EP2447344B1 - Diesel composition and process for improving oxidation stability of biodiesel - Google Patents

Diesel composition and process for improving oxidation stability of biodiesel Download PDF

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Publication number
EP2447344B1
EP2447344B1 EP10791159.6A EP10791159A EP2447344B1 EP 2447344 B1 EP2447344 B1 EP 2447344B1 EP 10791159 A EP10791159 A EP 10791159A EP 2447344 B1 EP2447344 B1 EP 2447344B1
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Prior art keywords
acid
phenylene diamine
anhydride
diesel
component
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German (de)
English (en)
French (fr)
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EP2447344A1 (en
EP2447344A4 (en
Inventor
Jianmin Lin
Yongguang Zhang
Jianrong Zhang
Hang Li
Shuai LI
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority claimed from CN 200910087970 external-priority patent/CN101928614B/zh
Priority claimed from CN 200910089959 external-priority patent/CN101987980B/zh
Priority claimed from CN200910090512.0A external-priority patent/CN101993744B/zh
Priority claimed from CN 200910090511 external-priority patent/CN101993743B/zh
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Publication of EP2447344A1 publication Critical patent/EP2447344A1/en
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    • C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
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    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
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    • C10L2200/0446—Diesel
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    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • the present invention relates to a diesel composition and a method of increasing the oxidation stability of biodiesel.
  • Biodiesel also called fatty acid methyl ester
  • oil crops such as soybeans and rapeseeds
  • the fruits of oil plants such as Elaeis and Pistacia chinesis Bunge
  • oil water plants such as algae as well as animal fats, used cooking oils thrown away by restaurants or families, and the like with alcohols (methanol, ethanol), and is a clean biofuel.
  • Biodiesel has three advantages of being renewable, clean and safe, and is strategically significant to the agricultural structure adjustment, energy safety and protection of the ecological environment. At present, China is a net importer of petroleum and has limited petroleum reserves, and importing petroleum in huge quantity threatens the energy safety in China; thus, the study on and production of biodiesel is practically significant in China.
  • Biodiesels having poor oxidation stability tends to produce the following aging products: 1) insoluble polymers (gelatines and fatlute), which will cause clogging of engine filters and coking of jet pumps, and result in an increased smoke discharge and difficulty in start-up; 2) soluble polymers, which can form resin-like materials in engines, and may possibly result in flameout and difficulty in start-up; 3) aging acids, which will erode metal parts in engines; 4) peroxides, which will cause aging and embrittlement of rubber parts, resulting in fuel leak.
  • insoluble polymers gelatines and fatlute
  • soluble polymers which can form resin-like materials in engines, and may possibly result in flameout and difficulty in start-up
  • 3) aging acids which will erode metal parts in engines
  • peroxides which will cause aging and embrittlement of rubber parts, resulting in fuel leak.
  • olefins, diolefins and non-hydrocarbons, such as sulphides and nitrides in petroleum diesel (usually known as diesel, petroleum diesel being introduced here is to be distinguished from biodiesel) produce a series of oxidation intermediate products in the presence of oxygen, and generate insoluble precipitates by condensation.
  • insoluble particles generated during the storage of petroleum diesel will influence the properties of the fuel, resulting in the clogging of filter systems, and causing the parts of fuel systems to malfunction, such that the atomization of the oil sprayed will be affected, leading to incomplete combustion, and even the formation of excess carbon deposit in engines to clog spray nozzles.
  • biodiesel Since the oxidation stability of biodiesel is inferior to that of petroleum diesel, the above problems will be worse if biodiesel is blended with petroleum diesel. The most obvious manifestation is that the stability of a biodiesel-containing blended fuel is inferior to that of petroleum diesel.
  • One way is to add antioxidants in pure biodiesel to delay its oxidation, hence mitigating the harms made by the aging products; the other way is to add stabilizers in petroleum diesel or a biodiesel-containing blended fuel to improve the stability of the blended fuel.
  • a stabilizer is capable of terminating, weakening or interfering with various oxidation reactions to inhibit oil deterioration and then improve the stability.
  • CN 1742072A discloses a process for increasing the storage stability of biodiesel, comprising adding a stock solution comprising 15-60 wt.% 2,4-di-tert-butylhydroxy toluene dissolved in biodiesel, into the biodiesel to be stabilized until the 2,4-di-tert-butylhydroxy toluene reaches a concentration of 0.005-2 wt.% with respect to the total solution of biodiesel.
  • CN 1847368A discloses a method of increasing the oxidation stability of biodiesel, comprising adding a bisphenol-type antioxidant, such as 4,4'-methylenebis[2,6-di-tert-butylphenol] or 2,2'-methylenebis[6-tert-butyl-4-methylphenol], to the biodiesel to be stabilized in a quantity of 10-20000 ppm (w/w).
  • a bisphenol-type antioxidant such as 4,4'-methylenebis[2,6-di-tert-butylphenol] or 2,2'-methylenebis[6-tert-butyl-4-methylphenol
  • CN 1847369A discloses a method of increasing the oxidation stability of biodiesel, comprising adding a primary antioxidant having a melting point of less than or equal to 40 °C to the biodiesel to be stabilized in an amount of from 10 to 20000 ppm (w/w), where the primary antioxidant comprises alkylphenol.
  • US2007/113467A1 discloses a fuel composition having an improved oxidation stability, which comprises biodiesel and at least one antioxidant selected from the group consisting of propyl gallate, 1,2,3-trihydroxybenzene, 2,6-di-tert-butyl-p-methylphenol, butylated hydroxyanisole, dilauryl thiodipropinate, tocopherol, and quinoline derivatives.
  • CN 101144040A and CN 101353601A disclose methods of improving the oxidation stability of biodiesel by using an arylamine-type antioxidant.
  • US 2009/0139135 A1 discloses a method for improving the stability of biodiesel comprising adding an alkyl phenol amine aldehyde condensate additive to the biodiesel.
  • WO 2008/124390 A2 refers to a fuel composition comprising a specific fatty acid ester, a nitrogen containing detergent and a phenolic antioxidant.
  • EP 1 847 583 A2 and EP 1 847 584 A2 relate to the prevention or retardation of the oxidation of oils derived from plant or animal materials.
  • One of the object of the present invention is to provide a diesel composition with an improved oxidation stability of biodiesel or a superior stability and a method of improving the oxidation stability of biodiesel in order to remove the above-mentioned disadvantages of the prior art of requiring a large amount of antioxidant and having a poor effect of improving the stability of a biodiesel-containing blended fuel.
  • the present invention provides according to claim 1 a diesel composition
  • a diesel composition comprising a base diesel and an additive composition.
  • Said base diesel comprises biodiesel
  • said additive composition comprises component (a) and component (b), wherein said component (a) is an arylamine-type antioxidant which is a substituted p-phenylene diamine, and said component (b) is one or more polyamines or derivatives thereof.
  • the present invention further provides a method of increasing the oxidation stability of biodiesel, comprising adding, in a biodiesel-containing base diesel, an additive, wherein said additive is the additive composition provided by the present invention.
  • the diesel composition of the present invention has a superior oxidation stability, and component (a) and component (b) surprisingly show synergism, i.e., a much better antioxidative effect than a single antioxidant.
  • Component (b) can be regarded as a co-antioxidant, which surprisingly greatly enhances the effect of the antioxidant.
  • the amount of component (a) in the biodiesel composition can be reduced considerably, and in particular when component (a) is expensive or is toxic or corrosive in some degree. It is of great significance to reduce the amount of component (a).
  • the diesel composition of the present invention has a remarkably improved antioxidative property due to the significant synergism of the components.
  • the amount of additive can be selected from a relatively wide range, such as 50-10000 ppm, preferably 80-8000 ppm, and more preferably 100-5000 ppm, on the basis of the amount of the base diesel.
  • the weight ratio of said component (b) to said component (a) is 0.01-100: 1, preferably 0.02-50: 1, more preferably 0.05-10: 1, even more preferably 0.2-5:1.
  • Component (a) is at least one arylamine-type antioxidant which is a substituted p-phenylene diamine.
  • Said substituted p-phenylene diamine-type antioxidant can be a product obtained by substitution of the hydrogen atom(s) of the amino group(s) (-NH 2 ) in the p-phenylene diamine with one or more of alkyl, aryl, aralkyl, alkylaryl, hydrocarbylacyl, hydrocarbylsulfonyl and hydrocarbylacyloxy.
  • substituents may be the same or different.
  • said substituted p-phenylene diamine-type antioxidant can be one or more of mono-alkyl substituted p-phenylene diamine, mono-aryl substituted p-phenylene diamine, mono-alkylaryl substituted p-phenylene diamine, mono-arylalkyl substituted p-phenylene diamine, mono-hydrocarbylacyl substituted p-phenylene diamine, mono-hydrocarbylsulfonyl substituted p-phenylene diamine, mono-hydrocarbylacyloxy substituted p-phenylene diamine, N-alkyl-N'-alkyl substituted p-phenylene diamine, N-aryl-N'-alkyl substituted p-phenylene diamine, N-alkyl-N'-alkylaryl substituted p-phenylene diamine, N-aryl-N'-alkyl substituted p-phenylene diamine, N-arylalkyl-N'-al
  • said substituted p-phenylene diamine-type antioxidant includes, but is not limited to, one or more of the following:
  • the substituted p-phenylene diamine-type antioxidant is preferably one or more dialkyl p-phenylene diamines wherein the hydrogen atoms of the amino groups therein are substituted by two alkyl radicals, two aryl radicals or one alkyl radical and one aryl radical, and particularly preferably one or more substituted dialkyl p-phenylene diamines, wherein the two amino groups therein are independently substituted with an alkyl radical having 4 to 10 carbon atoms or an aryl radical having 6 to 15 carbon atoms, such as, one or more of N,N'-diheptyl-p-phenylene diamine, N,N'-di-sec-butyl-p-phenylene diamine, N,N'-bis-(1-ethyl-3-methylamyl)p-phenylene diamine, N,N'-bis-(1,4-dimethylbutyl) p-phenylene diamine, N,N'-di
  • the component (a) is most preferably one or more of N,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylene diamine, N-octyl-N'-phenyl-p-phenylene diamine, N,N'-diheptyl-p-phenylene diamine, N,N'-di-sec-butyl-p-phenylene diamine, N,N'-dioctyl-p-phenylene diamine, N,N'-bis-(1-methylheptyl)p-phenylene diamine, N,N'-bis-(1-ethyl-3-methylamyl) p-phenylene diamine and N,N'-bis-(1,4-dimethylbutyl) p-phenylene diamine.
  • a polyamine is an organic amine having the structure shown by the structural formula (A):
  • the polyamine of component (b) is one or more of the following amines: a polyether diamine of formula (A1):
  • hydrocarbyl herein refers to hydrocarbon substituents, including aliphatic, alicyclic, aryl and heterocyclic substituents.
  • the aliphatic hydrocarbyl may be a saturated hydrocarbyl or unsaturated hydrocarbyl having a double or triple bond, including alkyl, alkenyl, and alkynyl.
  • alkyl in the present invention refers to linear or branched alkyl typically having 1 to 30, preferably 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, iso-amyl, 2-methylbutyl, neo-amyl, 3-amyl, n-hexyl, 4-methylamyl, 3-methylamyl, 2-methylamyl, 1-methylamyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, 1-methyl-2-methylpropyl, n-heptyl, n-octyl, n-
  • alkenyl in the present invention refers to linear or branched alkenyl having a double bond and typically having 2 to 30, preferably 2 to 6 carbon atoms, such as vinyl, 1-propenyl, 1-propyl-2-ene, 2-propenyl, 1-butenyl, 1-butyl-2-ene, 1-butyl-3-ene, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-1-propyl-2-ene, 2-methyl-1-propyl-2-ene, 1-pentenyl, 1-amyl-2-ene, 1-amyl-3-ene, 1-amyl-4-ene, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-1-butyl-2-ene, 2-methyl-1-butyl-2-ene, 3-methyl-1-butyl-2-ene, 1-methyl-1-butyl-3-ene, 2-methyl-1-butyl-2-ene, 1-methyl
  • alkynyl in the present invention refers to linear or branched alkynyl having a triple bond and typically having 2 to 30, preferably 2 to 6 carbon atoms, such as ethynyl, 1-propynyl, 1-propyl-2-yne, 1-butynyl, 1-butyl-2-yne, 1-butyl-3-yne, 1-pentynyl, 1-amyl-2-yne, 1-amyl-3-yne, 1-amyl-4-yne, 3-methyl-1-butynyl, 1-methyl-1-butyl-2-yne, 1-methyl-1-butyl-3-yne, 2-methyl-1-butyl-3-yne, 1-hexynyl, 1-hexyl-2-yne, 1-hexyl-3-yne, 1-hexyl-4-yne, 1-hexyl-5-yne, 3-methyl-1-pentynyl
  • alicyclic hydrocarbyl in the present invention refers to saturated cyclohydrocarbyl or unsaturated cyclohydrocarbyl having a double or a triple bond, including cycloalkyl and cycloalkenyl.
  • cycloalkyl is selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Cyclopropyl, cyclopentyl, cyclohexyl etc. are prefered, and cyclopropyl and cyclohexyl are more preferred.
  • cycloalkenyl is selected from the group consisting of cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, and the like, of which cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl etc. are preferred, and cyclopentenyl and cyclopentadienyl are more preferred.
  • aryl in the present invention refers to any functional groups or substituents derived from simple aromatic rings, such as phenyl, and substituted phenyl (e.g., benzyl, phenylethyl, methoxyphenyl, dinitrophenyl, tert-butoxycarbonylphenyl, and the like), and fused aromatic rings, such as, naphthyl, anthryl, phenanthrenyl, and substituted naphthyl, and the like.
  • simple aromatic rings such as phenyl, and substituted phenyl (e.g., benzyl, phenylethyl, methoxyphenyl, dinitrophenyl, tert-butoxycarbonylphenyl, and the like), and fused aromatic rings, such as, naphthyl, anthryl, phenanthrenyl, and substituted naphthyl, and the like.
  • heterocyclic substituent in the present invention comprises a 3-8 membered, saturated cyclic structure containing heteroatoms, or a 3-8 membered, unsaturated cyclic structure containing heteroatoms.
  • Said "3-8 membered, saturated cyclic structure containing heteroatoms” refers to a 3-8 membered cyclic structure having no unsaturated bonds in the ring, such as, azacyclopropane (aziridine), 2H-azacyclopropane, diazacyclopropane, azacyclobutane, 1,2-diazacyclobutane, pyrrolidine, imidazolidine, pyrazolidine, hydrogenated pyridone, piperidine , piperazine, ethylene oxide, dioxacyclopropane, thiacyclopropane, oxacyclobutane, 1,2-dioxacyclobutane, thiacyclobutane, tetrahydrofuran, tetrahydrothiophene, 1,3-dioxacyclopentane, 1,3-dithiacyclopentane, tetrahydropyran, 1,4-dioxacyclohe
  • Said "3-8 membered, unsaturated cyclic structure containing heteroatoms” refers to a 3-8 membered cyclic structure having unsaturated bonds, such as 3H-diazacyclopropene, azacyclobutadiene, 1,2-diazacyclobutene, pyrrole, dihydropyrrole, imidazole, 4,5-dihydroimidazole, pyrazole, 4,5-dihydropyrazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, pyridine, 2-pyridone, 4-pyridone, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,4,5-tetrazine, azacycloheptantriene, 1,2-diazacycloheptantriene, 1,3-diazacycloheptantriene, 1,
  • hydrocarbyl having 1 to 30 carbon atoms may further carry a group selected from the group consisting of carbonyl, hydroxy (-OH), carboxyl (-COOH), ester groups, acyl, alkoxy, nitro, cyano, halo and amino.
  • halo in the present invention refers to fluoro, chloro, bromo, iodo and the like, of which fluoro, chloro and bromo are preferred, and chloro is more preferred.
  • alkoxy in the present invention has a linear or branched alkyl and 1 to 30, preferably 1 to 18, carbon atoms, such as, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, 2-methylbutoxy, neo-pentoxy, 3-pentoxy, n-hexoxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy, 1-methyl-2-methylpropoxy, n-heptoxy, n-octoxy, n-nonyloxy, n-decyloxy, n-undecy
  • the "ester group” in the present invention has a linear or branched alkyl and 1 to 30, preferably 1 to 18, carbon atoms, such as, methyl ester group, ethyl ester group, n-propyl ester group, iso- propyl ester group, n-butyl ester group, iso-butyl ester group, sec-butyl ester group, tert-butyl ester group, n-pentyl ester group, iso-pentyl ester group, 2-methylbutyl ester group, neo-pentyl ester group, 3- pentyl ester group, n-hexyl ester group, 4-methylpentyl ester group, 3-methylpentyl ester group, 2-methylpentyl ester group, 1-methylpentyl ester group, n-heptyl ester group, n-octyl ester group, n-nonyl ester group, n-
  • acyl in the present invention has a linear or branched alkyl and 1 to 30, preferably 1 to 18, carbon atoms, such as, formyl, acetyl, n-propionyl, iso-propionyl, n-butyryl, iso-butyryl, sec-butyryl, tert-butyryl, n-valeryl, iso-valeryl, 2-methylbutyryl, neo-valeryl, 3-valeryl, n-hexanoyl, 4-methylvaleryl, 3-methylvaleryl, 2-methylvaleryl, 1-methylvaleryl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, n
  • hydrocarbylene in the present invention is formed by removal of one hydrogen atom from the “hydrocarbyl” defined above.
  • Said hydrocarbylene has 1 to 30, preferably 1 to 24 carbon atoms.
  • Said derivatives of polyamines are the reaction products of the ammonolysis reaction of one or more organic acids having 6 to 40 carbon atoms, acyl halides having 6 to 40 carbon atoms, or organic acid alkyl esters having 6 to 40 carbon atoms with the above-mentioned polyamines. Further preferred are the reaction products of the ammonolysis reaction of one or more monofatty acids having 6 to 40 carbon atoms, fatty acyl halides having 6 to 40 carbon atoms, or fatty acid alkyl esters having 6 to 40 carbon atoms with the above-mentioned polyamines.
  • Said ammonolysis reaction refers to a metathetic reaction of one or more of fatty acids, fatty acyl halides and fatty acid alkyl esters with ammonia and/or amine to produce an amide.
  • the reaction product of the above reaction can be used directly as component (b) without being isolated and purified, or the amidate alone therein can be used as component (b) after isolation and purification. Without isolation and purification, the mixture primarily comprises an amidate, and typically further comprises some unreacted starting materials and other reaction products, such as ammonium salts or alcohols. The specific composition of the mixture varies slightly depending on the reaction conditions.
  • the amidate according to the present invention is commercially available or obtained through a variety of known amidation reactions.
  • it is obtained by the ammonolysis reaction of an acid of formula (B1) or an ester of formula (B2) with a polyamine of formula (A) in a molar ratio of 1: (0.5-2).
  • said polyamine is present in a stoichiometric amount or a slightly excess amount relative to said acid, acyl halide or ester.
  • an organic monocarboxylic acid of formula (B1) or an organic monocarboxylate of formula (B2) reacts with a polyamine of formula (A) in a molar ratio of 1: (1-2), and the product obtained from the ammonolysis reaction is preferably used directly as component (b) of the present invention without being isolated and purified.
  • R is a hydrocarbyl having 6 to 40, preferably 8 to 36 carbon atoms.
  • R is a hydrocarbyl having 6 to 40, preferably 8 to 36 carbon atoms.
  • hydrocarbyl used herein is as defined above, and refers to hydrocarbon substituents, including aliphatic, alicyclic, aryl and heterocyclic substituents.
  • the aliphatic hydrocarbyl may be a saturated hydrocarbyl or unsaturated hydrocarbyl having a double or triple bond.
  • formula (B1) may be a fatty acid, a naphthenic acid, an aromatic acid, or a substituted aromatic acid, and preferably a fatty acid, which may be a monoacid, or a polyacid, such as a diacid.
  • Said acid can be an acid alone or a mixture of acids, such as one or more fatty acids of vegetable oils, e.g., palmitic acid, soybean oil acid, peanut oil acid, rapeseed oil acid, ricinoleic acid, and tall oil fatty acid, and is most preferably one or more liquid acids at normal temperature, e.g. oleic acid, linoleic acid, linolenic acid, dimer oleic acid, dimer linoleic acid, industrial dimer acids, soybean oil acid, peanut oil acid, rapeseed oil acid, ricinoleic acid, and tall oil fatty acid.
  • fatty acids of vegetable oils e.g., palmitic acid, soybean oil acid, peanut oil acid, rapeseed oil acid, ricinoleic acid, and tall oil fatty acid
  • liquid acids at normal temperature e.g. oleic acid, linoleic acid, linolenic acid, dimer oleic acid
  • the substituted aromatic acids are, for example, substituted benzoic acid and/or alkyl substituted salicylic acid, and the like.
  • the fatty acids according to the present invention are C6-C40 fatty acids, preferably one or more of caproic acid, adipic acid, octanoic acid, isooctanoic acid (2-ethylcaproic acid), capric acid, dodecanic acid (lauric acid), tetradecanoic acid, hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), oleic acid, linoleic acid, linolenic acid, ricinolic acid, eicosenoic acid, arachidic acid, erucic acid, docosenoic acid, dimers of oleic acid and/or linoleic acid, dimer oleic acid, dimer linoleic acid, industrial dimer acids,
  • R' is an alkyl having 1 to 5 carbon atoms, preferably methyl, ethyl, propyl, or isopropyl.
  • Formula (B2) is an ester of the acid of formula (B1), preferably a methyl ester of the acid of formula (B1) or a mixture thereof, and particularly preferably a biodiesel.
  • Component (b) preferably comprises one or more of the following amidates, wherein the carbonyl moiety of the amide has 6 to 40, preferably 8 to 36, carbon atoms:
  • Said derivatives of polyamines can also be the reaction products of the condensation reaction of the above-mentioned polyamines with C1-C6 aldehyde.
  • the condensation reaction of polyamines with aldehydes is commonly known in the art.
  • the products are predominantly substituted triazines or substituted methanes.
  • the reaction conditions generally include a molar ratio of total polyamines to C1-C6 aldehyde of 1: (0.1-10), preferably 1: 0.2-5, and more preferably 1: 0.3-3, in no presence of a solvent or at the present of a solvent, which is a hydrocarbon solvent, such as hexane, heptane, toluene, or xylene, added for refluxing and separating the reaction water, at a temperature of typically 80-150 °C, for a period of time such that the reaction no longer generates water, which is generally from 30 minutes to 10 hours.
  • a solvent which is a hydrocarbon solvent, such as hexane, heptane, toluene, or xylene
  • Said C1-C6 aldehyde is one or more of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, cyclohexanecarboxaldehyde and an aqueous solution of one or more of them, and preferably one or more of formaldehyde, acetaldehyde, propionaldehyde, cyclohexanecarboxaldehyde and an aqueous solution of one or more of them.
  • Said formaldehyde may be in the form of a formaldehyde solution or a polyformaldehyde.
  • Said ammonolysis reaction refers to a metathetic reaction of one or more of fatty acids, fatty acyl halides and fatty acid alkyl esters with polyamine to produce an amide.
  • the reaction product of the above reaction can be used directly as component (b) without being isolated and purified, or the amidate alone therein can be used as component (b) after isolation and purification. Without isolation and purification, the mixture primarily comprises an amidate, and typically further comprises some unreacted starting materials and other reaction products, such as ammonium salts or alcohols.
  • the specific composition of the mixture varies slightly depending on the reaction conditions.
  • the C6-C30 hydrocarbyl substituted organic dicarboxylic acid may be one or more of C6-C30 hydrocarbyl substituted maleic acid, butane dicarboxylic acid (succinic acid), fumaric acid, itaconic acid, citraconic acid, isatoic acid, and phthalic acid;
  • the C6-C30 hydrocarbyl substituted anhydride may be one or more of C6-C30 hydrocarbyl substituted maleic anhydride, succinic anhydride (butane dicarboxylic acid anhydride), itaconic anhydride, citraconic anhydride, isatoic anhydride and phthalic anhydride;
  • the C6-C30 hydrocarbyl substituted half ester may be a partially esterified product of the above C6-C30 hydrocarbyl substituted organic dicarboxylic acid or hydride with an alcohol, preferably a fatty alcohol.
  • the preferred acylating agent containing two acyl groups in a molecule is one or more of C6-C30 hydrocarbyl substituted succinic acid and C6-C30 hydrocarbyl substituted succinic anhydride.
  • the structural formula of the C6-C30 hydrocarbyl substituted succinic acid is shown by formula (B3)
  • the structural formula of the C6-C30 hydrocarbyl substituted succinic anhydride is shown by formula (B4): wherein R is a hydrocarbyl having 6 to 30 carbon atoms.
  • hydrocarbyl used herein is as defined above, and refers to hydrocarbon substituents, including aliphatic, alicyclic, aryl and heterocyclic substituents.
  • the aliphatic hydrocarbyl may be a saturated hydrocarbyl or unsaturated hydrocarbyl having a double or triple bond.
  • R is preferably an aliphatic hydrocarbyl having 8 to 24 carbon atoms, especially linear alkyl or alkenyl.
  • Representative C6-C30 hydrocarbyl substituted organic dicarboxylic acids useful as acylating agents in the present invention may be one or more of nonylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid, tridecylsuccinic acid, tetradecylsuccinic acid, pentadecylsuccinic acid, hexadecylsuccinic acid, octadecylsuccinic acid, nonenylsuccinic acid, decenylsuccinic acid, dodecenylsuccinic acid, tetradecenylsuccinic acid, cetenylsuccinic acid, octadecenesuccinic acid, and docosenylsuccinic acid.
  • Representative C6-C30 hydrocarbyl substituted anhydrides useful as acylating agents in the present invention may be one or more of nonylsuccinic anhydride, decylsuccinic anhydride, dodecylsuccinic anhydride, tridecylsuccinic anhydride, tetradecylsuccinic anhydride, pentadecylsuccinic anhydride, hexadecylsuccinic anhydride, octadecylsuccinic anhydride, nonenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, cetenylsuccinic anhydride, octadecenesuccinic anhydride, and docosenylsuccinic anhydride.
  • the process for preparing the above-mentioned C6-C30 hydrocarbyl substituted succinic anhydride is commonly known in the art, such as the thermal polymerization of a polyolefin having a corresponding chain length with maleic anhydride, or the substitution of a chlorinated hydrocarbon, e.g., a chlorinated polyolefin, with maleic anhydride.
  • a chlorinated hydrocarbon e.g., a chlorinated polyolefin
  • hydrocarbyl substituted succinic acid is commercially available or obtainable by a variety of methods known in the art, such as by hydrolysis of the corresponding hydrocarbyl substituted succinic anhydride by treating it with water or water vapor. Specific conditions and operations for hydrolysis are known by the person skilled in the art.
  • the reaction product of the ammonolysis reaction of a hydrocarbyl substituted succinic acid and/or succinic anhydride with a polyamine is related to both the reaction temperature and the molar ratio of the reactants.
  • a low reaction temperature about 100 °C
  • a high reaction temperature about 150 °C
  • two or more succinic acid and/or succinic anhydride molecules react with the same polyamine molecule to produce the so-called "double hanging" or "multiple hanging” reaction product.
  • the present invention preferably involves excess polyamine, which results in the production of a "mono-hanging" reaction product.
  • the additive composition of the present invention further comprises component (c), which is a metal deactivator capable of reacting with a metal surface and/or a metal chelator capable of reacting with or binding to a metal or metal ion.
  • component (c) is a metal deactivator capable of reacting with a metal surface and/or a metal chelator capable of reacting with or binding to a metal or metal ion.
  • the weight ratio of said component (a) to said component (c) is 1: 0-1, preferably 1: 0.01-1, further preferably 1: 1: 0.01-0.5, and even further preferably 1: 0.02-0.2.
  • said component (c) may be one or more of benzotriazole and derivatives thereof, thiadiazole and derivatives thereof, 8-hydroxyquinoline, ethylene diamine tetracarboxylic acids, hydrazides, ⁇ -diones, ⁇ -ketone esters, Schiff's bases, and organic polycarboxylic acid and derivatives thereof.
  • benzotriazole does not have an excellent solubility in biodiesel, it is generally modified by, basically, introduction thereto of an oil soluble group, such as a long-chain hydrocarbyl, in order to increase its solubility in biodiesel.
  • said benzotriazole derivatives may be various derivatives having a better solubility in biodiesel than benzotriazole.
  • said benzotriazole derivative may be one or more of an ammonium salt formed by benzotriazole and a fatty amine, and a product obtained by the Mannich reaction of benzotriazole, formaldehyde and a fatty amine.
  • Said ethylene diamine tetracarboxylic acids may be ethylene diamine tetraacetic acid (EDTA)
  • said hydrazides may be N-salicylidene-N'-salicyl hydrazide and/or N,N'-diacetyladipoyl dihydrazide.
  • Said ⁇ -dione is, for example, acetylacetone
  • said ⁇ -ketone ester is, for example, octylacetoacetate.
  • Said Schiff's base may be one or more of N,N'-disalicylidene-1,2-ethylene diamine, N,N'-disalicylidene -1,2-propylene diamine, N,N'-disalicylidene-1,2-cyclohexanediamine, and N,N'-disalicylidene-N'-methyldipropylene triamine.
  • Said organic polycarboxylic acid and derivatives thereof may be, for example, one or more of citric acid, tartaric acid, malic acid, succinic acid (butane dicarboxylic acid), maleic acid, phytic acid and derives thereof.
  • said component (c) is preferably one or more of benzotriazole, an ammonium salt formed from benzotriazole and a fatty amine, a product obtained by the Mannich reaction of benzotriazole, formaldehyde and a fatty amine (such as the commercially available additive T551), Schiff's base, organic polycarboxylic acids, and a product obtained by the condensation reaction of an organic polycarboxylic acid with a fatty amine or fatty alcohol (i.e., the amide or ester derivatives of organic polycarboxylic acids).
  • benzotriazole an ammonium salt formed from benzotriazole and a fatty amine
  • a product obtained by the Mannich reaction of benzotriazole, formaldehyde and a fatty amine such as the commercially available additive T551
  • Schiff's base such as the commercially available additive T551
  • organic polycarboxylic acids such as the commercially available additive T551
  • the additive composition of the present invention may further comprise one or more additional additives, such as flow improvers, cetane number improvers, antistatic agents, preservatives, rust inhibitors, and demulsifiers, if needed.
  • additional additives such as flow improvers, cetane number improvers, antistatic agents, preservatives, rust inhibitors, and demulsifiers, if needed.
  • the preparation of the additive composition of the present invention is simple, only requiring the mixing of the components for forming the additive composition homogeneously.
  • a solvent which can be a polar solvent, such as one or more of N,N-dimethylformamide (DMF), 1,4-dioxane, tetrahydrofuran (DHF), dimethyl sulphoxide (DMSO), pyrrolidone and methylpyrrolidone, or a hydrocarbon, in particularly an aromatic, such as benzene, toluene, xylene, an aromatic diluent oil and a mixture thereof and which can also be a biodiesel or a fatty alcohol, such as iso-octanol.
  • a solvent which can be a polar solvent, such as one or more of N,N-dimethylformamide (DMF), 1,4-dioxane, tetrahydrofuran (DHF), dimethyl sulphoxide (DMSO), pyrrol
  • the diesel composition of the present invention can be obtained by adding an additive composition according to the present invention into a base diesel, or by adding each of the components of additives according to the present invention into a base diesel, respectively.
  • the base diesel may be a pure biodiesel.
  • Said biodiesel refers to the fatty acid low-carbon alcohol esters produced by the transesterification (alcoholysis) of oils/fats with low-carbon alcohols (such as C 1 -C 5 fatty alcohols), and is commonly fatty acid methyl ester, i.e., a product of transesterification of an oil/fat with methanol.
  • Said transesterification may be any known or unknown process for the preparation of a biodiesel by the transesterification of an oil/fat with a low-carbon alcohol, such as, acid catalysis, base catalysis, enzyme catalysis, supercritical method and the like. Please refer to CN1473907A , DE3444893 , CN1472280A , CN1142993C , CN1111591C and CN1594504A for details.
  • Said oil/fat has a generally recognized meaning in the art, is a general term for oils and fats, and comprises fatty acid triglyceride as the main component. Generally, those that are liquid at ambient temperature are called oils, and those that are solid or semi-solid at ambient temperature are called fats. Said oils/fats include vegetable oils and animal fats, and additionally, oil materials from microorganisms and algae, and can even be waste oils/fats, such as used or deteriorated oils/fats including used cooking oils, sewer oils, garbage oils, and acidified oils from oil/fat factories.
  • Said vegetable oils may be oils from both herbs and woody plants, such as peanut oil, corn oil, cottonseed oil, rape seed oil, soybean oil, palm oil, safflower oil, flaxseed oil, coconut oil, oak oil, almond oil, walnut oil, castor oil, sesame oil, olive oil, Tall oil, sunflower oil, curcas oil, tung oil, sorbifolia oil, pistacia oil, and oils from halophytes, e.g., seaside mellow and cyperus beans.
  • Said animal fats may be lard, chicken fat, duck fat, goose fat, mutton fat, horse fat, tallow, whale fat, shark fat, and the like.
  • the base diesel may further comprise one or more additional diesels selected from the group consisting of petroleum diesel, Fischer-Tropsch synthetic diesel, hydrocracked biodiesel, and an oxygen-containing diesel concoction, wherein the ratio of the volume of said biodiesel to the volume of said additional diesels is preferably 1: 2-99.
  • additional diesels selected from the group consisting of petroleum diesel, Fischer-Tropsch synthetic diesel, hydrocracked biodiesel, and an oxygen-containing diesel concoction, wherein the ratio of the volume of said biodiesel to the volume of said additional diesels is preferably 1: 2-99.
  • Said petroleum diesel refers to a fuel for compression-ignited internal-combustion engines, obtained by subjecting a crude oil (petroleum) to various refining processes in a refinery, such as normal pressure-deduced process, catalytic cracking, catalytic reforming, carbonizing, hydrorefining, and hydrocracking, to produce a fraction having a distillation range between 160°C and 380 °C, and then formulating the fuel such that it will meet the national standard GB 252 for light diesels or the national standard GB 19147 for automobile diesels.
  • a crude oil petroleum
  • Fischer-Tropsch synthetic diesel primarily refers to GTL diesel (Gas To Liquid) or CTL diesel (Coal To Liquid) produced from natural gas or coal as the starting material, by Fischer-Tropsch (F-T) synthetic method, or BTL diesel (Biomass To Liquid) produce from plant fibers by Fischer-Tropsch synthetic method.
  • Fischer-Tropsch synthetic diesel is substantially free of sulphur and aromatic hydrocarbon, and is a very clear fuel. However, it has a very poor lubricity. Though it has a greatly improved lubricity after being mixed with biodiesel, the oxidation stability of the blended oil may be deteriorated. Thus, a biodiesel-containing blended fuel requires the addition of antioxidants, too.
  • Hydrocracked biodiesel also called second generation biodiesel, refers to the reaction products produced by the hydrogenation and cracking of animal fats and vegetable oils, which reaction products primarily comprise C 8 -C 24 alkanes, in particular C 12 -C 20 n-alkanes.
  • Such hydrocracked biodiesel has a high hexadecane value but a low sulphur content and aromatic hydrocarbon content, and, when used as a fuel for diesel engines or as a blending component thereof, can greatly decrease the discharge of contaminants from diesel engines.
  • An oxygen-containing diesel blending component refers to an oxygen-containing compound or a mixture thereof that can be blended with various fuels for diesel engines to meet some standards or requirements. They are generally alcohols and ethers, or mixtures thereof.
  • the alcohols may be, for example, C 1 -C 18 fatty alcohols, preferably C 1 -C 12 monofatty alcohols, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, lauryl alcohol and various isomers thereof.
  • said diesel composition when the base diesel is a biodiesel-containing blended fuel, said diesel composition can be obtained by directly mixing the additives, biodiesel and additional diesels, or by first mixing the additives and biodiesel, and then blending them with the additional diesels.
  • the additive components can be directly mixed with the ingredients of the base diesel, or can be premixed to obtain a mixture of additives which is subsequently mixed with the base diesel or the ingredients thereof.
  • the additive components, the biodiesel and the additional diesels are mixed in an order which is not particularly defined, and namely, they can be mixed in various orders.
  • the mixing can be performed at various conditions producing no detrimental effects on the additive composition and diesel composition, such as at ambient temperature.
  • the method of increasing the oxidation stability of biodiesel comprises blending an additive into a biodiesel-containing diesel component, wherein said additive is the above-mentioned additive composition of the present invention.
  • Preparation Examples 1-6 are used for showing the preparation of the reaction product of the ammonolysis reaction of a polyamine with a monoacylating agent.
  • Preparation Example 2 is the same as Preparation Example 1, except that the reactant contained 141.7g (0.75mol) tetraethylene pentamine. The reaction product was directly used as component (b).
  • dimer acid an acid number of 197mg KOH/g, a YH13-type high-purity dimer acid produced by YUANDA CHEMICALS CO., LTD., Yichun, Jiangxi Republic
  • pentaethylene hexamine in a molar ratio of the carboxyl of the dimer acid to pentaethylene hexamine of 1: 1, with the carboxyl of the dimer acid calculated on the basis of the acid number
  • Preparation Examples 7-10 are used for showing the synthesis of the condensation product of a polyamine with an aldehyde.
  • Preparation Examples 11-15 are used for showing the synthesis of the acylated product of a polyamine.
  • dodecenylsuccinic acid half ester an additive product with the trade name T747, produced by Lushun Chemical Plant, with an acid number of about 180mg KOH/g
  • T747 an additive product with the trade name
  • T747 produced by Lushun Chemical Plant, with an acid number of about 180mg KOH/g
  • triethylene tetramine in a molar ratio of triethylene tetramine to the carboxyl of the dodecenylsuccinic acid half ester of 1: 1, calculated on the basis of the acid number of T747
  • 150g aromatic diluent oil having a distillation range of 159-185 °C, which were heated and stirred. Nitrogen gas was used for bubbling to remove reaction water at 110 °C for 5 hours. About 5g water was separated. The resultant product was directly used as component (b).
  • Preparation Example 14 The process of Preparation Example 14 was conducted, except that 28.4g tetraethylene pentamine (0.15mol) was used for replacing 56.7g tetraethylene pentamine (0.3mol), and 108.2g aromatic diluent oil having a distillation range of 159-185 °C was used for replacing 136.5g aromatic diluent oil having a distillation range of 159-185 °C.
  • a mixture comprising about 50 wt.% of an ammonolysis reaction product comprising predominantly bis-dodecenylsuccinimide was obtained. Said mixture was directly used as component (b).
  • Examples 1-9 demonstrate the preparation of the additive composition of the present invention, wherein component (b) was a polyamine.
  • Antioxidant 88 N-(2-aminoethyl) piperazine - 1:0.2:0
  • Antioxidant 688 N,N-bis-(3-aminopropyl) methylamine - 1:0.5:0
  • Example 9 N,N'-di-sec-butyl-p-phenylene diamine N-(2-aminoethyl) piperazine - 1:8:0
  • component (a) or component (b) alone was used as a biodiesel antioxidant, was combined, according to the process of the present invention, with an organic amine beyond the scope of the amine of the present invention as component (b), forming the following comparative examples of the present invention:
  • component (b) was a polyamine derivative produced by the amination reaction of a monofatty acid or ester with a polyamine.
  • Examples 18-24 demonstrate the preparation of the additive composition of the present invention, wherein component (b) was a polyamine derivative produced by the amination reaction of an aldehyde with a polyamine.
  • Examples 25-31 demonstrate the preparation of the additive composition of the present invention, wherein component (b) was a polyamine derivative produced by the amination reaction of a diacylating agent with a polyamine.
  • the cottonseed oil biodiesel and rapeseed oil biodiesel were the products provided by Shijiazhuang Refining and Chemical Branch of Sinopec
  • the sewer oil biodiesel and acidified oil biodiesel were both provided by Longyan Zhuoyue New Energy Development Co., Ltd, Fujian
  • the petroleum diesel was the diesel of Beijing Standard B produced by Sinopec Yanshan Branch.
  • the oxidation stability of the biodiesel was tested by measuring its induction period at 110 °C using the EN14112:2003 method (Rancimat method) with an instrument of model 743 for measuring the oxidation stability of a fat or oil from Metrohm Surrey AG.
  • the results of the test were shown in Tables 5 to 8.
  • component (a) was a common antioxidant, which improved the oxidation stability of biodiesel in some degree, component (b) had no antioxidative effect or a relatively poor antioxidative effect when used alone, and component (a) and component (b) used alone were both listed as comparative examples of the present invention.
  • the oxidation stability of the biodiesel compositions of the present invention were significantly improved.
  • a biodiesel composition comprising a combination of component (a) with component (b) produced a much better effect than the sum of the effects produced by biodiesel compositions comprising component (a) or component (b) alone.
  • components (a) and (b) surprisingly produced an evident synergistic effect.
  • the effect was further enhanced by the addition of an optional component (c).
  • Example 3 Upon comparison of Example 3 with Example 4, it can be seen that the oxidation stability of a biodiesel composition comprising the optional component (c) was further enhanced.
  • Comparative Examples 1, 2 and 3 Upon comparison of Comparative Examples 1, 2 and 3 with Example 3, it can be seen that the combination of an amine-type compound beyond the scope of the present invention as component (b) with an antioxidant of component (a) did not produce any synergism, and on the contrary, led to disappearance of the antioxidative effect, indicating the presence of antagonism.
  • Component (b) in Comparative Example 1 was a mono-tertiary amine
  • components (b) in Comparative Examples 2 and 3 were di-tertiary amines, in which the nitrogen atom was not linked to the hydrogen atom in the molecular structure.
  • component (a) was a common antioxidant, which improved the oxidation stability of biodiesel in some degree, component (b) had no antioxidative effect or a relatively poor antioxidative effect when used alone, and component (a) and component (b) used alone were both listed as comparative examples of the present invention.
  • the biodiesel composition of the present invention had a significantly improved oxidation stability, showing that a biodiesel composition comprising a combination of component (a) with component (b) produced a much better effect than the sum of the effects produced by biodiesel compositions comprising component (a) or component (b) alone.
  • components (a) and (b) surprisingly produced an evident synergistic effect.
  • the effect was further enhanced by the addition of an optional component (c).
  • Example 10 Upon comparison of Example 10 with Example 11, it can be seen that the reaction product resulting from excess amine during the preparation of component (b) produced a slightly better effect. Upon comparison of Example 14 with Example 15, it can be seen that the oxidation stability of a biodiesel composition comprising the optional component (c) was further enhanced.
  • component (a) was a common antioxidant, which improved the oxidation stability of biodiesel in some degree, and component (b) did not improve the antioxidative effect of biodiesel or had a very poor antioxidative effect when used alone in a small amount.
  • the biodiesel composition of the present invention had a significantly improved oxidation stability.
  • a biodiesel composition comprising a combination of component (a) with component (b) produced a much better effect than the sum of the effects produced by biodiesel compositions comprising component (a) or component (b) alone.
  • components (a) and (b) surprisingly produced an evident synergistic effect.
  • Example 21 Upon comparison of Example 21 with Example 20, it can be seen that the oxidation stability of a biodiesel composition comprising the optional component (c) was further enhanced.
  • Table 8 Biodiesel Source of Additive Amount Added/(mg/kg) Induction Period at 110 °C/(hr) Rapeseed Oil - - 1.2
  • Example 25 600 23.8 Comparative Example a2 400 8.1 Comparative Example a2 600 10.4 Comparative Example b18 200 1.4 Comparative Example b18 600 3.6
  • Example 26 600 9.3 Comparative Example a6 400 4.2 Comparative Example a6 600 6.0
  • component (a) was a common antioxidant, which improved the oxidation stability of biodiesel in some degree, and component (b) had no antioxidative effect or a relatively poor antioxidative effect when used alone.
  • the biodiesel composition of the present invention had a significantly improved oxidation stability.
  • a biodiesel composition comprising a combination of component (a) with component (b) produced a much better effect than the sum of the effects produced by biodiesel compositions comprising component (a) or component (b) alone.
  • components (a) and (b) surprisingly produced an evident synergistic effect.
  • the effect was further enhanced by the addition of an optional component (c).
  • Example 28 Upon comparison of Example 28 with Example 29, it can be seen that the oxidation stability of a biodiesel composition comprising the optional component (c) was further enhanced.
  • Example 30 Upon comparison of Example 30 with Example 31, it can be seen that when component (b) was mono-alkenylsuccimide ("mono-hanging"), the combination of it with an antioxidant produced a better antioxidative effect than the combination of it with an antioxidant, when component (b) is bi-alkenylsuccimide ("double hanging").
  • Example 9 the freshly produced biodiesel was more susceptible to the antioxidant formulation of the present invention. It can be seen from Example 9 and its Comparative Examples that the use of a polyamine-type compound in the present invention greatly reduced the amount of an arylamine-type antioxidant which has some toxicity and dyeability, but produced a greatly improved effect than the arylamine-type antioxidant.
  • the induction periods of the diesel compositions, petroleum diesel and blended diesels at 110 °C were independently measured by the Pr EN15751:2008 method were measured with using a tester of model 743 for measuring the oxidation stability of a fat or oil from Metrohm Nurse AG.
  • the results of the test were shown in Tables 10 to 13.
  • the amount of total insolubles (unit: mg/100 mL) in the blended diesel compositions was measured using the SH/T 0175 method, so as to assess the stability of the diesel compositions.
  • the results of the test were shown in Tables 10 to 13.
  • the blended fuels comprising biodiesel all had deteriorated oxidation stability and stability than petroleum diesel.
  • the biodiesel composition comprising a mixture of component (a) and component (b) as additive had significantly improved oxidation stability and stability, and components (a) and (b) exhibited synergism, i.e., a significantly enhanced effect, compared with the use of one of them alone.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP10791159.6A 2009-06-26 2010-06-25 Diesel composition and process for improving oxidation stability of biodiesel Active EP2447344B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CN 200910087970 CN101928614B (zh) 2009-06-26 2009-06-26 一种柴油组合物和提高生物柴油氧化安定性的方法
CN 200910089959 CN101987980B (zh) 2009-07-30 2009-07-30 添加剂组合物和柴油组合物及提高生物柴油氧化安定性的方法
CN200910090512.0A CN101993744B (zh) 2009-08-19 2009-08-19 生物柴油组合物及提高生物柴油氧化安定性的方法
CN 200910090511 CN101993743B (zh) 2009-08-19 2009-08-19 添加剂组合物和柴油组合物及提高生物柴油氧化安定性的方法
PCT/CN2010/000950 WO2010148652A1 (zh) 2009-06-26 2010-06-25 柴油组合物及提高生物柴油氧化安定性的方法

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US20230192607A1 (en) * 2019-12-24 2023-06-22 Dana-Farber Cancer Institute, Inc. Transcriptional enhanced associate domain (tead) transcription factor inhibitors and uses thereof
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EP2447344A1 (en) 2012-05-02
EP2447344A4 (en) 2013-10-30
BRPI1012681A2 (pt) 2016-03-29
US20120124896A1 (en) 2012-05-24
WO2010148652A1 (zh) 2010-12-29
ES2749879T3 (es) 2020-03-24

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