CA2681753A1 - Antioxidant blends for fatty acid methyl esters (biodiesel) - Google Patents
Antioxidant blends for fatty acid methyl esters (biodiesel) Download PDFInfo
- Publication number
- CA2681753A1 CA2681753A1 CA002681753A CA2681753A CA2681753A1 CA 2681753 A1 CA2681753 A1 CA 2681753A1 CA 002681753 A CA002681753 A CA 002681753A CA 2681753 A CA2681753 A CA 2681753A CA 2681753 A1 CA2681753 A1 CA 2681753A1
- Authority
- CA
- Canada
- Prior art keywords
- tert
- biodiesel
- butylphenol
- ppm
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 117
- 235000019387 fatty acid methyl ester Nutrition 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000003963 antioxidant agent Substances 0.000 title description 40
- 230000003078 antioxidant effect Effects 0.000 title description 33
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003549 soybean oil Substances 0.000 claims description 72
- 235000012424 soybean oil Nutrition 0.000 claims description 72
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 13
- 239000008158 vegetable oil Substances 0.000 claims description 13
- 235000019482 Palm oil Nutrition 0.000 claims description 10
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 10
- 239000002540 palm oil Substances 0.000 claims description 10
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 9
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003240 coconut oil Substances 0.000 claims description 9
- 235000019864 coconut oil Nutrition 0.000 claims description 9
- 239000000828 canola oil Substances 0.000 claims description 8
- 235000019519 canola oil Nutrition 0.000 claims description 8
- VMZVBRIIHDRYGK-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VMZVBRIIHDRYGK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 7
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 7
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 6
- PXMJCECEFTYEKE-UHFFFAOYSA-N Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, methyl ester Chemical compound COC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PXMJCECEFTYEKE-UHFFFAOYSA-N 0.000 claims description 6
- 235000005687 corn oil Nutrition 0.000 claims description 6
- 239000002285 corn oil Substances 0.000 claims description 6
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 claims description 6
- PWNBRRGFUVBTQG-UHFFFAOYSA-N 1-n,4-n-di(propan-2-yl)benzene-1,4-diamine Chemical compound CC(C)NC1=CC=C(NC(C)C)C=C1 PWNBRRGFUVBTQG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 150000004702 methyl esters Chemical class 0.000 description 71
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 43
- 235000006708 antioxidants Nutrition 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 35
- 235000013824 polyphenols Nutrition 0.000 description 23
- 239000000306 component Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 methanol Chemical compound 0.000 description 3
- 238000000844 transformation Methods 0.000 description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 2
- QYDYPVFESGNLHU-ZHACJKMWSA-N Methyl (9E)-9-octadecenoate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OC QYDYPVFESGNLHU-ZHACJKMWSA-N 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QSQLTHHMFHEFIY-UHFFFAOYSA-N methyl behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC QSQLTHHMFHEFIY-UHFFFAOYSA-N 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ATBNMWWDBWBAHM-UHFFFAOYSA-N n-decyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCCC ATBNMWWDBWBAHM-UHFFFAOYSA-N 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- MYZDPUZXMFCPMU-LRIWMWCYSA-N (6r,8s,9r,10s,11s,13s,14s,17r)-2-bromo-6,9-difluoro-11,17-dihydroxy-17-(2-hydroxyacetyl)-10,13-dimethyl-6,7,8,11,12,14,15,16-octahydrocyclopenta[a]phenanthren-3-one Chemical compound O=C1C(Br)=C[C@]2(C)[C@@]3(F)[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3C[C@@H](F)C2=C1 MYZDPUZXMFCPMU-LRIWMWCYSA-N 0.000 description 1
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- VHQALVHKNXDJRY-UHFFFAOYSA-N 1-bromo-2-chloro-4-fluoro-3-methylbenzene Chemical compound CC1=C(F)C=CC(Br)=C1Cl VHQALVHKNXDJRY-UHFFFAOYSA-N 0.000 description 1
- JJULABXIXFRDCQ-UHFFFAOYSA-N 2,3,4-tritert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C JJULABXIXFRDCQ-UHFFFAOYSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- HWMKUXXLKIOVQZ-UHFFFAOYSA-N 3,6-dimethylpyridin-2-amine Chemical compound CC1=CC=C(C)C(N)=N1 HWMKUXXLKIOVQZ-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- AMOGMTLMADGEOQ-UHFFFAOYSA-N 8-tert-butyl-6,9,12,17-tetrahydroxy-16-methyl-2,4,14,19-tetraoxahexacyclo[8.7.2.0^{1,11}.0^{3,7}.0^{7,11}.0^{13,17}]nonadecane-5,15,18-trione Chemical compound O1C2OC(=O)C(O)C32C24C(O)C5OC(=O)C(C)C5(O)C21C(=O)OC4C(O)C3C(C)(C)C AMOGMTLMADGEOQ-UHFFFAOYSA-N 0.000 description 1
- FKLSONDBCYHMOQ-UHFFFAOYSA-N 9E-dodecenoic acid Natural products CCC=CCCCCCCCC(O)=O FKLSONDBCYHMOQ-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- OFIDNKMQBYGNIW-UHFFFAOYSA-N arachidonic acid methyl ester Natural products CCCCCC=CCC=CCC=CCC=CCCCC(=O)OC OFIDNKMQBYGNIW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 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
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PVVODBCDJBGMJL-CMDGGOBGSA-N methyl (e)-octadec-11-enoate Chemical compound CCCCCC\C=C\CCCCCCCCCC(=O)OC PVVODBCDJBGMJL-CMDGGOBGSA-N 0.000 description 1
- XEJYCWVISZMIDA-SEYXRHQNSA-N methyl (z)-icos-9-enoate Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(=O)OC XEJYCWVISZMIDA-SEYXRHQNSA-N 0.000 description 1
- OFIDNKMQBYGNIW-ZKWNWVNESA-N methyl arachidonate Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)OC OFIDNKMQBYGNIW-ZKWNWVNESA-N 0.000 description 1
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WTTJVINHCBCLGX-ZDVGBALWSA-N methyl linolelaidate Chemical compound CCCCC\C=C\C\C=C\CCCCCCCC(=O)OC WTTJVINHCBCLGX-ZDVGBALWSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGBRLVONZXHAKJ-UHFFFAOYSA-N n-eicosanoic acid methyl ester Natural products CCCCCCCCCCCCCCCCCCCC(=O)OC QGBRLVONZXHAKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- DTOSIQBPPRVQHS-UHFFFAOYSA-N α-Linolenic acid Chemical compound CCC=CCC=CCC=CCCCCCCCC(O)=O DTOSIQBPPRVQHS-UHFFFAOYSA-N 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1835—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom having at least two hydroxy substituted non condensed benzene rings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
- C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
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- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
This invention provides stabilized biodiesels comprising (1) biodiesel, such as fatty acid methyl ester (FAME), (2) mono- or bis-hindered phenolic derived from 2,6-di-tert- butylphenol, and (3) N,N'-di-substituted para-phenylene diamine. Also methods of stabilizing biodiesel are provided involving adding (2) and (3) to (1).
Description
ANTIOXIDANT BLENDS FOR FATTY ACID METHYL ESTERS (BIODIESEL) BACKGROUND
[0001] As worldwide energy demand continues to increase and reserves of fossil fuels shrink, the diversification of energy sources becomes increasingly important.
Biodiesel is one way to achieve diversification. Biodiesel is a generic name for mono-alkyl esters of long-chain fatty acids derived from renewable lipid sources such as vegetable oils, animal fats, or used cooking oils and fats. Biodiesel fuels have many names, depending on the feedstocks used to produce them, for example, fatty acid methyl ester (FAME), rapeseed methyl ester (RME), used vegetable oil methyl ester (UVOME), soybean oil methyl ester (SOME) or palm oil methyl ester (POME).
Biodiesel feedstocks vary widely in their fatty acid compositions (chain length and saturation).
[0001] As worldwide energy demand continues to increase and reserves of fossil fuels shrink, the diversification of energy sources becomes increasingly important.
Biodiesel is one way to achieve diversification. Biodiesel is a generic name for mono-alkyl esters of long-chain fatty acids derived from renewable lipid sources such as vegetable oils, animal fats, or used cooking oils and fats. Biodiesel fuels have many names, depending on the feedstocks used to produce them, for example, fatty acid methyl ester (FAME), rapeseed methyl ester (RME), used vegetable oil methyl ester (UVOME), soybean oil methyl ester (SOME) or palm oil methyl ester (POME).
Biodiesel feedstocks vary widely in their fatty acid compositions (chain length and saturation).
[0002] Biodiesel is typically produced by the reaction of a vegetable oil or an animal fat with an alcohol, such as methanol, in the presence of a catalyst to yield methyl esters (the biodiesel) and glycerine. The most commonly used catalyst, potassium hydroxide, is used in transesterification of a wide range of oils and fats, from vegetable to animal, from virgin to used, including those with the highest acid contents. The thus produced biodiesel can be distilled to remove excess alcohols and other impurities.
Other methods for production of biodiesel are known.
Other methods for production of biodiesel are known.
[0003] Freshly produced vegetable oils are protected from oxidation by the presence of naturally occurring antioxidants (for example, tocopherols). However, the manufacturing process for biodiesel tends to remove some of the natural antioxidants, leaving the fuel less protected from oxidative degradation. In addition, distillation of the biodiesel tends to remove essentially all the natural antioxidants leaving the fuel even further unprotected from oxidative degradation. Oxidation of biodiesel by contact with air and metal surfaces results in the formation of hydroperoxides . These induce free-radical chain reactions that lead to decomposition into low-molecular-weight, highly oxidized species (aldehydes, ketones, acids) and high-molecular-weight polymeric materials (gums). These gums tend to cause poor combustion and other engine problems such as deposits on injectors and pistons. The presence of high-molecular weight, insoluble gums generally leads to fuel-filter plugging.
[0004] The RANCIMAT test is a widely accepted method for measuring the oxidation stability of biodiesel. This test consists of bubbling air through biodiesel that has been heated to 110 C. The amount of short-chain acids present in the distillate (the cleavage products of the fatty acid oxidation) is a direct indication of the oxidation stability of the biodiesel. In Europe and Brazil, biodiesel has to fulfill a six-hour RANCIMAT
test requirement at the production plant and at the pump when refueling vehicles, irrespective of the age of the biodiesel. Other countries may institute similar requirements. Although freshly produced biodiesel may show an oxidation stability (measured by the RANCIMAT method) of more than six hours, this value will decrease over time under common storage conditions if no antioxidants are present.
test requirement at the production plant and at the pump when refueling vehicles, irrespective of the age of the biodiesel. Other countries may institute similar requirements. Although freshly produced biodiesel may show an oxidation stability (measured by the RANCIMAT method) of more than six hours, this value will decrease over time under common storage conditions if no antioxidants are present.
[0005] Antioxidants are used in hydrocarbon fuels to increase oxidation stability. The oxidation stability of biodiesel can also be increased by the addition of antioxidants.
However, given the relative youth of biodiesel fuels as compared to hydrocarbon fuels, antioxidant technology for biodiesel is not as well-developed.
However, given the relative youth of biodiesel fuels as compared to hydrocarbon fuels, antioxidant technology for biodiesel is not as well-developed.
[0006] Thus, there is a need for improved antioxidant compositions for use in biodiesel fuels and for biodiesel compositions comprising such antioxidant compositions that are economically suited for commercial use.
THE INVENTION
THE INVENTION
[0007] This invention meets the above-described needs by providing compositions derived from biodiesel, mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on the biodiesel.
Further, such compositions are provided wherein the biodiesel is crude biodiesel, and wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil, and wherein the crude biodiesel is a fatty acid methyl ester. Such compositions are provided wherein the biodiesel is distilled biodiesel, and wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil. Also, such compositions are provided wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel. Further, such compositions are provided wherein the ratio of the mono- or bis-hindered phenolic to N'N-di-substituted para-phenylene diamine varies from about 10:1 to about 1:10 by weight, in particular varies from about Fg. 53~3$r-6~a9 emF~nV.P.T .::::. ~ EP4. AiLTNICH ....::
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PCT US
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5:1 to about 1:5 by weight. Also provided are compositions derived from biodiesel, 2,4,6-tri=tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine varies from about 10:1 to about 1:10 by weight. This invention also provides compositions prepared by combining, or comprising, biodiesel, mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamine, wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on the biodiesel_ [0008] This invention also provides methods of improving oxidation stability of a composition comprising biodiesel by combining the composition and mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine such that the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to 5000 ppm based on the biodiesel. Also provided are such methods wherein the biodiesel is crude biodiesel, and wherein the crude biodiesel is derived from soybean oil, canala oil, palm oil, coconut oil, rapeseed oil, com oil, or used vegetable oil, and wherein the crude biodiesel is a fatty acid methyl ester. Also provided are such methods wherein the biodiesel is distilled biodiesel, and wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil. Also, such methods are provided wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel. Further, such methods are provided wherein the ratio of the mono- or bis-hindered phenolic to N'N-di'-substituted para-phenylene diamine is varies from about 10:1 to about 1:10 by weight, in particular varies from about 5:1 to about 1:5 by weight. Also provided are methods of improving oxidation stability of a composition comprising biodiesel by combining the composition, 2,4,6-tri=tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine varies from about 5:1 to about 1:5 by weight.
Further, such compositions are provided wherein the biodiesel is crude biodiesel, and wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil, and wherein the crude biodiesel is a fatty acid methyl ester. Such compositions are provided wherein the biodiesel is distilled biodiesel, and wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil. Also, such compositions are provided wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel. Further, such compositions are provided wherein the ratio of the mono- or bis-hindered phenolic to N'N-di-substituted para-phenylene diamine varies from about 10:1 to about 1:10 by weight, in particular varies from about Fg. 53~3$r-6~a9 emF~nV.P.T .::::. ~ EP4. AiLTNICH ....::
~ 22 [A~S. : >:.:::~"~,~:`:;:
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5:1 to about 1:5 by weight. Also provided are compositions derived from biodiesel, 2,4,6-tri=tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine varies from about 10:1 to about 1:10 by weight. This invention also provides compositions prepared by combining, or comprising, biodiesel, mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N, N'-di-substituted para-phenylene diamine, wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on the biodiesel_ [0008] This invention also provides methods of improving oxidation stability of a composition comprising biodiesel by combining the composition and mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine such that the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to 5000 ppm based on the biodiesel. Also provided are such methods wherein the biodiesel is crude biodiesel, and wherein the crude biodiesel is derived from soybean oil, canala oil, palm oil, coconut oil, rapeseed oil, com oil, or used vegetable oil, and wherein the crude biodiesel is a fatty acid methyl ester. Also provided are such methods wherein the biodiesel is distilled biodiesel, and wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil. Also, such methods are provided wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel. Further, such methods are provided wherein the ratio of the mono- or bis-hindered phenolic to N'N-di'-substituted para-phenylene diamine is varies from about 10:1 to about 1:10 by weight, in particular varies from about 5:1 to about 1:5 by weight. Also provided are methods of improving oxidation stability of a composition comprising biodiesel by combining the composition, 2,4,6-tri=tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine varies from about 5:1 to about 1:5 by weight.
[0009] In this invention, the mono- or bis-hindered phenolic derived from 2;6-di-tert-butylphenol =can comprise ortho-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4'-mefihylenebis(2,6-di-tert-butylphenoi), 3,5-di-tert-butyl-4-hydroxythydrocinnamic acid, methyl ester, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic AMENDED SHEET
at the EPO on Jan 14, 2009 22:10:52. Page 9 of 14 m:1.iy.:a;i:91)nn:::y.R:'nnFaX 2253887239 PA:.:.TFnrr::n.Pv..T::::.. EPO.
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acid, C7-C9 branched alkyl esters, 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol;
butylated hydroxytoluene, or 2,4,6-tri-tert-butyiphenol; and the N, N'-di-substituted para-phenylene diamine can comprise N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyi-p,phenylenediamine, or N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
at the EPO on Jan 14, 2009 22:10:52. Page 9 of 14 m:1.iy.:a;i:91)nn:::y.R:'nnFaX 2253887239 PA:.:.TFnrr::n.Pv..T::::.. EPO.
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acid, C7-C9 branched alkyl esters, 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol;
butylated hydroxytoluene, or 2,4,6-tri-tert-butyiphenol; and the N, N'-di-substituted para-phenylene diamine can comprise N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyi-p,phenylenediamine, or N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
[0010] In some of the compositions and/or methods of the present invention, the weight ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is greater than about 1j n some embodiments, greater than about 1.25, and in other embodiments, greater than about 1.5.
[0011] A glossary of terms is provided prior to the claims.
[0012] We were surprised to discover the substantial increase in oxidation stability of biodiesel provided by this invention. We did not have reason to expect that the combinations of biodiesels and antioxidants as described and claimed herein would provide the benefits shown by the examples provided herein.
Mono or bis-hindered phenollics.derived from 2 6-di-tert-bu I heno@
Mono or bis-hindered phenollics.derived from 2 6-di-tert-bu I heno@
[0013] Suitable mono or bis-hindered phenolics derived from 2,6-di-tert-butylphenols can comprise 2,6-di-tert-butylphenol (e.g., the product comprising 2,6-di-tert-butylphenol sold under the trademark ETHANOX 4701); 2,4,6-tri-tert-butylphenol;
combinations of ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and 2,4,6-tri-tert-butylphenol (e.g., the product comprising ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and 2,4,6-tri-tert-butylphenol sold under the trademark ETHANOX 4733);
combinations of 2,6-di4ert-butylphenol and 2,4,64ri-tert-butyiphenol (e.g., the product comprising 2,6-di-tert-butjrlphenol and 2,4,6-tri-tert-butyfphenol sold under the trademark ETHANOX
4735); 4,:4'-methylenebis(2,6-di-tert-butylphenol) (e_g_, the product comprising 4,4'-methylenebis(2,6-di-tert-butylphenol) sold under the trademark ETHANOX 4702);
3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, methyl ester (e.g., the product comprising 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester sold under the trademark ETHANOX 4750); 3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, C7-C9 branched alkyl esters (e.g., the product comprising 3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, C7-C9 branched alkyl esters sold under the trademark ETHANOX 4716); 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol (e.g., the product comprising 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol sold under the trademark ETHANOX 4703); butylated hydroxytoluene (BHT); essentially 100% 2,4,6-AMENDED SHEET
<;~ed at the EPO on Jan14, 2009 22:10:52. Page 10 of 14 = : ~; :::~~~~;1:~;~3t~9' tri-tert-butylphenol (TTBP), or combinations thereof. In this invention, concentration of the mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol can be from about 0.0025 wt% to about 0.25 wt% of the total biodiesel.
N,N'-di-substituted para-phenylene diamines [0014] Suitable N,N'-di-substituted para-phenylene diamines can comprise N,N'-di-sec-butyl-p-phenylenediamine (PDA), N,N'- diisopropyl-p-phenylenediamine, N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, or combinations thereof. In this invention, concentration of the N, N'-dis-substituted para-phenylene diamine can be from about 0.0025 wt% to about 0.25 wt% of the total biodiesel.
Biodiesels [0015] As used herein, unless otherwise distinguished, the term biodiesel comprises crude biodiesel, distilled biodiesel, or any individual chemical component of either.
Crude biodiesel comprises 8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl ester, or fatty acid methyl ester derived from a vegetable or animal source. Processes for producing crude biodiesel are well know to those skilled in the art. Example individual chemical components of fatty acid methyl ester include methyl stearate (n-octadecanoic acid, methyl ester), methyl oleate (9-octadecenoic acid, methyl ester), methyl vaccenate (1 1-octadecenoic acid methyl ester), methyl linoleate (9,12-octadecadienoic acid, methyl ester), or methyl linoleniate (9,12,15-octadecatrienoic acid, methyl ester), caprylic acid methyl ester, capric acid methyl ester, lauric acid methyl ester, myristic acid methyl ester, palmitic acid methyl ester, arachidic acid methyl ester, behenic acid methyl ester, lauroleic acid methyl ester, myristoleic acid methyl ester, palmitoleic acid methyl ester, elaidic acid methyl ester, gadoleic acid methyl ester, arachidonic acid methyl ester, erucic acid methyl ester, and the like.
combinations of ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and 2,4,6-tri-tert-butylphenol (e.g., the product comprising ortho-tert-butylphenol, 2,6-di-tert-butylphenol, and 2,4,6-tri-tert-butylphenol sold under the trademark ETHANOX 4733);
combinations of 2,6-di4ert-butylphenol and 2,4,64ri-tert-butyiphenol (e.g., the product comprising 2,6-di-tert-butjrlphenol and 2,4,6-tri-tert-butyfphenol sold under the trademark ETHANOX
4735); 4,:4'-methylenebis(2,6-di-tert-butylphenol) (e_g_, the product comprising 4,4'-methylenebis(2,6-di-tert-butylphenol) sold under the trademark ETHANOX 4702);
3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, methyl ester (e.g., the product comprising 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester sold under the trademark ETHANOX 4750); 3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, C7-C9 branched alkyl esters (e.g., the product comprising 3,5-di-tert-butyl-4-hydroxy hydrocinnamic acid, C7-C9 branched alkyl esters sold under the trademark ETHANOX 4716); 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol (e.g., the product comprising 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol sold under the trademark ETHANOX 4703); butylated hydroxytoluene (BHT); essentially 100% 2,4,6-AMENDED SHEET
<;~ed at the EPO on Jan14, 2009 22:10:52. Page 10 of 14 = : ~; :::~~~~;1:~;~3t~9' tri-tert-butylphenol (TTBP), or combinations thereof. In this invention, concentration of the mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol can be from about 0.0025 wt% to about 0.25 wt% of the total biodiesel.
N,N'-di-substituted para-phenylene diamines [0014] Suitable N,N'-di-substituted para-phenylene diamines can comprise N,N'-di-sec-butyl-p-phenylenediamine (PDA), N,N'- diisopropyl-p-phenylenediamine, N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine, or combinations thereof. In this invention, concentration of the N, N'-dis-substituted para-phenylene diamine can be from about 0.0025 wt% to about 0.25 wt% of the total biodiesel.
Biodiesels [0015] As used herein, unless otherwise distinguished, the term biodiesel comprises crude biodiesel, distilled biodiesel, or any individual chemical component of either.
Crude biodiesel comprises 8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl ester, or fatty acid methyl ester derived from a vegetable or animal source. Processes for producing crude biodiesel are well know to those skilled in the art. Example individual chemical components of fatty acid methyl ester include methyl stearate (n-octadecanoic acid, methyl ester), methyl oleate (9-octadecenoic acid, methyl ester), methyl vaccenate (1 1-octadecenoic acid methyl ester), methyl linoleate (9,12-octadecadienoic acid, methyl ester), or methyl linoleniate (9,12,15-octadecatrienoic acid, methyl ester), caprylic acid methyl ester, capric acid methyl ester, lauric acid methyl ester, myristic acid methyl ester, palmitic acid methyl ester, arachidic acid methyl ester, behenic acid methyl ester, lauroleic acid methyl ester, myristoleic acid methyl ester, palmitoleic acid methyl ester, elaidic acid methyl ester, gadoleic acid methyl ester, arachidonic acid methyl ester, erucic acid methyl ester, and the like.
[0016] Distilled biodiesel comprises crude biodiesel that has been subjected to at least one distillation step, e.g., to remove excess alcohols, residual glycerine, and other impurities, and includes biodiesel obtained as a specific cut or fraction produced during the distillation of crude biodiesel. Methods of distilling crude biodiesel are well known to those skilled in the art.
[0017] Crude biodiesel can be derived from any suitable vegetable or animal source, including for example soybean oil, low erucic acid rapeseed oil (Canola Oil), high erucic acid rapeseed oil, palm oil, used cooking oil, vegetable oil, coconut oil, corn oil, cottonseed oil, safflower oil, sunflower oil, peanut oil, sugar cane oil, lard, tallow, poultry fat, yellow grease, and the like. Fatty acid methyl ester in crude biodiesel can be produced, e.g., by a transesterification reaction between a vegetable or animal based triglyceride and methanol using a catalyst, as is familiar to those skilled in the art.
[0018] Crude biodiesel or distilled biodiesel can be subjected to additional chemical treatment, e.g., to reduce unsaturation.
Combinations [0019] Compositions according to this invention comprising, or prepared by combining, biodiesel, mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol (component (2)), and N,N'-di-substituted para-phenylene diamine (component (3)), can comprise, or be prepared by combining, from about 50 ppm to about 5000 ppm of components (2) and (3), based on the amount of the biodiesel, and can comprise, or be prepared by combining, from about 100 ppm to about 2500 ppm of components (2) and (3), based on the amount of the biodiesel.
Combinations [0019] Compositions according to this invention comprising, or prepared by combining, biodiesel, mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol (component (2)), and N,N'-di-substituted para-phenylene diamine (component (3)), can comprise, or be prepared by combining, from about 50 ppm to about 5000 ppm of components (2) and (3), based on the amount of the biodiesel, and can comprise, or be prepared by combining, from about 100 ppm to about 2500 ppm of components (2) and (3), based on the amount of the biodiesel.
[0020] Methods of improving oxidation stability of biodiesel according to this invention can comprise combining the biodiesel and from about 50 ppm to about 5000 ppm of antioxidant component comprising mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol and N,N'-di-substituted para-phenylene diamine. Such methods can also comprising combining the biodiesel component and from about 100 ppm to about 2500 ppm of antioxidant component comprising mono or bis-hindered phenolic derived from 2,6-di-tert-butylphenol and N,N'-di-substituted para-phenylene diamine.
Examples [0021] The following examples are illustrative of the principles of this invention. It is understood that this invention is not limited to any one specific embodiment exemplified herein, whether in the examples or the remainder of this patent application.
Examples [0021] The following examples are illustrative of the principles of this invention. It is understood that this invention is not limited to any one specific embodiment exemplified herein, whether in the examples or the remainder of this patent application.
[0022] In each example summarized in Tablel, the identified biodiesel sample and antioxidant composition were combined. In some of the comparative examples, no antioxidant composition was added to the identified biodiesel. In the examples in which the biodiesel was distilled, the biodiesel was distilled using standard techniques known to those skilled in the art. In each example, the oxidation stability of the combination (or of just the biodiesel in certain of the comparative examples) was tested with the RANCIMAT test using RANCIMAT test method (DIN EN 14112). In each instance the sample size was 3 grams, the temperature was 110 C, the air source was purified dry air, and the flow rate was 10 LIhr. The data in Table 1 clearly shows the benefits of this invention. For example, for soybean oil methyl ester, distilled, with no antioxidant added, the highest RANCIMAT result was 1.7 hour (see comparative example nos.
39); whereas, for soybean oil methyl ester, distilled, with antioxidant added in accordance with this invention, the RANCIMAT results ranged from 3.87 hours to 11.19 hours (see example nos. 1 - 22). For soybean oil methyl ester, not distilled, with no antioxidant added, the highest RANCIMAT result was 4.63 hours (see comparative example nos. 40 and 41); whereas, for soybean oil methyl ester, not distilled, with antioxidant added in accordance with this invention, the RANCIMAT results ranged from 6.46 hours to 9.28 hours (see example nos. 23 - 32). Comparing comparative example nos. 42 and 44, both of which show results of combining soybean oil methyl ester, distilled and antioxidant composition of 300 ppm ETHANOX 4733 and 100 ppm of a component not of this invention, to example nos. 1, 3, 5, and 6 of this invention, each of which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of less than 300 ppm ETHANOX 4733 and PDA, shows that each of example nos. 1, 3, 5, and 6 has a better RANCIMAT result (8.76 hrs, 9.53 hrs, 6.91 hrs, and 5.89 hrs, respectively) than either of comparative example nos.
42 and 44 (2.94 hrs and 2.88 hrs, respectively). Comparing comparative example nos. 43, 45, and 46, each of which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of 300 ppm ETHANOX 4702 and 100 ppm of a component not of this invention, to example 2 of this invention, which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of 200 ppm ETHANOX
4702 and 200 ppm PDA, shows that example no. 2 has a better RANCIMAT result (10.52 hrs) than any of example nos. 43, 45, and 46 (3.6 hrs, 3.87 hrs, and 4.06 hrs, respectively). Comparing comparative example nos. 50, 51, and 52, each of which shows results of combining soybean oil methyl ester, not distilled and antioxidant composition of varying amounts (200 ppm to 600 ppm) of TTBP, to example nos.
32 of this invention, each of which shows results of combining soybean oil methyl ester, not distilled and antioxidant composition of 200 ppm or less of TTBP and PDA, shows that each of example nos. 27 - 32 has a better RANCIMAT result (8.1 hrs, 9.28 hrs, 8.38 hrs, 7.77 hrs, 6.95 hrs, and 6.46 hrs, respectively) than any of comparative example nos. 50, 51, or 52 (5.28 hrs, 5.53 hrs, and 5.84 hrs, respectively).
In particular, comparing comparative example no. 50 (with an antioxidant composition of 200 ppm TTBP, and a RANCIMAT result of 5.28 hrs.) with example no. 28 of this invention (with an antioxidant composition of 200 ppm TTBP and 200 ppm PDA, and a RANCIMAT result of 9.28 hrs) it can be seen that this invention provides a substantial benefit. A similar comparison, based on antioxidant composition of ETHANOX
compared to antioxidant compositions of this invention including ETHANOX 4703, can be made between comparative example no. 48 and example nos. 3, 7, 8, and 9 of this invention. Comparative example no. 47 shows use of 381 ppm PDA as an antioxidant with distilled biodiesel gives a RANCIMAT result of 6.39 hrs. While some of the examples of this invention using a distilled biodiesel and an antioxidant of PDA with a mono or bis-hindered phenolic show a lower RANCIMAT result, none of these examples use near 381 ppm PDA. The relatively high cost of PDA, and relatively low cost of phenolics, makes it beneficial to be able to use smaller amounts of PDA with a phenolic, in accordance with this invention, and yet obtain acceptable RANCIMAT
results. See, e.g., examples nos. 2 and 3 of this invention where, with a distilled biodiesel, only 200 ppm PDA is used with a phenolic and RANCIMAT results of 8.76 hrs and 10.52 hrs are obtained. Also, in each of the examples of this invention using a distilled biodiesel and an antioxidant of PDA and phenolic that shows a RANCIMAT
result lower than 6.39 hrs, the phenolic in the antioxidant is ETHANOX 4733;
the lowest such RANCIMAT result being 3.87 hrs. Comparing this to comparative example nos.
42 and 44 (RANCIMAT results of 2.94 hrs and 2.88 hrs), where ETHANOX 4733 is used with amines not of this invention, shows improved results with antioxidant compositions of this invention. Comparative example no. 49 shows use of 200 ppm PDA as an antioxidant with biodiesel (not distilled) gives a RANCIMAT result of 9.01 hrs. Comparative example no. 50 shows use of 200 ppm TTBP as an antioxidant with biodiesel (not distilled) gives a RANCIMAT result of 5.28 hrs. When a combination of 100 ppm TTBP and 100 ppm PDA of this invention is used as an antioxidant with biodiesel (not distilled) a RANCIMAT result of 8.1 hrs is obtained (example no. 27).
The result of 8.1 hrs with the TTBP/PDA combination is significantly better than the 5.28 hrs obtained with the TTBP alone. Also, the result of 8.1 hrs with the TTBP/PDA
combination is only slightly lower than the 9.01 hrs obtained with the PDA
alone and yet provides a commercially significant cost advantage. While some of the examples of this invention using a biodiesel (not distilled) and an antioxidant of PDA
with a mono or bis-hindered phenolic show a lower RANCIMAT result, none of these examples use near 200 ppm PDA.
Table 1 Example No. Biodiesel Sample Antioxidant Result (Hrs) Composition (ppm based on Biodiesel) 1 soybean oil methyl ester, 200 ppm ETHANOX 8.76 distilled 4733, 200 ppm PDA
2 soybean oil methyl ester, 200 ppm PDA, 200 10.52 distilled ppm ETHANOX 4702 3 soybean oil methyl ester, 200 ppm PDA, 200 9.53 distilled ppm ETHANOX 4703 4 soybean oil methyl ester, 85 ppm ETHANOX 5.85 distilled 4733, 295 ppm PDA
soybean oil methyl ester, 183 ppm ETHANOX 6.91 distilled 4733, 206 ppm PDA
6 soybean oil methyl ester, 296 ppm ETHANOX 5.89 distilled 4733, 98 ppm PDA
7 soybean oil methyl ester, 318 ppm PDA, 104 9.3 distilled ppm ETHANOX 4703 8 soybean oil methyl ester, 204 ppm PDA, 202 7.88 distilled ppm ETHANOX 4703 9 soybean oil methyl ester, 105 ppm PDA, 297 6.56 distilled ppm ETHANOX 4703 soybean oil methyl ester, 100 ppm ETHANOX 4.45 distilled 4733, 100 ppm PDA
11 soybean oil methyl ester, 200 ppm ETHANOX 6.5 distilled 4733, 200 ppm PDA
12 soybean oil methyl ester, 300 ppm ETHANOX 8.35 distilled 4733, 300 ppm PDA
13 soybean oil methyl ester, 150 ppm ETHANOX 3.87 distilled 4733, 50 ppm PDA
14 soybean oil methyl ester, 300 ppm ETHANOX 5.47 distilled 4733, 100 ppm PDA
15 soybean oil methyl ester, 450 ppm ETHANOX 6.78 distilled 4733, 150 ppm PDA
16 soybean oil methyl ester, 100 ppm ETHANOX 4.34 distilled 4733, 100 ppm PDA
17 soybean oil methyl ester, 200 ppm ETHANOX 6.54 distilled 4733, 200 ppm PDA
18 soybean oil methyl ester, 300 ppm ETHANOX 8.42 distilled 4733, 300 ppm PDA
19 soybean oil methyl ester, 400 ppm ETHANOX 9.69 distilled 4733, 400 ppm PDA
20 soybean oil methyl ester, 500 ppm ETHANOX 11.19 distilled 4733, 500 ppm PDA
21 soybean oil methyl ester, 375 ppm ETHANOX 6.15 distilled 4733, 125 ppm PDA
22 soybean oil methyl ester, 375 ppm ETHANOX 6.07 distilled 4733, 125 ppm PDA
39); whereas, for soybean oil methyl ester, distilled, with antioxidant added in accordance with this invention, the RANCIMAT results ranged from 3.87 hours to 11.19 hours (see example nos. 1 - 22). For soybean oil methyl ester, not distilled, with no antioxidant added, the highest RANCIMAT result was 4.63 hours (see comparative example nos. 40 and 41); whereas, for soybean oil methyl ester, not distilled, with antioxidant added in accordance with this invention, the RANCIMAT results ranged from 6.46 hours to 9.28 hours (see example nos. 23 - 32). Comparing comparative example nos. 42 and 44, both of which show results of combining soybean oil methyl ester, distilled and antioxidant composition of 300 ppm ETHANOX 4733 and 100 ppm of a component not of this invention, to example nos. 1, 3, 5, and 6 of this invention, each of which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of less than 300 ppm ETHANOX 4733 and PDA, shows that each of example nos. 1, 3, 5, and 6 has a better RANCIMAT result (8.76 hrs, 9.53 hrs, 6.91 hrs, and 5.89 hrs, respectively) than either of comparative example nos.
42 and 44 (2.94 hrs and 2.88 hrs, respectively). Comparing comparative example nos. 43, 45, and 46, each of which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of 300 ppm ETHANOX 4702 and 100 ppm of a component not of this invention, to example 2 of this invention, which shows results of combining soybean oil methyl ester, distilled and antioxidant composition of 200 ppm ETHANOX
4702 and 200 ppm PDA, shows that example no. 2 has a better RANCIMAT result (10.52 hrs) than any of example nos. 43, 45, and 46 (3.6 hrs, 3.87 hrs, and 4.06 hrs, respectively). Comparing comparative example nos. 50, 51, and 52, each of which shows results of combining soybean oil methyl ester, not distilled and antioxidant composition of varying amounts (200 ppm to 600 ppm) of TTBP, to example nos.
32 of this invention, each of which shows results of combining soybean oil methyl ester, not distilled and antioxidant composition of 200 ppm or less of TTBP and PDA, shows that each of example nos. 27 - 32 has a better RANCIMAT result (8.1 hrs, 9.28 hrs, 8.38 hrs, 7.77 hrs, 6.95 hrs, and 6.46 hrs, respectively) than any of comparative example nos. 50, 51, or 52 (5.28 hrs, 5.53 hrs, and 5.84 hrs, respectively).
In particular, comparing comparative example no. 50 (with an antioxidant composition of 200 ppm TTBP, and a RANCIMAT result of 5.28 hrs.) with example no. 28 of this invention (with an antioxidant composition of 200 ppm TTBP and 200 ppm PDA, and a RANCIMAT result of 9.28 hrs) it can be seen that this invention provides a substantial benefit. A similar comparison, based on antioxidant composition of ETHANOX
compared to antioxidant compositions of this invention including ETHANOX 4703, can be made between comparative example no. 48 and example nos. 3, 7, 8, and 9 of this invention. Comparative example no. 47 shows use of 381 ppm PDA as an antioxidant with distilled biodiesel gives a RANCIMAT result of 6.39 hrs. While some of the examples of this invention using a distilled biodiesel and an antioxidant of PDA with a mono or bis-hindered phenolic show a lower RANCIMAT result, none of these examples use near 381 ppm PDA. The relatively high cost of PDA, and relatively low cost of phenolics, makes it beneficial to be able to use smaller amounts of PDA with a phenolic, in accordance with this invention, and yet obtain acceptable RANCIMAT
results. See, e.g., examples nos. 2 and 3 of this invention where, with a distilled biodiesel, only 200 ppm PDA is used with a phenolic and RANCIMAT results of 8.76 hrs and 10.52 hrs are obtained. Also, in each of the examples of this invention using a distilled biodiesel and an antioxidant of PDA and phenolic that shows a RANCIMAT
result lower than 6.39 hrs, the phenolic in the antioxidant is ETHANOX 4733;
the lowest such RANCIMAT result being 3.87 hrs. Comparing this to comparative example nos.
42 and 44 (RANCIMAT results of 2.94 hrs and 2.88 hrs), where ETHANOX 4733 is used with amines not of this invention, shows improved results with antioxidant compositions of this invention. Comparative example no. 49 shows use of 200 ppm PDA as an antioxidant with biodiesel (not distilled) gives a RANCIMAT result of 9.01 hrs. Comparative example no. 50 shows use of 200 ppm TTBP as an antioxidant with biodiesel (not distilled) gives a RANCIMAT result of 5.28 hrs. When a combination of 100 ppm TTBP and 100 ppm PDA of this invention is used as an antioxidant with biodiesel (not distilled) a RANCIMAT result of 8.1 hrs is obtained (example no. 27).
The result of 8.1 hrs with the TTBP/PDA combination is significantly better than the 5.28 hrs obtained with the TTBP alone. Also, the result of 8.1 hrs with the TTBP/PDA
combination is only slightly lower than the 9.01 hrs obtained with the PDA
alone and yet provides a commercially significant cost advantage. While some of the examples of this invention using a biodiesel (not distilled) and an antioxidant of PDA
with a mono or bis-hindered phenolic show a lower RANCIMAT result, none of these examples use near 200 ppm PDA.
Table 1 Example No. Biodiesel Sample Antioxidant Result (Hrs) Composition (ppm based on Biodiesel) 1 soybean oil methyl ester, 200 ppm ETHANOX 8.76 distilled 4733, 200 ppm PDA
2 soybean oil methyl ester, 200 ppm PDA, 200 10.52 distilled ppm ETHANOX 4702 3 soybean oil methyl ester, 200 ppm PDA, 200 9.53 distilled ppm ETHANOX 4703 4 soybean oil methyl ester, 85 ppm ETHANOX 5.85 distilled 4733, 295 ppm PDA
soybean oil methyl ester, 183 ppm ETHANOX 6.91 distilled 4733, 206 ppm PDA
6 soybean oil methyl ester, 296 ppm ETHANOX 5.89 distilled 4733, 98 ppm PDA
7 soybean oil methyl ester, 318 ppm PDA, 104 9.3 distilled ppm ETHANOX 4703 8 soybean oil methyl ester, 204 ppm PDA, 202 7.88 distilled ppm ETHANOX 4703 9 soybean oil methyl ester, 105 ppm PDA, 297 6.56 distilled ppm ETHANOX 4703 soybean oil methyl ester, 100 ppm ETHANOX 4.45 distilled 4733, 100 ppm PDA
11 soybean oil methyl ester, 200 ppm ETHANOX 6.5 distilled 4733, 200 ppm PDA
12 soybean oil methyl ester, 300 ppm ETHANOX 8.35 distilled 4733, 300 ppm PDA
13 soybean oil methyl ester, 150 ppm ETHANOX 3.87 distilled 4733, 50 ppm PDA
14 soybean oil methyl ester, 300 ppm ETHANOX 5.47 distilled 4733, 100 ppm PDA
15 soybean oil methyl ester, 450 ppm ETHANOX 6.78 distilled 4733, 150 ppm PDA
16 soybean oil methyl ester, 100 ppm ETHANOX 4.34 distilled 4733, 100 ppm PDA
17 soybean oil methyl ester, 200 ppm ETHANOX 6.54 distilled 4733, 200 ppm PDA
18 soybean oil methyl ester, 300 ppm ETHANOX 8.42 distilled 4733, 300 ppm PDA
19 soybean oil methyl ester, 400 ppm ETHANOX 9.69 distilled 4733, 400 ppm PDA
20 soybean oil methyl ester, 500 ppm ETHANOX 11.19 distilled 4733, 500 ppm PDA
21 soybean oil methyl ester, 375 ppm ETHANOX 6.15 distilled 4733, 125 ppm PDA
22 soybean oil methyl ester, 375 ppm ETHANOX 6.07 distilled 4733, 125 ppm PDA
23 soybean oil methyl ester, 100 ppm ETHANOX 7.74 not distilled 4733, 100 ppm PDA
24 soybean oil methyl ester, 200 ppm ETHANOX 9.04 not distilled 4733, 200 ppm PDA
25 soybean oil methyl ester, 150 ppm ETHANOX 6.82 not distilled 4733, 50 ppm PDA
26 soybean oil methyl ester, 300 ppm ETHANOX 8.3 not distilled 4733, 100 ppm PDA
27 soybean oil methyl ester, 100 ppm PDA, 100 8.1 not distilled ppm TTBP
28 soybean oil methyl ester, 200 ppm PDA, 200 9.28 not distilled ppm TTBP
29 soybean oil methyl ester, 100 ppm PDA, 300 8.38 not distilled ppm TTBP
30 soybean oil methyl ester, 100 ppm PDA, 100 7.77 not distilled ppm TTBP
31 soybean oil methyl ester, 75 ppm PDA, 75 ppm 6.95 not distilled TTBP
32 soybean oil methyl ester, 50 ppm PDA, 50 ppm 6.46 not distilled TTBP
33 soybean oil methyl ester, none 1.57 (comparative) distilled 34 soybean oil methyl ester, none 1.58 (comparative) distilled 35 soybean oil methyl ester, none 1.7 (comparative) distilled 36 soybean oil methyl ester, none 1.58 (comparative) distilled 37 soybean oil methyl ester, none 1.56 (comparative) distilled 38 soybean oil methyl ester, none 1.59 (comparative) distilled 39 soybean oil methyl ester, none 1.61 (comparative) distilled 40 soybean oil methyl ester, none 4.63 (comparative) not distilled 41 soybean oil methyl ester, none 4.49 (comparative) not distilled 42 soybean oil methyl ester, 300 ppm ETHANOX 2.94 (comparative) distilled 4733, 100 ppm didecylmethylamine 43 soybean oil methyl ester, 300 ppm ETHANOX 3.6 (comparative) distilled 4702, 100 ppm didecylmethylamine 44 soybean oil methyl ester, 300 ppm ETHANOX 2.88 (comparative) distilled 4733, 100 ppm dilauryl thiodipropionate 45 soybean oil methyl ester, 300 ppm ETHANOX 3.87 (comparative) distilled 4702, 100 ppm dilauryl thiodipropionate 46 soybean oil methyl ester, 300 ppm ETHANOX 4.06 (comparative) distilled 4702, 100 ppm N, N' disalicylidene propylenediamine 47 soybean oil methyl ester, 381 ppm PDA 6.39 (comparative) distilled 48 soybean oil methyl ester, 471 ppm ETHANOX 3.14 (comparative) distilled 4703 49 soybean oil methyl ester, 200 ppm PDA 9.01 (comparative) not distilled 50 soybean oil methyl ester, 200 ppm TTBP 5.28 (comparative) not distilled 51 soybean oil methyl ester, 400 ppm TTBP 5.53 (comparative) not distilled 52 soybean oil methyl ester, 600 ppm TTBP 5.84 (comparative) not distilled [0023] It is to be understood that the reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to being combined with or coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting combination or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or in forming a combination to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any, which occur in situ as a reaction is conducted is what the claim is intended to cover. Thus the fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, combining, blending or mixing operations, if conducted in accordance with this disclosure and with the application of common sense and the ordinary skill of a chemist, is thus wholly immaterial for an accurate understanding and appreciation of the true meaning and substance of this disclosure and the claims thereof.
[0024] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims below.
Glossary [0025] Biodiesel comprises crude biodiesel, distilled biodiesel, or any individual chemical component of either.
[0026] Crude biodiesel comprises 8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl ester, or fatty acid methyl ester derived from a vegetable or animal source.
[0027] Distilled biodiesel comprises crude biodiesel that has been subjected to at least one distillation step, e.g., to remove excess alcohols, residual glycerine, and other impurities, and includes biodiesel obtained as a specific cut or fraction produced during the distillation of crude biodiesel.
[0028] TTBP comprises essentially 100% 2,4,6-tri-tert-butylphenol.
[0024] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims below.
Glossary [0025] Biodiesel comprises crude biodiesel, distilled biodiesel, or any individual chemical component of either.
[0026] Crude biodiesel comprises 8 carbon to 22 carbon saturated, mono-unsaturated, di-unsaturated, or tri-unsaturated methyl ester, or fatty acid methyl ester derived from a vegetable or animal source.
[0027] Distilled biodiesel comprises crude biodiesel that has been subjected to at least one distillation step, e.g., to remove excess alcohols, residual glycerine, and other impurities, and includes biodiesel obtained as a specific cut or fraction produced during the distillation of crude biodiesel.
[0028] TTBP comprises essentially 100% 2,4,6-tri-tert-butylphenol.
Claims (19)
1. A composition comprising a biodiesel, a mono- or bis-hindered phenolic derived from 2,6-di-tert-butyl phenol, and a N,N'-di-substituted para-phenylene diamine, wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to about 5000 ppm based on the biodiesel.
2. The composition of claim 1 wherein (a) the biodiesel consists essentially of crude biodiesel;
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N, N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
3. The composition of claim 2 wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil.
4. The composition of claim 2 wherein the crude biodiesel is a fatty acid methyl ester.
5. The composition of claim 1 wherein (a) the biodiesel consists essentially of distilled biodiesel;
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
{i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
{i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
6. The composition of claim 5 wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, com oil, or used vegetable oil.
7. The composition of claim 1 wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel.
8. The composition according to claim 2 wherein the weight ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is: a) greater than about 1; b) greater than about 1.25; or c) greater than about 1.5.
9. A composition comprising biodiesel, 2,4,6-tri-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the weight ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is a) greater than about 1.
10. A composition comprising biodiesel, 2,4,6-tri-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine, wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is from about 10:1 to about 1:10 by weight.
11. A method of improving oxidation stability of a composition comprising biodiesel by combining the composition and mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol, and N,N'-di-substituted para-phenylene diamine such that the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 50 ppm to 5000 ppm based on the biodiesel.
12. The method of claim 11 wherein (a) the biodiesel consists essentially of crude biodiesel;
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
13. The method of claim 12 wherein the crude biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, com oil, or used vegetable oil.
14. The method of claim 12 wherein the crude biodiesel is a fatty acid methyl ester.
15. The method of claim 11 wherein (a) the biodiesel consists essentially of distilled biodiesel;
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
(b) the mono- or bis-hindered phenolic derived from 2,6-di-tert-butylphenol is:
(i) ortho-tert-butylphenol, (ii) 2,6-di-tert-butylphenol, (iii) 2,4,6-tri-tert-butylphenol, (iv) 4,4'-methylenebis(2,6-di-tert-butylphenol), (v) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, methyl ester, (vi) 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-C9 branched alkyl esters, (vii) 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, or (viii) butylated hydroxytoluene; and (c) the N,N'-di-substituted para-phenylene diamine is:
(i) N,N'-di-sec-butyl-p-phenylenediamine, (ii) N,N'- diisopropyl-p-phenylenediamine, or (iii) N,N'-bis-(1,4-dimethylpentyl)-p-phenylenediamine.
16. The method of claim 15 wherein the distilled biodiesel is derived from soybean oil, canola oil, palm oil, coconut oil, rapeseed oil, corn oil, or used vegetable oil.
17. The method of claim 11 wherein the combined amount of the mono- or bis-hindered phenolic and the N,N'-di-substituted para-phenylene diamine is from about 100 ppm to 2500 ppm based on the biodiesel.
18. The method according to claim 15 wherein the weight ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is a) greater than about 1.
19. The method according to claim 15 wherein the ratio of the 2,4,6-tri-tert-butylphenol to the N,N'-di-substituted para-phenylene diamine is from about 10:1 to about 1:10 by weight.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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US90855107P | 2007-03-28 | 2007-03-28 | |
US90854607P | 2007-03-28 | 2007-03-28 | |
US60/908,551 | 2007-03-28 | ||
US60/908,546 | 2007-03-28 | ||
PCT/US2008/056763 WO2008121526A1 (en) | 2007-03-28 | 2008-03-13 | Antioxidant blends for fatty acid methyl esters (biodiesel) |
Publications (1)
Publication Number | Publication Date |
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CA2681753A1 true CA2681753A1 (en) | 2008-10-09 |
Family
ID=39639792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002681753A Abandoned CA2681753A1 (en) | 2007-03-28 | 2008-03-13 | Antioxidant blends for fatty acid methyl esters (biodiesel) |
Country Status (11)
Country | Link |
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US (1) | US20100107481A1 (en) |
EP (1) | EP2137283A1 (en) |
JP (1) | JP2010522809A (en) |
KR (1) | KR20100015881A (en) |
CN (1) | CN101688137A (en) |
AU (1) | AU2008232984A1 (en) |
BR (1) | BRPI0809615A8 (en) |
CA (1) | CA2681753A1 (en) |
RU (1) | RU2009139760A (en) |
TW (1) | TW200848502A (en) |
WO (1) | WO2008121526A1 (en) |
Families Citing this family (10)
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CA2696885C (en) * | 2007-08-24 | 2015-10-13 | Albemarle Corporation | Antioxidant blends suitable for use in biodiesels |
GR1006805B (en) | 2009-02-26 | 2010-06-16 | Dorivale Holdings Limited, | Biodiesel containing non-phenolic additives and thereby possesing enhanced oxidative stability and low acid number. |
US20110023351A1 (en) * | 2009-07-31 | 2011-02-03 | Exxonmobil Research And Engineering Company | Biodiesel and biodiesel blend fuels |
US8367593B2 (en) | 2009-10-02 | 2013-02-05 | Exxonmobil Research And Engineering Company | Method for improving the resistance to one or more of corrosion, oxidation, sludge and deposit formation of lubricating oil compositions for biodiesel fueled engines |
US8680029B2 (en) | 2009-10-02 | 2014-03-25 | Exxonmobil Research And Engineering Company | Lubricating oil compositions for biodiesel fueled engines |
PL2533877T3 (en) | 2010-02-12 | 2020-08-24 | Donaldson Company, Inc. | Liquid filters |
US20120233912A1 (en) * | 2011-03-18 | 2012-09-20 | Otkrytoe Aktsionernoe Obschestvo "Sterlitamaxky Neftekhimichesky Zavod" | Antioxidant additive composition, a solution thereof, and a method for improving the storage stability of biodiesel fuel (variants) |
CN105985865B (en) * | 2015-02-02 | 2019-07-05 | 中国石油天然气股份有限公司 | Storage method of inedible animal and vegetable oil |
CN106367138B (en) * | 2016-10-29 | 2018-04-17 | 重庆众商众信科技有限公司 | A kind of preparation method of oxidation and corrosion type clean fuel |
CN114436886B (en) * | 2022-01-12 | 2023-07-21 | 烟台新特路新材料科技有限公司 | Long-chain amide compound and application thereof, and composite lubricant and preparation method thereof |
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US2739131A (en) * | 1952-03-28 | 1956-03-20 | Eastman Kodak Co | Color stabilization of arylamine antioxidants employing hydroquinone and derivatives thereof |
DE2141490A1 (en) * | 1971-08-19 | 1973-03-01 | Basf Ag | COLOR STABLE OXIDATION INHIBITORS |
JPS5684794A (en) * | 1979-12-14 | 1981-07-10 | Nikki Universal Co Ltd | Antioxidant for fuel oil |
US5509944A (en) * | 1994-08-09 | 1996-04-23 | Exxon Chemical Patents Inc. | Stabilization of gasoline and gasoline mixtures |
US5525126A (en) * | 1994-10-31 | 1996-06-11 | Agricultural Utilization Research Institute | Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst |
US5580482A (en) * | 1995-01-13 | 1996-12-03 | Ciba-Geigy Corporation | Stabilized lubricant compositions |
US5711767A (en) * | 1996-07-11 | 1998-01-27 | Ciba Specialty Chemicals Corporation | Stabilizers for the prevention of gum formation in gasoline |
US20060201056A1 (en) * | 2000-04-14 | 2006-09-14 | Oryxe Energy International, Inc. | Biodiesel fuel additive |
CN1514871A (en) * | 2001-03-22 | 2004-07-21 | 奥瑞克斯能源国际公司 | Use of plant-derived, oil-extracted material for reduced emissions |
DE102005015474A1 (en) * | 2005-04-04 | 2006-10-05 | Degussa Ag | Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound as primary antioxidant to the biodiesel |
US7964002B2 (en) * | 2006-06-14 | 2011-06-21 | Chemtura Corporation | Antioxidant additive for biodiesel fuels |
-
2008
- 2008-03-13 CA CA002681753A patent/CA2681753A1/en not_active Abandoned
- 2008-03-13 WO PCT/US2008/056763 patent/WO2008121526A1/en active Application Filing
- 2008-03-13 BR BRPI0809615A patent/BRPI0809615A8/en not_active IP Right Cessation
- 2008-03-13 JP JP2010501053A patent/JP2010522809A/en not_active Withdrawn
- 2008-03-13 EP EP08732069A patent/EP2137283A1/en not_active Withdrawn
- 2008-03-13 CN CN200880010251A patent/CN101688137A/en active Pending
- 2008-03-13 AU AU2008232984A patent/AU2008232984A1/en not_active Abandoned
- 2008-03-13 RU RU2009139760/05A patent/RU2009139760A/en unknown
- 2008-03-13 KR KR1020097022265A patent/KR20100015881A/en not_active Application Discontinuation
- 2008-03-13 US US12/593,383 patent/US20100107481A1/en not_active Abandoned
- 2008-03-26 TW TW097110658A patent/TW200848502A/en unknown
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CN101688137A (en) | 2010-03-31 |
BRPI0809615A8 (en) | 2017-02-21 |
WO2008121526A1 (en) | 2008-10-09 |
JP2010522809A (en) | 2010-07-08 |
AU2008232984A1 (en) | 2008-10-09 |
US20100107481A1 (en) | 2010-05-06 |
KR20100015881A (en) | 2010-02-12 |
EP2137283A1 (en) | 2009-12-30 |
BRPI0809615A2 (en) | 2016-07-12 |
TW200848502A (en) | 2008-12-16 |
RU2009139760A (en) | 2011-05-10 |
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