US2610915A - Winterized glyceride oil and process of producing the same - Google Patents
Winterized glyceride oil and process of producing the same Download PDFInfo
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- US2610915A US2610915A US175659A US17565950A US2610915A US 2610915 A US2610915 A US 2610915A US 175659 A US175659 A US 175659A US 17565950 A US17565950 A US 17565950A US 2610915 A US2610915 A US 2610915A
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- oil
- glyceride
- melting point
- fatty material
- cold test
- Prior art date
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- 125000005456 glyceride group Chemical group 0.000 title description 45
- 238000000034 method Methods 0.000 title description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- -1 VINYL COMPOUNDS Chemical class 0.000 claims description 5
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 56
- 235000019198 oils Nutrition 0.000 description 56
- 239000000463 material Substances 0.000 description 33
- 239000000470 constituent Substances 0.000 description 31
- 238000002844 melting Methods 0.000 description 29
- 230000008018 melting Effects 0.000 description 29
- 239000013078 crystal Substances 0.000 description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000012343 cottonseed oil Nutrition 0.000 description 7
- 238000009882 destearinating Methods 0.000 description 7
- 239000003925 fat Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 240000008415 Lactuca sativa Species 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000008268 mayonnaise Substances 0.000 description 5
- 235000010746 mayonnaise Nutrition 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 235000012045 salad Nutrition 0.000 description 5
- 235000002316 solid fats Nutrition 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002385 cottonseed oil Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010699 lard oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- PVNIQBQSYATKKL-UHFFFAOYSA-N Glycerol trihexadecanoate Natural products CCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCC PVNIQBQSYATKKL-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings or cooking oils characterised by ingredients other than fatty acid triglycerides
- A23D9/013—Other fatty acid esters, e.g. phosphatides
-
- 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
- C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
- C11B7/0083—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils with addition of auxiliary substances, e.g. cristallisation promotors, filter aids, melting point depressors
Definitions
- This invention relates to treating fatty glyceride material, and it has to do more particularly with the manufacture of an improved glyceride o1
- an important problem is the removal of the high melting point glycerides which are normally solid at room temperatures and Which tend to separate from the oil at relatively high temperatures.
- the conditioning of a glyceride fatty material to effectuate separation of the liquid fats from the undesirable solid fats must be carefully controlled in order to obtain the solid fat in a crystalline form suitable for filtration. Under the best conditions, filtration is inefficient, for the solid fats often separate as extremely small particles and remain suspended in the oil as colloidal dispersions, thus making the straining operation very difficult.
- compositions hereinafter to be described and referred to as crystal inhibiting and modifying agents are extremely useful in prolonging the cold test of glyceride oils and in facilitating the Winterizing process.
- Another object of the present invention is to provide a method of improving the Winterizing of glyceride oils.
- Still another object of the invention is to provide a glyceride oil having an improved cold test.
- a still further object of the present invention is to provide an improved glyceride oil which will remain clear and homogeneous for long periods of time at relatively low temperatures.
- Another object of the invention is to provide an improved glyceride oil which will exhibit good stability at relatively low temperatures when incorporated in an emulsion.
- the invention contemplates the addition to a glyceride oil or glyceride fatty material, either before or after winterization, of a small amount of an oil-soluble polymerization product of esters having vinyl or substituted vinyl group, according to the following general formula; namely, esters of the formula wherein X is a hydrogen atom and alkyl or aromatic hydrocarbon group, and Y is o Jae-R in which R is a monovalent hydrocarbon radical containing more than 4 carbon atoms or an ether derivative of said hydrocarbon radical.
- esters of acrylic acid or of its alpha-alkyl or alpha-aryl substitution products and monohydric alcohols containing more than 4 carbon atoms such as octyl, decyl, lauryl, or cetyl esters of acrylic acid, alpha-methacrylic acid, and other alpha-substituted homogenous or acrylic acid, as more fully described in U. S. Patent 2,091,627.
- the most effective polymers for the present purpose are the oil-soluble polymerized esters of acrylic acid or alpha-methacrylic acid and monohydric, saturated, primary aliphatic alcohols containing from 12 to 18 carbon atoms or molecules, such as lauryl, cetyl, or octadecyl esters.
- esters need not be pure but may be mixtures of one or more of the higher aliphatic alcohols and the acrylic or methacrylic acid polymerization products. A mixture of two or more of the foregoing polymers may also be used.
- polymers are preferably prepared by heating the monomeric esters or mixtures thereof at 70-100 C. in the presence of small amounts of polymerization-inducing catalysts, such as peroxides or ozonides, as more fully disclosed in U. S. Patents 2,100,993 and 2,114,233.
- polymerization-inducing catalysts such as peroxides or ozonides
- the amount of the foregoing crystal modifiers used ranges from .005 to 1.0 per cent. Where it is desired to add the crystal modifier prior to the Winterizing operation to facilitate filtration, it is often advantageous to add additional amounts to replace that which may be removed with the solid matter during filtration. Larger amounts of the crystallization inhibitor may be used but generally is not commercially advisable.
- Example I To 100 grains of winterized cottonseed salad oil having a cold test of about 9 hours was added 1.0 per cent of the oil-soluble polymerization product of an ester of alpha-methacrylic acid and lauryl alcohol. After the said polymerization product is uniformly distributed throughout the oil, a cold test of the treated oil gave a value of 45 hours.
- Example III To a sample of winterized cottonseed oil having a cold test of 15 hours, 0.02 per cent of cetylalpha-methacrylate soluble in oil was added and uniformly distributed therethrough. The oil containing the above crystal-inhibiting agent exhibited a cold test of 60 hours.
- Example I Mayonnaise made with a winterized cottonseed salad oil containing 0.02 per cent n-oetyl-acrylate soluble in oil was placed in a cooler maintained at a temperature of 28 F., and the mayonnaise emulsion did not break until after being held seven days at the said temperature.
- Example V A sample of refined and bleached cottonseed oil containing 0.20 per cent lauryl-alpha-methacrylate soluble in oil was placed in a cooler maintained at 45 F. for three days. Upon filtering the sample by gravity through a standard filter cloth, the yield of oil from the sample containing the above crystal-inhibiting agent was 82 per cent. The yield of the control sample of the refined and bleached cottonseed oil was '71 per cent.
- Example VI To a sample of white grease was added 0.10 per cent of an ester of alpha-methacrylic acid and octadecyl alcohol soluble in oil and the sample seeded for five days at F. The yield of oil upon pressing the white grease treated in the foregoing manner was per cent. The yield from the control chamber of the white grease containing no crystal-inhibiting agent was 55 per cent.
- Example VII A sample of crude sperm oil containing 0.05 per cent n-lauryl acrylate soluble in oil was seeded in 45 F. for six days and then pressed. The yield of winterized sperm oil treated in the foregoing manner was 82 per cent. The yield of the control sample of the sperm oil was per cent.
- the above-described crystal inhibitors and modifiers may be added to the glyceride materials before or after winterization.
- the addition of the crystal modifier before winterization serves primarily to facilitate and improve the Winterizing operation.
- crystal formation is retarded in the presence of the additive, once the crystals are formed they are of such form as to settle quickly, and because of the nature of the crystals a sharp separation of the undesired solids from the liquid constituents of the oil is possible.
- An advantage of the improved filtering operation is that the yields of oils are greatly increased over the Winterizing process as hitherto practiced. Often it is desirable to add an additional small amount of the additive after the winterization operation so as to replace that which was filtered out along with the high melting glyceride crystals.
- the materials described above are added to the oil after it has been winterized, the extent of lengthening the cold test depending on the quality of oil chosen, the additive being more efiective'in an oil having an original 'longer cold test than in an oil of shorter cold test.
- Another important advantage of the invention flows from the use of oil treated with the described agents in emulsions.
- An emulsion, such as mayonnaise, containing a vegetable oil treated in the foregoing manner will remain stable for muchlonger periods of time than has been hitherto possible to maintain such emulsions.
- the invention described herein has particular application to the manufacture of salad oils, the invention is not limited to such an operation. It should be understood that the invention is useful in treating various fatty glyceride materials wherein a solid or crystalline fraction is separated from a liquid fraction as in the separation of a crystalline fraction from animal oils such as lard oil, oleo oil, sperm oil, and animal fats and greases used in the preparation of lard oil and the like.
- crystal modifying agents herein described may also be used to modify the crystal structure of the solid phase whereby it may be more readily separated from the liquid phase when extracted with a suitable solvent.
- a glyceride oil composition of improved cold .test comprising a glyceride oil having incorporated therein a small amount of an oil-soluble product to improve the cold test thereof, said product being the polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl compounds according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula and -(
- a glyceride oil composition of improved cold test comprising a glyceride oil having incorporated therein a small amount of an oil-soluble product to improve the cold test thereof, said product being a polymerization product of a substituted vinyl compound according to the general formula wherein X is an alkyl radical and R is an allphatic monohydric saturated alcohol radical having more than 12 carbon atoms.
- a glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having in-v corporated therein a small amount of an oilsoluble product to improve the cold test thereof, said product being the polymerization product of an ester of acrylic acid and a monohydric saturated alcohol containing more than 12 carbon atoms per molecule.
- a glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having incorporated therein a small amount of an oilsoluble product to improve the cold test thereof, said product being the polymerization product of an alpha-alkyl substituted acrylic acid and a monohydric saturated alcohol containing more than 12 carbon atoms per molecule.
- a glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having incorporated therein a small amount of an oil-soluble polymerization product in an amount between .005 and 1.0 per cent by weight to improve the cold test thereof, said product being a member of a group consisting of lauryl, cetyl, and octadecyl esters of alpha-methacrylic acid.
- a method of separating a glyceride fatty material into higher and lower melting point constituents by fractionating the liquefied fatty material the improvement which comprises dispersing throughout the said fatty material a small amountof an oil soluble crystal modifying product to increase the rate at which the relatively high melting point crystals settle, said product being the polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl radicals according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula t oo-R and wherein R. is selected from the group consisting of a monovalent hydrocarbon radical containing more than 4 carbon atoms and oxy derivatives thereof.
- An improved method of separating a glyceride fatty material into higher and lower melting point constituents which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl radicals according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula and wherein R is selected from the group consisting of a monovalent hydrocarbon radical containing more than 4 carbon atoms and oxy derivatives thereof, cooling the said fatty material containing the added polymerization product to crystalide fatty material into higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization 7 product of a substituted vinyl compound.
- An improved method of separating a glyceride fatty material into'higher and lower melting point constituents which comprises dispersing throughout a liquefied glyceride fatty material a "small amount of an oil-soluble polymerization product of an ester of acrylic acid and monohydric saturated alcohol containing more than 12 carbon atoms per molecule, cooling the said fatty material containing the added polymerization product to crystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
- An improved method of separating a glyceride fatty material into higher and lower melting point constituents which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product of an alpha-alkyl aryl substituted acrylic acid and monohydric saturated alcohol containing more than 12 carbon atoms per molecule, cooling the said fatty material containing the added polymerization product to crystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
- An improved method of separating a glyceride fatty material into higher and lower melting point constituents which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product selected from the group consisting of polymerized lauryl esters of alpha-methacrylic acid, cetyl esters of alpha-methacrylic acid, and octadecyl esters of alpha-methacrylic acid, cooling the said fatty material containing the added polymerization product tocrystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Description
fiatenteci Sept. 16, 1952 WINTERIZED GLYCERIDE 011. AND PROCESS OF PRODUCING THE SAME Karl F. Mattil, Chicago, 111., assignor to Swift &
Company, Chicago, 111., a corporation of Illinois No Drawing. Application July 24, 1950, Serial No. 175,659
11 Claims.
This invention relates to treating fatty glyceride material, and it has to do more particularly with the manufacture of an improved glyceride o1 In the processing of glyceride fatty material an important problem is the removal of the high melting point glycerides which are normally solid at room temperatures and Which tend to separate from the oil at relatively high temperatures. The conditioning of a glyceride fatty material to effectuate separation of the liquid fats from the undesirable solid fats must be carefully controlled in order to obtain the solid fat in a crystalline form suitable for filtration. Under the best conditions, filtration is inefficient, for the solid fats often separate as extremely small particles and remain suspended in the oil as colloidal dispersions, thus making the straining operation very difficult.
I have now discovered that certain compositions hereinafter to be described and referred to as crystal inhibiting and modifying agents are extremely useful in prolonging the cold test of glyceride oils and in facilitating the Winterizing process.
In winterizing" a glyceride oil or processing a fatty material such as sperm oil or white grease to obtain lard oil, the conditioning of the oil or fatty material to effectuate separation of the liquid fats from the solid fats must be carefully controlled in order to obtain the solid fat in a crystalline form suitable for filtration. Under the best present-day conditions filtration is ineflicient, for the solid fats often separate as extremely small particles and remain suspended in the oil as colloidal dispersions, thus making the straining operation very diflicult. The difficulties attending the process of Winterizing as hitherto practiced may be overcome by incorporating into the glyceride oil or glyceride fatty material, such as sperm oil or white grease, a small amount of the crystal inhibitors and modifiers, hereinafter described. I have found that the addition of such substance profoundly affects crystallization whereby the crystals of the solid fats are rendered firmer and better defined. The form f the crystals is so improved that a more facile and complete separation of the undesirable solids from the liquid constituents of the oil is effected. In addition to improving winterization, these substances are usually present in sufiicient amounts to lengthen substantially the cold test of the oil, although this effect is not so pronounced as that which results when the crystal inhibitor is added after the oil has been winterized.
An important object of the present invention is,
therefore, to provide an improved method for separating the solidified fat crystals from the liquid fats in glyceride fatty material.
Another object of the present invention is to provide a method of improving the Winterizing of glyceride oils.
Still another object of the invention is to provide a glyceride oil having an improved cold test.
A still further object of the present invention is to provide an improved glyceride oil which will remain clear and homogeneous for long periods of time at relatively low temperatures. v
Another object of the invention is to provide an improved glyceride oil which will exhibit good stability at relatively low temperatures when incorporated in an emulsion.
Additional objects of the invention will be apparent from the description and claims to follow.
Broadly, the invention contemplates the addition to a glyceride oil or glyceride fatty material, either before or after winterization, of a small amount of an oil-soluble polymerization product of esters having vinyl or substituted vinyl group, according to the following general formula; namely, esters of the formula wherein X is a hydrogen atom and alkyl or aromatic hydrocarbon group, and Y is o Jae-R in which R is a monovalent hydrocarbon radical containing more than 4 carbon atoms or an ether derivative of said hydrocarbon radical.
' Compounds of the above type are the esters of acrylic acid or of its alpha-alkyl or alpha-aryl substitution products and monohydric alcohols containing more than 4 carbon atoms, such as octyl, decyl, lauryl, or cetyl esters of acrylic acid, alpha-methacrylic acid, and other alpha-substituted homogenous or acrylic acid, as more fully described in U. S. Patent 2,091,627.
The most effective polymers for the present purpose are the oil-soluble polymerized esters of acrylic acid or alpha-methacrylic acid and monohydric, saturated, primary aliphatic alcohols containing from 12 to 18 carbon atoms or molecules, such as lauryl, cetyl, or octadecyl esters.
These esters need not be pure but may be mixtures of one or more of the higher aliphatic alcohols and the acrylic or methacrylic acid polymerization products. A mixture of two or more of the foregoing polymers may also be used.
These polymers are preferably prepared by heating the monomeric esters or mixtures thereof at 70-100 C. in the presence of small amounts of polymerization-inducing catalysts, such as peroxides or ozonides, as more fully disclosed in U. S. Patents 2,100,993 and 2,114,233.
Preferably the amount of the foregoing crystal modifiers used ranges from .005 to 1.0 per cent. Where it is desired to add the crystal modifier prior to the Winterizing operation to facilitate filtration, it is often advantageous to add additional amounts to replace that which may be removed with the solid matter during filtration. Larger amounts of the crystallization inhibitor may be used but generally is not commercially advisable.
The following examples illustrate how the invention may be practiced, and are not intended to limit the scope of the invention:
Example I To 100 grains of winterized cottonseed salad oil having a cold test of about 9 hours was added 1.0 per cent of the oil-soluble polymerization product of an ester of alpha-methacrylic acid and lauryl alcohol. After the said polymerization product is uniformly distributed throughout the oil, a cold test of the treated oil gave a value of 45 hours.
Example [I To 100 grams of winterized cottonseed salad oil having a cold test of about 9 hours was added 0.10 per cent of the oil-soluble polymerization product of an ester of alpha-methacrylic acid and lauryl alcohol. The cold test of the treated salad oil gave a value of 35 hours.
Example III To a sample of winterized cottonseed oil having a cold test of 15 hours, 0.02 per cent of cetylalpha-methacrylate soluble in oil was added and uniformly distributed therethrough. The oil containing the above crystal-inhibiting agent exhibited a cold test of 60 hours.
Example I V Mayonnaise made with a winterized cottonseed salad oil containing 0.02 per cent n-oetyl-acrylate soluble in oil was placed in a cooler maintained at a temperature of 28 F., and the mayonnaise emulsion did not break until after being held seven days at the said temperature. A similar sample of mayonnaise stood up for two days when placed in a cooler maintained at a temperature of 24 F. The control sample of mayonnaise consisting of a winterized cottonseed oil having the same initial cold test but which was not treated with a crystal-inhibiting agent broke in less than one day at 24 F. and less than three days at 28 F.
Example V A sample of refined and bleached cottonseed oil containing 0.20 per cent lauryl-alpha-methacrylate soluble in oil was placed in a cooler maintained at 45 F. for three days. Upon filtering the sample by gravity through a standard filter cloth, the yield of oil from the sample containing the above crystal-inhibiting agent was 82 per cent. The yield of the control sample of the refined and bleached cottonseed oil was '71 per cent.
Example VI To a sample of white grease was added 0.10 per cent of an ester of alpha-methacrylic acid and octadecyl alcohol soluble in oil and the sample seeded for five days at F. The yield of oil upon pressing the white grease treated in the foregoing manner was per cent. The yield from the control chamber of the white grease containing no crystal-inhibiting agent was 55 per cent.
Example VII A sample of crude sperm oil containing 0.05 per cent n-lauryl acrylate soluble in oil was seeded in 45 F. for six days and then pressed. The yield of winterized sperm oil treated in the foregoing manner was 82 per cent. The yield of the control sample of the sperm oil was per cent.
As hereinbefore mentioned, the above-described crystal inhibitors and modifiers may be added to the glyceride materials before or after winterization. The addition of the crystal modifier before winterization serves primarily to facilitate and improve the Winterizing operation. Although crystal formation is retarded in the presence of the additive, once the crystals are formed they are of such form as to settle quickly, and because of the nature of the crystals a sharp separation of the undesired solids from the liquid constituents of the oil is possible. An advantage of the improved filtering operation is that the yields of oils are greatly increased over the Winterizing process as hitherto practiced. Often it is desirable to add an additional small amount of the additive after the winterization operation so as to replace that which was filtered out along with the high melting glyceride crystals.
In case it is desired to have a glyceride oil of very long cold test, the materials described above are added to the oil after it has been winterized, the extent of lengthening the cold test depending on the quality of oil chosen, the additive being more efiective'in an oil having an original 'longer cold test than in an oil of shorter cold test.
Another important advantage of the invention flows from the use of oil treated with the described agents in emulsions. An emulsion, such as mayonnaise, containing a vegetable oil treated in the foregoing manner will remain stable for muchlonger periods of time than has been hitherto possible to maintain such emulsions.
While the invention described herein has particular application to the manufacture of salad oils, the invention is not limited to such an operation. It should be understood that the invention is useful in treating various fatty glyceride materials wherein a solid or crystalline fraction is separated from a liquid fraction as in the separation of a crystalline fraction from animal oils such as lard oil, oleo oil, sperm oil, and animal fats and greases used in the preparation of lard oil and the like. In treating various vegetable and animal oils it is often desirable to separate a solid fraction such as stearin, palmitin, spermaceti and other high melting point fractions by crystallizing such fraction with or without the presence of a solvent and then separating the crystallized fraction by cold settling, pressing, centrifuging of filtration. The crystal modifying agents herein described may also be used to modify the crystal structure of the solid phase whereby it may be more readily separated from the liquid phase when extracted with a suitable solvent.
Obviously many modifications and variations of the invention hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
I c aim:
l. A glyceride oil composition of improved cold .test, comprising a glyceride oil having incorporated therein a small amount of an oil-soluble product to improve the cold test thereof, said product being the polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl compounds according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula and -(||JOR wherein R is selected from the group consisting of a monovalent hydrocarbon radical containing more than 4 carbon atoms and oxy derivatives thereof.
2. A glyceride oil composition of improved cold test comprising a glyceride oil having incorporated therein a small amount of an oil-soluble product to improve the cold test thereof, said product being a polymerization product of a substituted vinyl compound according to the general formula wherein X is an alkyl radical and R is an allphatic monohydric saturated alcohol radical having more than 12 carbon atoms.
3. A glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having in-v corporated therein a small amount of an oilsoluble product to improve the cold test thereof, said product being the polymerization product of an ester of acrylic acid and a monohydric saturated alcohol containing more than 12 carbon atoms per molecule.
4. A glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having incorporated therein a small amount of an oilsoluble product to improve the cold test thereof, said product being the polymerization product of an alpha-alkyl substituted acrylic acid and a monohydric saturated alcohol containing more than 12 carbon atoms per molecule.
5. A glyceride oil composition of improved cold test comprising a glyceride oil containing relatively high melting point constituents having incorporated therein a small amount of an oil-soluble polymerization product in an amount between .005 and 1.0 per cent by weight to improve the cold test thereof, said product being a member of a group consisting of lauryl, cetyl, and octadecyl esters of alpha-methacrylic acid.
6. In a method of separating a glyceride fatty material into higher and lower melting point constituents by fractionating the liquefied fatty material, the improvement which comprises dispersing throughout the said fatty material a small amountof an oil soluble crystal modifying product to increase the rate at which the relatively high melting point crystals settle, said product being the polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl radicals according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula t oo-R and wherein R. is selected from the group consisting of a monovalent hydrocarbon radical containing more than 4 carbon atoms and oxy derivatives thereof.
7. An improved method of separating a glyceride fatty material into higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product of esters containing a radical selected from the group consisting of vinyl and substituted vinyl radicals according to the general formula wherein X is selected from the group consisting of hydrogen and alkyl and aromatic hydrocarbon radicals and Y is selected from the group having the formula and wherein R is selected from the group consisting of a monovalent hydrocarbon radical containing more than 4 carbon atoms and oxy derivatives thereof, cooling the said fatty material containing the added polymerization product to crystalide fatty material into higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization 7 product of a substituted vinyl compound. having the general formula X CH2=-% JO-R wherein X is an alkyl radical and R is an aliphatic monohydric saturated alcohol radical having more than 12 carbon atoms, cooling the said fatty material containing the added polymerization product to crystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better dofined to facilitate separation from the said lower melting point constituents.
9. An improved method of separating a glyceride fatty material into'higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a "small amount of an oil-soluble polymerization product of an ester of acrylic acid and monohydric saturated alcohol containing more than 12 carbon atoms per molecule, cooling the said fatty material containing the added polymerization product to crystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
10. An improved method of separating a glyceride fatty material into higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product of an alpha-alkyl aryl substituted acrylic acid and monohydric saturated alcohol containing more than 12 carbon atoms per molecule, cooling the said fatty material containing the added polymerization product to crystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
11. An improved method of separating a glyceride fatty material into higher and lower melting point constituents, which comprises dispersing throughout a liquefied glyceride fatty material a small amount of an oil-soluble polymerization product selected from the group consisting of polymerized lauryl esters of alpha-methacrylic acid, cetyl esters of alpha-methacrylic acid, and octadecyl esters of alpha-methacrylic acid, cooling the said fatty material containing the added polymerization product tocrystallize the higher melting point constituents, and separating the said constituents from the lower melting point constituents remaining in the liquid glyceride fatty material, the crystals of said higher melting point constituents formed on cooling being similar and better defined to facilitate separation from the said lower melting point constituents.
' "KARL F. MATTIL.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,079,336 Ralston et a1 May 4, 1937 2,266,591 Eckey Dec. 16, 1941 2,418,668 Royce Apr. 8, 1947 2,518,917 Mattil l Aug. 15, 1950
Claims (1)
1. A GLYCERIDE OIL COMPOSITION OF IMPROVED COLD TEST COMPRISING A GLYCERIDE OIL HAVING INCORPORATED THEREIN A SMALL AMOUNT OF AN OIL-SOLUBLE PRODUCT TO IMPROVE THE COLD TEST THEREOF, SAID PRODUCT BEING THE POLYMERIZATION PRODUCT OF ESTERS CONTAINING A RADICAL SELECTED FROM THE GROUP CONSISTING OF VINYL AND SUBSTITUTED VINYL COMPOUNDS ACCORDING TO THE GENERAL FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US175659A US2610915A (en) | 1950-07-24 | 1950-07-24 | Winterized glyceride oil and process of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US175659A US2610915A (en) | 1950-07-24 | 1950-07-24 | Winterized glyceride oil and process of producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2610915A true US2610915A (en) | 1952-09-16 |
Family
ID=22641123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US175659A Expired - Lifetime US2610915A (en) | 1950-07-24 | 1950-07-24 | Winterized glyceride oil and process of producing the same |
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| Country | Link |
|---|---|
| US (1) | US2610915A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2903363A (en) * | 1954-09-17 | 1959-09-08 | Gerald W Farr | Solvent fractionation of winterized cottonseed oil bottoms |
| US3145223A (en) * | 1961-09-22 | 1964-08-18 | Pennsalt Chemicals Corp | Winterizing glyceride oils |
| US3173936A (en) * | 1962-05-09 | 1965-03-16 | Pennsalt Chemicals Corp | Winterizing glyceride oils |
| US3290340A (en) * | 1963-06-17 | 1966-12-06 | Procter & Gamble | 1-palmitoyl-2, 3-di |
| EP0543356A2 (en) * | 1991-11-22 | 1993-05-26 | Röhm Gmbh | Process for making compositions with improved low temperature behaviour |
| WO1994022320A1 (en) * | 1993-04-02 | 1994-10-13 | Opta Food Ingredients, Inc. | Fat soluble polymers and their use in foods |
| WO1995004122A1 (en) * | 1993-07-27 | 1995-02-09 | Unilever N.V. | Fractionation of triglyceride oils |
| US5621125A (en) * | 1993-07-30 | 1997-04-15 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Fractionation of triglyceride oils utilizing ceramide-base crystallization modifiers |
| US5872270A (en) * | 1994-12-23 | 1999-02-16 | Van Den Bergh Foods Company, Division Of Conopco, Inc. | Fractionation of triglyceride oils |
| US6162934A (en) * | 1997-02-06 | 2000-12-19 | Lipton, Division Of Conopco, Inc. | Fractionation of triglyceride fats |
| US20030068426A1 (en) * | 2001-10-05 | 2003-04-10 | Malaysian Palm Oil Board | Process to prevent and delay clouding in palm olein |
| US11566160B2 (en) | 2020-07-24 | 2023-01-31 | Baker Hughes Oilfield Operations Llc | Additives for winterization of paraffin inhibitors |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2079336A (en) * | 1935-03-01 | 1937-05-04 | Armour & Co | Shortening compound and processes of preparing the same |
| US2266591A (en) * | 1938-10-14 | 1941-12-16 | Procter & Gamble | Process of improving salad oils |
| US2418668A (en) * | 1943-03-30 | 1947-04-08 | Southern Cotton Oil Company | Improvement in winter vegetable oils |
| US2518917A (en) * | 1945-10-22 | 1950-08-15 | Swift & Co | Treatment of glyceride oils |
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1950
- 1950-07-24 US US175659A patent/US2610915A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2079336A (en) * | 1935-03-01 | 1937-05-04 | Armour & Co | Shortening compound and processes of preparing the same |
| US2266591A (en) * | 1938-10-14 | 1941-12-16 | Procter & Gamble | Process of improving salad oils |
| US2418668A (en) * | 1943-03-30 | 1947-04-08 | Southern Cotton Oil Company | Improvement in winter vegetable oils |
| US2518917A (en) * | 1945-10-22 | 1950-08-15 | Swift & Co | Treatment of glyceride oils |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2903363A (en) * | 1954-09-17 | 1959-09-08 | Gerald W Farr | Solvent fractionation of winterized cottonseed oil bottoms |
| US3145223A (en) * | 1961-09-22 | 1964-08-18 | Pennsalt Chemicals Corp | Winterizing glyceride oils |
| US3173936A (en) * | 1962-05-09 | 1965-03-16 | Pennsalt Chemicals Corp | Winterizing glyceride oils |
| US3290340A (en) * | 1963-06-17 | 1966-12-06 | Procter & Gamble | 1-palmitoyl-2, 3-di |
| EP0543356A2 (en) * | 1991-11-22 | 1993-05-26 | Röhm Gmbh | Process for making compositions with improved low temperature behaviour |
| EP0543356A3 (en) * | 1991-11-22 | 1993-10-20 | Roehm Gmbh | Process for making compositions with improved low temperature behaviour |
| WO1994022320A1 (en) * | 1993-04-02 | 1994-10-13 | Opta Food Ingredients, Inc. | Fat soluble polymers and their use in foods |
| US5602265A (en) * | 1993-07-27 | 1997-02-11 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Fractionation of triglyceride oils |
| WO1995004122A1 (en) * | 1993-07-27 | 1995-02-09 | Unilever N.V. | Fractionation of triglyceride oils |
| EP0805196A1 (en) * | 1993-07-27 | 1997-11-05 | Unilever Plc | Fractionation of triglyceride oils |
| US5621125A (en) * | 1993-07-30 | 1997-04-15 | Van Den Bergh Foods Co., Division Of Conopco, Inc. | Fractionation of triglyceride oils utilizing ceramide-base crystallization modifiers |
| US5872270A (en) * | 1994-12-23 | 1999-02-16 | Van Den Bergh Foods Company, Division Of Conopco, Inc. | Fractionation of triglyceride oils |
| US6162934A (en) * | 1997-02-06 | 2000-12-19 | Lipton, Division Of Conopco, Inc. | Fractionation of triglyceride fats |
| US20030068426A1 (en) * | 2001-10-05 | 2003-04-10 | Malaysian Palm Oil Board | Process to prevent and delay clouding in palm olein |
| US11566160B2 (en) | 2020-07-24 | 2023-01-31 | Baker Hughes Oilfield Operations Llc | Additives for winterization of paraffin inhibitors |
| US11814575B2 (en) | 2020-07-24 | 2023-11-14 | Baker Hughes Oilfield Operations Llc | Additives for winterization of paraffin inhibitors |
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