WO1997043907A1 - High stability canola oils - Google Patents
High stability canola oils Download PDFInfo
- Publication number
- WO1997043907A1 WO1997043907A1 PCT/US1997/009326 US9709326W WO9743907A1 WO 1997043907 A1 WO1997043907 A1 WO 1997043907A1 US 9709326 W US9709326 W US 9709326W WO 9743907 A1 WO9743907 A1 WO 9743907A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oil
- acid content
- fatty acid
- hours
- hydrogenated
- Prior art date
Links
- 239000000828 canola oil Substances 0.000 title claims abstract description 78
- 239000003921 oil Substances 0.000 claims abstract description 203
- 235000019198 oils Nutrition 0.000 claims abstract description 203
- 239000000194 fatty acid Substances 0.000 claims abstract description 86
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 60
- 229930195729 fatty acid Natural products 0.000 claims abstract description 60
- 235000019519 canola oil Nutrition 0.000 claims abstract description 56
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 21
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005642 Oleic acid Substances 0.000 claims abstract description 15
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 241000219193 Brassicaceae Species 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 59
- 239000003963 antioxidant agent Substances 0.000 claims description 27
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 26
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 13
- 229960004488 linolenic acid Drugs 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 7
- 230000002068 genetic effect Effects 0.000 claims description 7
- 235000020778 linoleic acid Nutrition 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 6
- 108010005155 delta-12 fatty acid desaturase Proteins 0.000 claims description 6
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 58
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 29
- 235000011331 Brassica Nutrition 0.000 abstract description 10
- 241000219198 Brassica Species 0.000 abstract description 10
- 235000010692 trans-unsaturated fatty acids Nutrition 0.000 abstract description 9
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 abstract description 5
- 235000020982 trans-saturated fatty acids Nutrition 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 21
- 239000000796 flavoring agent Substances 0.000 description 19
- 235000019634 flavors Nutrition 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 150000002978 peroxides Chemical class 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 235000012343 cottonseed oil Nutrition 0.000 description 8
- 239000002385 cottonseed oil Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 7
- 235000006008 Brassica napus var napus Nutrition 0.000 description 7
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 7
- 244000188595 Brassica sinapistrum Species 0.000 description 7
- 244000068988 Glycine max Species 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 235000019645 odor Nutrition 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000003549 soybean oil Substances 0.000 description 7
- 235000012424 soybean oil Nutrition 0.000 description 7
- -1 C24 fatty acid Chemical class 0.000 description 5
- 239000003925 fat Substances 0.000 description 5
- 235000019197 fats Nutrition 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 125000004383 glucosinolate group Chemical group 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 235000003441 saturated fatty acids Nutrition 0.000 description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 238000001030 gas--liquid chromatography Methods 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 240000002791 Brassica napus Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 235000019892 Stellar Nutrition 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000008173 hydrogenated soybean oil Substances 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000003976 plant breeding Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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
- C11B7/00—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils
- C11B7/0075—Separation of mixtures of fats or fatty oils into their constituents, e.g. saturated oils from unsaturated oils by differences of melting or solidifying points
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/06—Preservation of finished products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
Definitions
- the present invention relates to hydrogenated canola oil having improved oxidative stability and performance attributes, and to Brassica seeds, plant lines and progeny thereof from which such an oil is derived.
- Canola oil has the lowest level of saturated fatty acids of all vegetable oils. As consumers become more aware of the health impact of lipid nutrition, consumption of canola oil in the U.S. has increased.
- canola oil extracted from many natural and commercial varieties of rapeseed contains a relatively high ⁇ -linolenic acid content (C l ⁇ :3 ; all cis 9,12,15 octadecatrienoic acid; ALA) .
- the oil is unstable and easily oxidized during cooking, which in turn creates off-flavors and compromises the sensory characteristics of foods cooked in such oils. It also develops unacceptable off odors and rancid flavors during storage.
- Hydrogenation can be used to improve performance attributes by lowering the amount of linoleic and ⁇ - linolenic acids in the oil. Hydrogenation converts cis mono- and cis poly-unsaturated fatty acids, into trans- fatty acids and saturated fatty acids. Saturated and trans-fatty acids are not desirable for health reasons. It would be desirable to reduce the level of polyunsaturates in order to improve the oxidative stability and the shelf life of these oils while minimizing the increase in trans-fatty acids and saturated fatty acids. Different vegetable oils can be blended to reduce the ⁇ -lmolenic acid content and improve performance attributes.
- ⁇ -Lmolenic acid has been reported to have a relatively low oxidative stability. In general, the oxidative stability of oleic acid is about 10 fold greater than that of Imoleic acid, and the oxidative stability of Imoleic acid is about 2 fold greater than that of linolemc acid.
- an oil has a Mettler Drop Point (MDP) of more than about 30°C, a trans-fatty acid content of about 36% or less, an IV of from about 68 to about 75 and a minimum AOM value of about 280 hours in the absence of added antioxidants.
- MDP Mettler Drop Point
- this oil is produced from a starting oil extracted from Brassi caceae seeds that have a fatty acid profile comprising an oleic acid content of about 72% to about 80%, a linoleic acid content of about 5% to about 12% and an ⁇ -linolenic acid content of about 1% to about 5%.
- the fatty acid profile in such seeds may be controlled by heritable genetic change that is present in seeds designated as IMC-130 and deposited as ATCC accession number 75446.
- the hydrogenated oil can be separated to obtain a liquid oil fraction that has an MDP of less than about 20°C, a trans-fatty acid content of about 31% or less, an IV of from about 72 to about 77 and a minimum AOM value of about 290 hours in the absence of added antioxidants.
- the liquid oil fraction can have a minimum AOM value about 330 hours.
- a hydrogenated canola oil- has an MDP of more than about 30°C, a trans- fatty acid content of about 40% or less, an IV of from about 68 to about 77, a total C18:l content of about 80% or greater and a minimum AOM value of about 300 hours in the absence of - 4 - added antioxidants.
- the hydrogenated oil can be separated to obtain a liquid oil fraction that has an MDP of less than about 20°C, a trans-fatty acid content of about 40% or less, an IV of from about 75 to about 81, a total C18:l fatty acid content of about 86% or greater and a minimum AOM value of about 350 hours in the absence of added antioxidants.
- Such an oil may have a total saturated fatty acid content of less than about 9.5%.
- such an oil is produced from a starting oil extracted from Brassicaceae seeds having a fatty acid profile comprising an oleic acid content of about 80% to about 87%, a Imoleic acid content of about 2% to about 5% and an ⁇ -linolemc acid content of about 1% to about 4%.
- Such seeds can possess defects in both the first and second forms of delta-12 fatty acid desaturase found in Brassi caceae lines.
- the fatty acid profile may be controlled by heritable genetic change m a line designated 6Q4275A-1-4 and having ATCC accession number 97569.
- a method of producing a canola oil is disclosed herein.
- the method comprises the steps of providing a starting refined, bleached non- hydrogenated canola oil that has an oleic acid content of from about 72% to about 80%, a Imoleic acid content of from about 5% to about 12% and an ce-lmolenic acid content of from about 1% to about 5%; and hydrogenating the starting oil to an IV of from about 68 to about 75.
- the hydrogenated oil has an MDP of more than about 30°C, a trans-fatty acid content of about 36% or less and a minimum AOM value of about 280 hours in the absence of added antioxidants.
- the method may further comprise the step of separating the hydrogenated oil into a solid fraction and a liquid canola oil fraction.
- the liquid fraction has an MDP of less than about 20°C, a trans- fatty acid content of less than about 31%, an IV of from about 72 to about 77 and a minimum AOM value of about 290 hours in the absence of added antioxidants.
- the starting oil may be extracted from Brassi caceae seeds designated IMC-130 and having ATCC accession number 75446.
- Another method of producing a canola oil comprises the steps of providing a starting refined, bleached non- hydrogenated canola oil that has an oleic acid content of from about 80% to about 87%, a Imoleic acid content of from about 2% to about 5% and an ⁇ -l ⁇ nolen ⁇ c acid content of from about 1% to about 4%; and hydrogenating the starting oil to an IV of from about 68 to about 77.
- the hydrogenated oil has an MDP of more than about 30°C, a trans-fatty acid content of about 40% or less and a minimum AOM value of about 300 hours in the absence of added antioxidants.
- the method may further comprise the step of separating the hydrogenated oil into a solid fraction and a liquid canola oil fraction.
- the liquid fraction has an MDP of less than about 20°C, a trans- fatty acid content of about 40% or less, an IV of from about 75 to about 81, a total C18-.1 fatty acid content of greater than about 85% or greater and a minimum AOM value of about 350 hours in the absence of added antioxidants.
- the starting oil may be extracted from Brassi caceae seeds having defects m both the first and second forms of delta-12 fatty acid desaturase.
- the starting oil may be extracted from Brassicaceae seeds designated 6Q4275A-1-4 and having ATCC accession number 97569.
- the present invention provides a hydrogenated canola oil that is low m saturated fatty acids and low in trans- fatty acids.
- the oil has superior oxidative stability, sensory characteristics and frying attributes when compared to known canola oils.
- the modified oil is liquid at or below room temperature.
- total saturated fatty acids include myristic (C14:0) , palmitic (C16:0) , stearic (C18:0) , arachidic (C20:0) , behenic (C22:0) , and lignoceric (C24:0) acids.
- Trans-fatty acids include any trans isomer of a C 14 through C 24 fatty acid.
- Total C18:l fatty acid refers to isomers of C18 monounsaturated fatty acids.
- Total CIS:2 fatty acid refers to isomers of C18 diunsaturated fatty acids.
- Total C18:3 fatty acids refers to isomers of C18 triunsaturated fatty acids.
- “functionality” or “performance attributes” means properties or characteristics of the canola oil and includes flavor stability, fry stability, and oxidative stability.
- Oxidative stability relates to how easily components of an oil oxidize, and can be measured, for example, by instrumental analyses such as Active Oxygen Method (AOM) American Oil Chemists' Society Official Method Cd 12-57 for Fat Stability:Active Oxygen Method (rev'd 1989) ; Rancimat (Laubli, M.W. and Bruttel, P.A., JOACS 63:792-795 (1986)) and Oil Stability Index (OSI) values, AOCS Method Cd 12b-92.
- AOM Active Oxygen Method
- Rancimat Libli, M.W. and Bruttel, P.A., JOACS 63:792-795 (1986)
- OSI Oil Stability Index
- “Canola” refers to rapeseed (Brassica) that has an erucic acid (C 22 i) content of at most 2 percent by weight based on the total fatty acid content of a seed, preferably at most 0.5 percent by weight and most preferably essentially 0 percent by weight and that produces, after crushing, an air-dried meal containing less than 30 micromoles ( ⁇ mol) of glucosinolates per gram of defatted (oil-free) meal.
- a starting canola oil for use in the invention typically has been refined and bleached by methods known in the art.
- the starting refined, bleached (RB) canola oil may be further processed before hydrogenation, provided that such processing does not interfere with the subsequent hydrogenation process.
- a starting canola oil preferably is derived from seeds having a low total glucosinolate content .
- an RB oil derived from seeds having a low total glucosinolate content generally has a lower sulfur content, compared to an RB oil derived from seeds having a high total glucosinolate content.
- Brassi caceae lines producing seeds having a low total glucosinolate content are described m U.S. Application Serial No. 08/290,660, incorporated herein by reference.
- the sulfur content of the starting oil is generally less than about 3.8 ppm, preferably less than about 3.0 ppm. In preferred embodiments, the oil has a sulfur content of less than about 1.5 ppm.
- an oil of the invention is hydrogenated such that the oil has a Mettler Drop Point (MDP) of from about 30°C to about 45°C, preferably less than about 40°C, more preferably less than about 35°C.
- the iodine value (IV) is about 68 to about 75, preferably from about 70 to about 73.
- Such an oil possesses a relatively low trans-fatty acid content of less than about 36% wt . %. In preferred embodiments the trans-fatty acid content is less than about 31%, preferably less than about 27%, more preferably less than about 25%.
- the stearic acid content of an oil of this embodiment typically is from about 10% to about 15%, preferably from about 10% to about 12%.
- the total saturated fatty acid content is from about 10% to about 20%, preferably from about 13% to about 18%.
- the total C18:l fatty acid content of such an oil is greater than about 75%, preferably greater than about 80%.
- Such an oil has a high oxidative stability.
- oxidative stability is measured by the active oxygen method (AOM)
- the AOM value is from about 280 hours to about 350 hours, preferably from about 300 hours to about 350 hours. In preferred embodiments, the AOM value is from about 325 hours to about 350 hours.
- a starting canola oil is hydrogenated and fractionated to obtain an oil that is liquid at or below room temperature.
- an oil has a MDP of less than about 20°C, preferably less than about 18°C.
- An oil of the second embodiment possesses a low trans-fatty acid content of from about 20% to about 33%, preferably from about 23% to about 26%.
- An oil of this embodiment also possesses a low saturated fatty acid content.
- the stearic acid content typically is from about 7.5% to about 9.5%.
- the total saturated fatty acid content is from about 10% to about 14%, preferably from about 11% to about 12%.
- An oil of this embodiment possesses a total C18:l fatty acid content of about 79% to about 87%, preferably from about 81% to about 83%.
- the IV is from about 72 to about 77, preferably from about 73 to about 76. Such an oil has a high oxidative stability
- An oil of these embodiments can be produced, for example, by hydrogenation of a starting canola oil extracted from Brassica seeds having a fatty acid profile comprising an oleic acid content of about 72% to about 80%, a linoleic acid content of about 5% to about 12% and an ⁇ -linolenic acid content of about 1% to less than about 5%.
- Seeds having the indicated fatty acid profile are produced, for example, by canola lines IMC-130 (ATCC Accession No. 75446) and A13.30137, disclosed in U.S. Patent Application 08/425,108, filed June 6, 1995, which is incorporated herein by reference.
- Progeny of crosses between a first Brassi ca line (such as IMC-130) and an agronomically elite line are also suitable for producing such a starting canola oil, provided that the progeny possess the fatty acid profile of the first Brassica line and that the starting oil derived from the progeny can be hydrogenated as disclosed herein. Plant breeding techniques for producing such progeny are known in the art.
- starting canola oil has been hydrogenated such that the oil has a MDP of about 30°C to about 45°C, preferably less than about 40°C, preferably less than about 35°C.
- the IV is about 68 to 77, preferably from about 70 to 75.
- Such an oil possesses an unusually high oxidative stability of from about 300 AOM hours to about 500 AOM hours, preferably from about 400 hours to about 500 hours, more preferably a minimum of about 425 hours.
- Such an oil possesses a stearic acid content of about 5% to about 15%, a saturated fatty acid content of about 8% to about 20% and a trans-fatty acid content of about 20% to about 45%, preferably from about 25% to about 40%, more preferably from about 27% to about 32%.
- the total C18 : 1 content is from about 78% to about 88%, preferably from about 80% to about 85%.
- a starting canola oil has been hydrogenated and fractionated to obtain an oil that has a MDP of less than about 20°C, preferably less than about 18°C.
- the oil has an IV of about 75 to about 81, preferably from about 78 to about 80.
- An oil of this embodiment possesses a low trans- fatty acid content of from about 20% to about 35%, preferably from about 25% to about 30%, more preferably about 30%.
- An oil of this embodiment also possesses a low saturated fatty acid content.
- the stearic acid content of such an oil is from about 3% to about 6%, preferably from about 4% to about 5%.
- the total saturated fatty acid content is typically less than about 10%, preferably less than about 9.5%, more preferably about 9% or less.
- An oil of this embodiment possesses a total C18:l fatty acid content of greater than about 85%, preferably greater than about 86%, more preferably greater than about 87%, and up to about 92%.
- An oil of this embodiment possesses a very high oxidative stability.
- such an oil possesses an AOM value of from about 350 hours to about 550 hours, preferably from about 400 hours to about 550 hours, more preferably a minimum of about 450 AOM hours.
- An oil of the latter two embodiments may be produced by hydrogenation of a canola oil extracted from Brassi ca seeds.
- Such seeds have a fatty acid profile comprising an oleic acid content of from about 80% to about 87%, a Imoleic acid content of from about 2% to about 5% and an alpha-lmolenic acid content of from about 1% to about 4%.
- Brassica seeds having such a fatty acid profile may be produced, for example, by canola lines that contain defects in both fad.2 genes of
- Brassica i.e., delta-12 fatty acid desaturase genes. Lines having defects m both delta-12 fatty acid desaturase genes are described m U.S. Patent Application Serial No. 08/572,027, filed December 14, 1995, which is incorporated herein by reference.
- An illustrative example of a Brassica line suitable for preparing a starting canola oil for the latter two embodiments is a line known as 6Q4275A-1-4 (ATCC Accession No. 97569) , also referred to herein as 6Q4275.
- Progeny of crosses between a first Brassica line (such as 6Q4275) and an agronomically elite line are also suitable for producing such a starting canola oil, provided that the progeny possess the fatty acid profile of the first Brassi ca line and that the oil extracted from the progeny can be hydrogenated as disclosed herein. Means for making such crosses and producing progeny are known m the art.
- progeny line suitable for making the starting canola oil is 93GS34-179, a line derived from a cross of 6Q4275 X Cyclone.
- Line 93GS34- 179 (also referred to herein as 93GS or 93GS34) retains the fatty acid composition of 6Q4275 and has desirable agronomic characteristics.
- Applicants have made a deposit of seeds of the Brassica lines indicated in Table 1 with the American Type Culture Collection (ATCC) , Rockville, Maryland 20853 U.S.A.
- the seeds deposited with the ATCC are taken from the same deposit maintained by Cargill, Incorporated, Wayzata, Minnesota, since prior to the filing date of this application.
- These deposits will be maintained upon issuance of a patent without restriction in the ATCC depository, which is a public depository, for a period of 30 years, or 5 years after the most recent request, or for the effective life of the patent, whichever is longer, and will be replaced if the deposit becomes non- viable during that period.
- canola varieties suitable for preparing an oil of the invention may be obtained from progeny of the above-identified lines by known canola breeding methods including, but not limited to, outcrossmg, backcrossmg, recurrent selection, microspore culture and genetic transformation. Progeny are selected that retain the genetic loci conferring the fatty acid profile and oil quality characteristics of the parent due to heritable genetic change that is present m the parent.
- a method according to the invention comprises hydrogenation of a refined, bleached (RB) rapeseed oil under mild reaction conditions.
- a nickel catalyst typically is used to promote hydrogenation.
- a suitable catalyst has a high lmolenic selectivity and a low trans-isomerization selectivity m order to use lower reaction temperatures (e.g., 155°C) . Lower reaction temperatures permit hydrogenation of polyunsaturates in the oil while minimizing the formation of trans and saturated fatty acids.
- a suitable reaction temperature is from about 90°C to about 180°C, preferably from about 140°C to about 160°C.
- a high linoleic selectivity is also desirable m the catalyst.
- Suitable catalysts include Nysosel-545 and Nysosel-655 nickel catalysts (Engelhard Corporation, Jackson, MS) .
- a suitable catalyst concentration is about 0.13 wt%. At this concentration, glucosmolates and other sulfur-contaming compounds inherent in canola oil do not significantly interfere with the hydrogenation reaction. Hoffman, G. , The Chemistry and Technology of Edible Oils and Fats and High Fat Products, Academic Press, London, pp. 206-217 (1989) .
- the hydrogenated material is fractionated to obtain a liquid oil fraction having a low trans-fatty acid content and a low saturated fatty acid content.
- the unfractionated product is separated after hydrogenation into a solid fraction and a liquid canola oil fraction by techniques known in the art, e.g., plate and frame filtration, dry fractionation, or pressure filtration. Dry fractionation procedures may be used to separate the liquid and solid fractions of partially hydrogenated oils, e.g., a partially hydrogenated oil is crystallized at 21°C for 15 hours, cent ⁇ fuged, and the liquid is separated. Alternatively, the liquid from the crystallized mixture is separated by pressure or vacuum filtration.
- Pressure filtration typically uses an inert gas, e.g., N 2 from about 14.7 psi to about 300 psi (101.3 kPa to 2067 9 kPa) . See, e.g., EP 262 113, WO95/04123, and W095/26391. Liquid yields tend to be higher with pressure filtration. In addition, a combination of the above procedures can be used to separate the liquid and solid fractions.
- the hydrogenated and hydrogenated/fractionated liquid canola oils disclosed herein advantageously have a lower trans-fatty acid content compared to high oxidative stability soybean oils and cottonseed/soybean oil blends.
- Such liquid canola oils can have 30-40% less trans-fatty acids compared to the trans-fatty acid content of such soybean and soybean/cottonseed oils.
- the MDP of such hydrogenated and fractionated canola oils can be more than 5°C lower than commercially available high AOM soybean or soybean/ cottonseed oils, (10°C MDP versus 16°C MDP) .
- the partially hydrogenated canola oils disclosed herein unexpectedly have high AOM values, despite the fact that the total C18:3 content is generally greater than 0.1% by weight, typically ranging from about 0.2% to about 0.8% by weight for oils having an IV of about 68 to about 80. At a given AOM value, a higher total C18:3 content, m combination with a low trans-fatty acid and total saturated fatty acid content, is preferred for nutritional reasons.
- the canola oils disclosed herein achieve such a desired combination of properties.
- Hydrogenated and hydrogenated/fractionated canola oils disclosed herein may comprise substantially all of a final product. If desired, such oils can have various compounds added to form a final product, e.g., stabilizers, flavorings, emulsifiers, anti-spattering agents, colorants and/or antioxidants. Addition of antioxidants to hydrogenated or hydrogenated/fractionated canola oils disclosed herein significantly increases oxidative stability.
- Hydrogenated and hydrogenated/fractionated canola oils may be used in food applications, e.g., frying oils, margarines or spreads, coating agents or confectionary fats.
- such oils may be used m industrial applications, e.g., energy transfer agents and friction- reducing agents.
- Energy transfer fluids include hydraulic fluids and lubricants. Friction-reducing fluids include cutting fluids, processing oils, motor oils and annealing agents.
- the hydrogenated and hydrogenated/fractionated oils disclosed herein provide an extended useful life and increased storage stability because of their high oxidative stability. Viscosity is more easily controlled with such oils compared to vegetable oils having lower oxidative stability.
- the oils disclosed herein are biodegradable, thereby providing environmental benefits. If desired, the oils disclosed herein may be blended or mixed with other oils to meet the performance characteristics desired m the final product.
- IMC-129 (a high oleic acid variety) and IMC-01 (a low ff-hnolenic acid variety) were the parent lines crossed to generate IMC-130.
- IMC-01 is described in U.S. Patent application Serial No. 08/290,660, incorporated herein by reference
- IMC-129 is described in U.S. Patent application Serial No. 08/416,497, incorporated herein by reference .
- IMC-130 seed was crushed and refined, bleached deodorized oil was prepared by a pilot plant process as described in Example 1 of U.S. Patent application
- Fatty Acid Composition of Refined, Bleached and Deodorized Oils Fatty Acid Composition (%) Variety C 16 0 C 18 0 C 1B ⁇ C 18 2 C 18 3 Total
- IMC-130, IMC-144, IMC-01, and IMC-129 oils were evaluated for AOM hours under the methods outlined in the American Oil Chemists' Society (AOCS) Official Method Cd 12-57 for Fat Stabili ty : Acti ve Oxygen Method (rev'd. 1989) . Each oil sample was prepared m duplicate.
- AOCS American Oil Chemists' Society
- IMC-130 oil was found to have significantly higher AOM hours after similar pilot plant processing than other oils tested
- the greater oxidative stability of IMC-130 oil compared to IMC-144 oil or IMC- 01 oil can be attributed to a lower polyunsaturated fatty acid content.
- the greater oxidative stability of IMC-130 oil compared to IMC-129 oil cannot be attributed solely to fatty acid composition because IMC- 130 oil and IMC-129 oil have similar fatty acid compositions.
- IMC-130 oil can have slightly higher levels of polyunsaturates (Table 2) These results indicate that oxidative stability is not solely related to fatty acid composition.
- IMC-129 and IMC-130 seed were crushed and processed by commercial processing methods to form refined, bleached, deodorized canola oil as described in Example 5 of U.S. Application Serial No. 08/425,108, filed June 6, 1995, incorporated herein by reference.
- Oxidative stability of each oil was determined by measuring the increase m Peroxide Value and in para- Anisidme Value generated under accelerated aging conditions using a modified Schaal oven test.
- the test oil ⁇ 200 g) was placed in an 500 ml uncovered amber glass bottle with a 4.3 cm opening, and placed m a 60°C convection oven.
- One bottle was prepared for each evaluation. Results are found in Table 4 and Table 5.
- the peroxide value was measured using the AOCS
- the para-amsidme value was measured using the AOCS Official Method Cd 18-90.
- Aldehydes generated from the oxidation of the triacylglycerol was measured by the p-anisidme value.
- the p-anisidme value was 100 times the optical density measured at 350 nm in a 1 cm cell of a solution containing 1.00 g of the oil in 100 ml of a mixture of solvent and reagent according to the method referenced, and is absorbance/g.
- Reduced development of aldehydes during storage is an indicator of improved oxidative stability of the oil. - 18 -
- the IMC-130 deodorized oil was analyzed for fatty acid composition via gas chromatography.
- the percent fatty acids were C 160 of 3.6%, C 18.0 of 2.2%, C 1B ⁇ of 74.3%, C 18;2 of 11.9%, C 183 of 4.8% and total polyunsaturated of 16.7%.
- These data can be compared to the values for IMC- 144, IMC-129 and Brand A oils as shown m Table 2.
- the data demonstrate that IMC-130 maintains reduced levels of linolenic acid (C 18 2 ) , ⁇ -linolenic (C 18 3 ) , and total polyunsaturated fatty acids when compared to canola oils IMC-144 and Brand A.
- Table 6 provides data on the AOM hours of the IMC- 130 oil processed as described above (commercial processing) , compared to IMC-129, IMC-144, and IMC-01.
- the IMC-130 oil was evaluated for AOM hours under the methods outlined in the American Oil Chemists' (AOCS) Official Method Cd 12-57 for Fat Stability: Active Oxygen Method (rev'd 1989) .
- the higher AOM hours of IMC- 130 reflects its greater oil stability. Each oil sample was prepared in duplicate.
- IMC-130 and 6Q4275 using pilot plant procedures or commercial plant procedures.
- Hydrogenation consumption was calculated by closing the hydrogen valve to the reactor and recording the pressure drop of hydrogen from either 30 or 45 psi for a 5 minute interval .
- Hydrogenation reaction conditions for each reaction are shown in Table 8.
- the product was stirred for 10 minutes with 0.5 wt% Celite (bleaching earth) and filtered through a Buchner funnel using a Whatman #5 and GF/F filter paper and 2-3 mm of silica gel (enough to cover the filter paper) . This method was shown to reduce the amount of nickel catalyst m the filtrate down to 0.2 ppm. If desired, a citric acid treatment can be used to further reduce the nickel down to ⁇ 0.11 ppm. An aliquot of the filtrate was then analyzed for IV, fatty acid composition, and oxidative stability as described below.
- the hydrogenated material was melted on a steam bath and homogenized. Samples were then placed in centrifuge tubes, balanced, sealed, and left m a water bath at 13°C for 15 hours. The following day, the tubes were taken out and centrifuged at 10,000 RPM (10,000xG) for 20 minutes in a Beckman J-21C centrifuge. The supernatant was decanted and labeled the liquid fraction. The pellet was melted by steam bath, poured into an appropriate container, and labeled the solid fraction. Each fraction was analyzed as described below.
- Trans-fatty acid levels and IV values of the final hydrogenated products, liquid fractions and solid fractions were determined by gas liquid chromatography (GLC) .
- the GLC method is described in AOCS Official Method Ce lc-89 (1991) .
- Schaal Oven Stability was calculated from peroxide values.
- the fatty acid composition, iodine values, and tocopherol content also were determined.
- Each sample was tested at 110°C for oxidative stability using an Oxidative Stability Index instrument, Omnion, Inc., Rockland, MA.
- AOM hours were calculated using the OSI software according to the manufacturers instructions.
- the Oxidative Stability Index instrument was used to determine the oxidative stability of oils and fats according to AOCS Official Method Cd 12b-92 (revised 1993) .
- the method is an automated replacement for the Active Oxygen Method (AOM) procedure, AOCS Official Method Cd 12-57.
- a reaction temperature of 155°C kept the average hydrogenation rate >2 psi/mm with an increase in trans- fatty acid formation ranging between 21% to 35% (Tables 8 and 9) .
- the reaction temperature and the trans content can be lowered further by choosing a catalyst having higher activity and higher Imolenic acid and Imoleic acid selectivity.
- a hydrogenation pressure of 45 psi gave the best consumption rate of hydrogen in the reaction.
- the fatty acid composition, iodine values and oxidative stability of hydrogenated and hydrogenated /fractionated oils are shown in Table 9.
- the AOM value was 351 hours for the liquid fraction of reaction 2689-28-L.
- RBD 6Q4275 canola oil had an AOM value of 307 hours in the liquid fraction of reaction 2695-11-L.
- the results shown in Table 9 demonstrate that a high oxidative stability canola oil that is liquid at or below room temperature can be produced from a starting IMC-130 oil or a starting 6Q4275 oil.
- a Pounds per square inch in the Parr Reactor.
- b Iodine Values determined by AOCS Tg 1a-64 methodology.
- F refers to the hydrogenated product
- S refers to the solid fraction
- L refers to the liquid after dry fractionation/centrifugation at 1
- b The fatty acid composition determined by AOCS method Ce 1c-89 methodology.
- c IV, determined by AOCS method Ce 1c-89.
- d AOM hours as calculated from Oil Stability Index values.
- the RBD 6Q4275 canola oil used in this Example was seven months old and had a PV of 1.67 meq/kg. Water washing and Celite treatment were carried out on the RBD 6Q4275 oil to remove citric acid. The 6Q4275 oil was extracted 3 times with 20% (v/v) water to oil. After extraction, the oil was mixed for 10 minutes with 0.5% Celite and filtered through glass membrane filter paper that was layered with a thin coat of silica gel. The Celite addition and filtration procedure was repeated two more times to remove any polar contaminants.
- the reaction was heated to 155°C and the hydrogen pressure was equilibrated at 45 psi. Hydrogen usage rate was calculated by closing the hydrogen valve to the reactor and recording the pressure drop of hydrogen from 45 psi for a 5 minute interval. After completing the hydrogenation, the samples were treated with Celite and filtered through silica gel as described in Example 3. The reaction times, hydrogenation pressures and other reaction conditions are shown in Table 10.
- Example 3 IV and trans-fatty acid contents of hydrogenated and hydrogenated/fractionated products were determined by GLC as described in Example 3. Oxidative stability and fatty acid composition were determined as described m Example 3. The wmterizmg/centrifugation fractionation procedure was the same as in Example 3 , except that the bath temperature was set at 21°C and centrifugation was carried out for 25 minutes.
- Table 11 summarizes the results for hydrogenated and hydrogenated/fractionated IMC-130 canola oil.
- the IV ranged from about 66-76; the trans-fatty acid content was between 26% to 29%.
- the saturated fatty acid content for the liquid fraction was less than 14%.
- Hydrogenated 6Q4275 and IMC-130 oils had high oxidative stability values even though the total C18:3 fatty acid content was greater than 0.2%. In contrast, known partially hydrogenated canola oils typically have less than 0.2% total C18:3 at correspondingly high oxidative stability values. Characteristics of the liquid fraction of 2 hydrogenated IMC-130 oil samples are shown in Table 13. Both oil samples had a lower trans-fatty acid content compared to commercially available soybean and soybean/cottonseed oils of similar oxidative stability. The 65A-L oil (Table 13) had a superior flavor score, lower color score, lower SFI and lower MDP compared to commercially available soybean and cottonseed/soybean oils of similar oxidative stability. 6Q4275 oils also have superior properties compared to commercially available cottonseed/soybean oils of similar oxidative stability.
- Example 3 The non-hydrogenated oils of Example 3 were mixed with the antioxidants indicated m Table 14. Samples were then tested for oxidative stability as described in Example 3. Flavor scores were determined by AOCS method Cg 2-83. A score of greater than 7 indicates a slight to bland flavor, and is a preferred oil quality. As shown in Table 14, the oxidative stability of non-hydrogenated IMC-130 oil increased up to 2-fold when antioxidants were added, yet maintained preferred flavor scores. Non-hydrogenated 6Q4275 oil increased 3-fold m oxidative stability and had an improved flavor score when antioxidant TBHQ was added. Hydrogenated and hydrogenated/fractionated IMC-130 and 6Q4275 oils also show significant increases in oxidative stability when antioxidants are added, while maintaining superior flavor scores.
- IMC-130 and 93GS34-179 seed were crushed and processed by commercial processing methods to produce refined, bleached and deodorized IMC-130 and refined and bleached 93GS34-179. Typical profiles of these starting oils are shown in Table 15.
- the individual samples of hydrogenated IMC-130 and 93GS oil were bleached and deodorized m the following manner.
- the oil was heated to 60-65°C and 0.1% TriSyl S627, 1.0% of Supreme 120 FF bleaching clay was added and mixed. Oil temperature was increased to 108-112°C under vacuum. After mixing for 20 minutes, the samples were cooled to 70-75°C and 1.0 kg of filter aid was added. The samples were filtered using a stainless steel filter press (T.shriver & Co. Ltd.) Subsequently, the bleached oil was deodorized at 250°C for IMC-130 and 260°C for 93GS, using a Johnson-Loft packed tower contmous deodorizer.
- the fatty acid profile and iodine values of the hydrogenated products was determined as described in Example 3. The results are reported in Table 17. The average oxidative stability for the two IMC-130 samples was about 386 AOM hours, whereas the average oxidative stability of the two 93GS samples was about 326 AOM hours. Using refined and bleached IMC-130 oil instead of refined, bleached and deodorized IMC-130 oil may further increase the oxidative stability of the final product .
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fats And Perfumes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97926830A EP0921728B1 (en) | 1996-05-21 | 1997-05-21 | High stability canola oils |
DE69735630T DE69735630T2 (en) | 1996-05-21 | 1997-05-21 | CANOLA OILS WITH HIGH STABILITY |
JP54298997A JP4323569B2 (en) | 1996-05-21 | 1997-05-21 | Very stable canola oil |
CA002255628A CA2255628C (en) | 1996-05-21 | 1997-05-21 | High stability canola oils |
AU31505/97A AU724638B2 (en) | 1996-05-21 | 1997-05-21 | High stability canola oils |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/651,684 US5885643A (en) | 1996-05-21 | 1996-05-21 | High stability canola oils |
US08/651,684 | 1996-05-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997043907A1 true WO1997043907A1 (en) | 1997-11-27 |
Family
ID=24613804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/009326 WO1997043907A1 (en) | 1996-05-21 | 1997-05-21 | High stability canola oils |
Country Status (8)
Country | Link |
---|---|
US (1) | US5885643A (en) |
EP (1) | EP0921728B1 (en) |
JP (1) | JP4323569B2 (en) |
AT (1) | ATE322171T1 (en) |
AU (1) | AU724638B2 (en) |
CA (1) | CA2255628C (en) |
DE (1) | DE69735630T2 (en) |
WO (1) | WO1997043907A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002542829A (en) * | 1999-05-03 | 2002-12-17 | カルジーン エルエルシー | Method for producing plants with higher oleic acid content |
EP1402781A1 (en) * | 2001-06-05 | 2004-03-31 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Coated organic acid preparations for preserving bakery products |
WO2004111164A1 (en) * | 2003-06-10 | 2004-12-23 | Archer-Daniels-Midland Company | Method for the production of fatty acids having a low trans-fatty acid content |
EP1753298A2 (en) * | 2004-04-29 | 2007-02-21 | GFA Brands, Inc. | Oxidative stabilization of omega-3 fatty acids in low linoleic acid-containing peanut butter |
EP1802563A1 (en) * | 2004-09-16 | 2007-07-04 | Cargill, Incorporated | Canola oil from hybrid brassica varieties |
US8637740B2 (en) | 2008-11-04 | 2014-01-28 | Dow Agrosciences, Llc. | Omega-9 quality Brassica juncea |
EP2724620A1 (en) * | 2012-10-26 | 2014-04-30 | Walter RAU Neusser Öl und Fett AG | Oleochmical composition |
US9185861B2 (en) | 2010-05-25 | 2015-11-17 | Cargill, Incorporated | Brassica plants yielding oils with a low alpha linolenic acid content |
US9334483B2 (en) | 2009-12-18 | 2016-05-10 | Cargill, Incorporated | Brassica plants with mutant FATA2 alleles yielding oils with a low total saturated fatty acid content |
US9695434B2 (en) | 2010-05-25 | 2017-07-04 | Cargill, Incorporated | Brassica plants yielding oils with a low alpha linolenic acid content |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5949017A (en) * | 1996-06-18 | 1999-09-07 | Abb Power T&D Company Inc. | Electrical transformers containing electrical insulation fluids comprising high oleic acid oil compositions |
CA2816178A1 (en) | 1998-10-02 | 2000-04-13 | Cargill, Incorporated | Vegetable oil having elevated stearic acid content |
US6713117B1 (en) * | 1998-10-02 | 2004-03-30 | Dharma Kodali | Vegetable oil having elevated stearic acid content |
US7592015B2 (en) * | 1999-06-04 | 2009-09-22 | Consejo Superior De Investigaciones Cientificas | Use of high oleic high stearic oils |
US6388113B1 (en) | 1999-06-04 | 2002-05-14 | Consejo Superior De Investigaciones Cientificas ( Csic) | High oleic/high stearic sunflower oils |
ES2265945T3 (en) * | 1999-06-04 | 2007-03-01 | Consejo Superior De Investigaciones Cientificas | PLANTS, SEEDS AND SUNFLOWER OILS WITH A HIGH CONTENT OF OLEICO AND HIGH OF ESTEARICO. |
WO2001024617A1 (en) * | 1999-10-01 | 2001-04-12 | The State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Low erucic acid mutant meadowfoam plants and oils produced from them |
JP4799727B2 (en) * | 2000-10-31 | 2011-10-26 | 花王株式会社 | Production of oleic acid |
MY128504A (en) * | 2001-09-25 | 2007-02-28 | Pennzoil Quaker State Co | Environmentally friendly lubricants |
US7585990B2 (en) * | 2003-07-31 | 2009-09-08 | Cargill, Incorporated | Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils |
US7820841B2 (en) * | 2003-07-31 | 2010-10-26 | Cargill, Incorporated | Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils |
US20080199582A1 (en) * | 2004-07-02 | 2008-08-21 | Cargill, Incorporated | Fat Products Containing Little or No Trans Fatty Acids |
NO325550B1 (en) * | 2006-10-31 | 2008-06-16 | Due Miljo As | Procedures for the purification of oils and their use in food and feed |
US20110159074A1 (en) * | 2009-12-30 | 2011-06-30 | Raphael Warren | Wipe Article Comprising Lotion Composition Comprising Omega-6 Fatty Acid And Method Of Improving Skin Barrier Function |
SG2014010045A (en) * | 2011-08-24 | 2014-08-28 | J Oil Mills Inc | Oxidized partially hydrogenated oil |
CA2883897C (en) * | 2012-09-11 | 2021-05-04 | Dow Agrosciences Llc | Omega-9 canola oil blended with dha |
KR102098155B1 (en) * | 2012-11-14 | 2020-04-07 | 제이-오일 밀스, 인코포레이티드 | Sweetness and/or milk flavor enhancer |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992003919A1 (en) * | 1990-08-30 | 1992-03-19 | E.I. Du Pont De Nemours And Company | Seeds, plants and oils with altered fatty acid profiles |
WO1994015478A1 (en) * | 1992-12-31 | 1994-07-21 | Unilever N.V. | Improved oil and fractionation process |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5285206A (en) * | 1976-01-09 | 1977-07-15 | Asahi Denka Kogyo Kk | Production of highly stable liquid oil |
US4748041A (en) * | 1986-03-06 | 1988-05-31 | Durkee Industrial Foods Corp. | Shelf stable non-aqueous squeezable composition |
ES2063054T3 (en) * | 1987-12-31 | 1995-01-01 | Pioneer Hi Bred Int | Rapeseed production with modified oleic acid content. |
US4948811A (en) * | 1988-01-26 | 1990-08-14 | The Procter & Gamble Company | Salad/cooking oil balanced for health benefits |
JPH05505512A (en) * | 1989-03-06 | 1993-08-19 | パイオニア ハイ―ブレッド インターナショナル インコーポレイテッド | Production of improved rapeseed showing increased oleic acid content |
US5861187A (en) * | 1990-08-30 | 1999-01-19 | Cargill, Incorporated | Oil from canola seed with altered fatty acid profiles and a method of producing oil |
ATE116104T1 (en) * | 1991-03-11 | 1995-01-15 | Unilever Nv | OILS WITH HIGH STABILITY. |
CA2119859C (en) * | 1991-09-30 | 2002-02-26 | Lorin R. Debonte | A canola variety producing a seed with reduced glucosinolates and linolenic acid yielding an oil with low sulfur, improved sensory characteristics and increased oxidative stability |
US5750827A (en) * | 1991-09-30 | 1998-05-12 | Cargill Incorporated | Canola variety producing a seed with reduced glucosinolates and linolenic acid yielding an oil with low sulfur, improved sensory characteristics and increased oxidative stability |
WO1994024849A1 (en) * | 1993-04-27 | 1994-11-10 | Cargill, Incorporated | Non-hydrogenated canola oil for food applications |
AU709039B2 (en) * | 1993-06-17 | 1999-08-19 | Cargill Incorporated | Pourable canola oil for food applications |
US5912041A (en) * | 1993-06-17 | 1999-06-15 | Cargill, Incorporated | Canola shortening for food applications |
-
1996
- 1996-05-21 US US08/651,684 patent/US5885643A/en not_active Expired - Fee Related
-
1997
- 1997-05-21 CA CA002255628A patent/CA2255628C/en not_active Expired - Fee Related
- 1997-05-21 EP EP97926830A patent/EP0921728B1/en not_active Revoked
- 1997-05-21 AU AU31505/97A patent/AU724638B2/en not_active Ceased
- 1997-05-21 JP JP54298997A patent/JP4323569B2/en not_active Expired - Fee Related
- 1997-05-21 DE DE69735630T patent/DE69735630T2/en not_active Revoked
- 1997-05-21 WO PCT/US1997/009326 patent/WO1997043907A1/en active IP Right Grant
- 1997-05-21 AT AT97926830T patent/ATE322171T1/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992003919A1 (en) * | 1990-08-30 | 1992-03-19 | E.I. Du Pont De Nemours And Company | Seeds, plants and oils with altered fatty acid profiles |
WO1994015478A1 (en) * | 1992-12-31 | 1994-07-21 | Unilever N.V. | Improved oil and fractionation process |
Non-Patent Citations (1)
Title |
---|
UNICHEMA INTERNATIONAL, "Hydrogenation of Canola Oil", March 1992, page 6. * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002542829A (en) * | 1999-05-03 | 2002-12-17 | カルジーン エルエルシー | Method for producing plants with higher oleic acid content |
EP1402781A1 (en) * | 2001-06-05 | 2004-03-31 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Coated organic acid preparations for preserving bakery products |
EP1402781A4 (en) * | 2001-06-05 | 2005-03-02 | Ueno Seiyaku Oyo Kenkyujo Kk | Coated organic acid preparations for preserving bakery products |
WO2004111164A1 (en) * | 2003-06-10 | 2004-12-23 | Archer-Daniels-Midland Company | Method for the production of fatty acids having a low trans-fatty acid content |
US7126019B2 (en) | 2003-06-10 | 2006-10-24 | Archer-Daniels-Midland Company | Method for the production of fatty acids having a low trans-fatty acid content |
KR101050437B1 (en) * | 2003-06-10 | 2011-07-19 | 카오 코퍼레이션 | Process for producing fatty acids with low trans-fatty acid content |
EP1753298A4 (en) * | 2004-04-29 | 2009-07-22 | Gfa Brands Inc | Oxidative stabilization of omega-3 fatty acids in low linoleic acid-containing peanut butter |
AU2005244141B2 (en) * | 2004-04-29 | 2010-08-26 | Gfa Brands, Inc. | Oxidative stabilization of omega-3 fatty acids in low linoleic acid-containing peanut butter |
EP1753298A2 (en) * | 2004-04-29 | 2007-02-21 | GFA Brands, Inc. | Oxidative stabilization of omega-3 fatty acids in low linoleic acid-containing peanut butter |
EP1802563A4 (en) * | 2004-09-16 | 2008-10-22 | Cargill Inc | Canola oil from hybrid brassica varieties |
EP1802563A1 (en) * | 2004-09-16 | 2007-07-04 | Cargill, Incorporated | Canola oil from hybrid brassica varieties |
US8080680B2 (en) | 2004-09-16 | 2011-12-20 | Cargill, Incorporateed | Canola oil from hybrid Brassica varieties |
US8637740B2 (en) | 2008-11-04 | 2014-01-28 | Dow Agrosciences, Llc. | Omega-9 quality Brassica juncea |
US9334483B2 (en) | 2009-12-18 | 2016-05-10 | Cargill, Incorporated | Brassica plants with mutant FATA2 alleles yielding oils with a low total saturated fatty acid content |
US10709079B2 (en) | 2009-12-18 | 2020-07-14 | Cargill, Incorporated | Brassica plants yielding oils with a low total saturated fatty acid content |
US9185861B2 (en) | 2010-05-25 | 2015-11-17 | Cargill, Incorporated | Brassica plants yielding oils with a low alpha linolenic acid content |
US9695434B2 (en) | 2010-05-25 | 2017-07-04 | Cargill, Incorporated | Brassica plants yielding oils with a low alpha linolenic acid content |
EP2724620A1 (en) * | 2012-10-26 | 2014-04-30 | Walter RAU Neusser Öl und Fett AG | Oleochmical composition |
Also Published As
Publication number | Publication date |
---|---|
DE69735630D1 (en) | 2006-05-18 |
CA2255628A1 (en) | 1997-11-27 |
EP0921728A4 (en) | 2000-02-23 |
DE69735630T2 (en) | 2007-01-11 |
AU3150597A (en) | 1997-12-09 |
US5885643A (en) | 1999-03-23 |
EP0921728A1 (en) | 1999-06-16 |
CA2255628C (en) | 2002-12-17 |
JP4323569B2 (en) | 2009-09-02 |
EP0921728B1 (en) | 2006-04-05 |
JP2000511230A (en) | 2000-08-29 |
AU724638B2 (en) | 2000-09-28 |
ATE322171T1 (en) | 2006-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5885643A (en) | High stability canola oils | |
US10314317B2 (en) | Seed oil compositions | |
US5767338A (en) | Brassica napus plants which produce non-hydrogenated canola oil for food applications | |
CA2249568C (en) | Soybean oil having high oxidative stability | |
US5912041A (en) | Canola shortening for food applications | |
CA2388889C (en) | Soybean oil having high oxidative stability | |
AU2004202766B2 (en) | Soybean oil having high oxidative stability | |
MXPA00011080A (en) | Fat products from high stearic soybean oil and a method for the production thereof | |
CA2340573A1 (en) | Non-hydrogenated canola oil for food applications | |
AU4374701A (en) | Soybean oil having high oxidative stability |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2255628 Country of ref document: CA Ref country code: CA Ref document number: 2255628 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1997926830 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1997926830 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1997926830 Country of ref document: EP |