, which method comprises adding to the oil .01 to 1% of caustic soda as a water solution, agitating the mixture to effect thorough contact between the oil and the caustic soda, then adding a strong mineral acid in an amount equivalent to all of the caustic soda added, and removing the 8 resultant salts of the strong mineral acid and sodium.
10. A method of treating soya bean oil containing break constituents for purposes of overcoming the tendency to produce break when the oil is heated, which method comprises agitating the oil with .0l to 1% of caustic soda at a temperature of to 100 C. until the oil is thoroughly contacted with the caustic soda, then adding a strong mineral acid in an amount equivalent to all of the caustic soda added, drying the oil and removing the salts of sodium and the strong mineral acid therefrom.
11. A process as defined in claim 10 in which the oil is subsequently bleached by contacting it With an adsorbent clay.
12. A process as dened in claim 10 in which the oil is subsequently bleached by contacting it with an acid activated clay.
13. A process as defined in claim 10 in which the oil is subsequently bleached by contacting it with fullers earth.
ROGER. M. CHRISTENSON.
REFERENCES @FEED The following references are of record in the le of this patent:
UNTED STATES PATENTS Jakobsen Aug. 31, 1948 OTHER REFERENCES Bailey: Oil & Fat Products (1945), Interscience Pub. Inc.. page 507.
Claims (1)
1. A METHOD OF TREATING OIL CONTAINING BREAK CONSTITUENTS FOR PURPOSES OF OVERCOMING A TENDENCY TO PRODUCE BREAK, WHICH PROCESS COMPRISES TREATING THE OIL WITH AN ALKALI, THEN FURTHER TREATING THE OIL WITH A STRONG ACID IN AN AMOUNT APPROXIMATELY EQUIVALENT TO THE TOTAL ALKALI WITH WHICH THE OIL WAS TREATED AND SUBSEQUENTLY REMOVING THE RESULTANT SALT OF THE ALKALI AND THE ACID.
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US47130A US2510379A (en) | 1948-08-31 | 1948-08-31 | Preparation of break-free glyceride oils |
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US47130A US2510379A (en) | 1948-08-31 | 1948-08-31 | Preparation of break-free glyceride oils |
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US2510379A true US2510379A (en) | 1950-06-06 |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2702813A (en) * | 1952-03-05 | 1955-02-22 | Laval Separator Co De | Refining of fatty oils and fats |
US2727051A (en) * | 1952-06-21 | 1955-12-13 | Sherwin Williams Co | Color improvement of drying oils |
US2744922A (en) * | 1951-12-10 | 1956-05-08 | Separator Ab | Method of soap-making |
US2824885A (en) * | 1955-01-03 | 1958-02-25 | Ranchers Cotton Oil | Refining triglyceride oils |
US2896486A (en) * | 1952-08-28 | 1959-07-28 | Wallace Mcclung Donnelly | Process of cold rolling steel sheets |
US3147291A (en) * | 1960-12-12 | 1964-09-01 | Pellerins Margarinfabrik Ab | Method for purifying fat |
DE1186162B (en) * | 1959-09-21 | 1965-01-28 | Pellerins Margarinfabrik Ab | Process for removing small amounts of soap and alkali from refined fats |
US3943155A (en) * | 1974-05-13 | 1976-03-09 | The Procter & Gamble Company | Simultaneous refining and dewaxing of crude vegetable oil |
FR2442882A1 (en) * | 1978-11-30 | 1980-06-27 | Showa Sangyo Co | PROCESS FOR REFINING ANIMAL OR VEGETABLE OILS AND FATS |
FR2459828A1 (en) * | 1979-06-25 | 1981-01-16 | Showa Sangyo Co | PROCESS FOR REFINING ANIMAL OR VEGETABLE OILS AND FATS |
US4609500A (en) * | 1981-10-15 | 1986-09-02 | Cpc International Inc. | Refining of oil and product thereof |
US11912958B2 (en) | 2018-06-11 | 2024-02-27 | Poet Research, Inc. | Methods of refining a grain oil composition |
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US1147392A (en) * | 1913-11-04 | 1915-07-20 | Conrad A Dieterich | Method of refining oils and fats. |
US2164012A (en) * | 1937-05-19 | 1939-06-27 | Shell Dev | Treatment of nonmineral fatty matter raffinates |
US2448434A (en) * | 1946-10-05 | 1948-08-31 | Gen Mills Inc | Process for producing nonbreak oil |
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US1147392A (en) * | 1913-11-04 | 1915-07-20 | Conrad A Dieterich | Method of refining oils and fats. |
US2164012A (en) * | 1937-05-19 | 1939-06-27 | Shell Dev | Treatment of nonmineral fatty matter raffinates |
US2448434A (en) * | 1946-10-05 | 1948-08-31 | Gen Mills Inc | Process for producing nonbreak oil |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2744922A (en) * | 1951-12-10 | 1956-05-08 | Separator Ab | Method of soap-making |
US2702813A (en) * | 1952-03-05 | 1955-02-22 | Laval Separator Co De | Refining of fatty oils and fats |
US2727051A (en) * | 1952-06-21 | 1955-12-13 | Sherwin Williams Co | Color improvement of drying oils |
US2896486A (en) * | 1952-08-28 | 1959-07-28 | Wallace Mcclung Donnelly | Process of cold rolling steel sheets |
US2824885A (en) * | 1955-01-03 | 1958-02-25 | Ranchers Cotton Oil | Refining triglyceride oils |
DE1186162B (en) * | 1959-09-21 | 1965-01-28 | Pellerins Margarinfabrik Ab | Process for removing small amounts of soap and alkali from refined fats |
US3147291A (en) * | 1960-12-12 | 1964-09-01 | Pellerins Margarinfabrik Ab | Method for purifying fat |
US3943155A (en) * | 1974-05-13 | 1976-03-09 | The Procter & Gamble Company | Simultaneous refining and dewaxing of crude vegetable oil |
FR2442882A1 (en) * | 1978-11-30 | 1980-06-27 | Showa Sangyo Co | PROCESS FOR REFINING ANIMAL OR VEGETABLE OILS AND FATS |
US4280962A (en) * | 1978-11-30 | 1981-07-28 | Showa Sangyo Co., Ltd. | Methods for refining oils and fats |
FR2459828A1 (en) * | 1979-06-25 | 1981-01-16 | Showa Sangyo Co | PROCESS FOR REFINING ANIMAL OR VEGETABLE OILS AND FATS |
US4609500A (en) * | 1981-10-15 | 1986-09-02 | Cpc International Inc. | Refining of oil and product thereof |
US11912958B2 (en) | 2018-06-11 | 2024-02-27 | Poet Research, Inc. | Methods of refining a grain oil composition |
US11952553B2 (en) | 2018-06-11 | 2024-04-09 | Poet Research, Inc. | Methods of refining a grain oil composition |
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