WO2016187798A1 - 车用燃料添加剂组合物及其用途 - Google Patents

车用燃料添加剂组合物及其用途 Download PDF

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WO2016187798A1
WO2016187798A1 PCT/CN2015/079766 CN2015079766W WO2016187798A1 WO 2016187798 A1 WO2016187798 A1 WO 2016187798A1 CN 2015079766 W CN2015079766 W CN 2015079766W WO 2016187798 A1 WO2016187798 A1 WO 2016187798A1
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formula
compound
alkyl
additive composition
fuel additive
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PCT/CN2015/079766
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English (en)
French (fr)
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李洪国
高潮
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高化学株式会社
李洪国
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Priority to CN201580005927.7A priority Critical patent/CN106459794B/zh
Priority to PCT/CN2015/079766 priority patent/WO2016187798A1/zh
Publication of WO2016187798A1 publication Critical patent/WO2016187798A1/zh

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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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • 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

Definitions

  • This invention relates to automotive fuel additive compositions and uses thereof.
  • Diesel engines are widely used and developed due to their high thermal efficiency and low fuel consumption.
  • diesel engines have high NOx and soot emissions, which are harmful to the environment.
  • PM2.5 refers to fine particles with a diameter of 2.5 ⁇ m or less in air, which can be suspended in the air for a long time. The higher the concentration in the air, the more serious the air pollution. According to the survey and statistics, part of the cause of PM2.5 is caused by the exhaust gas of diesel engines. Therefore, how to reduce the emission of harmful substances from diesel engines has a profound impact on China's economic development and national health.
  • Oxygenated fuel additives that have been developed include alcohols, ethers, and esters.
  • Oxygenated fuel additives include alcohols, ethers, and esters.
  • Lu Kejiu et al. Emission test of ethylene glycol dimethyl ether-diesel blended fuel for diesel fuel, vehicle engine, No. 2, 75-77, 2009, describes the addition of ethylene glycol dimethyl ether to diesel fuel.
  • the smoke of the mixed fuel tends to decrease with the increase of the content of ethylene glycol dimethyl ether.
  • JP-A-110-148086 describes a fuel additive composed of ethylene glycol dimethyl ether and 1,3-dimethoxypropane, which is added to diesel fuel to increase the cetane number of diesel fuel, but 1,3-two
  • the low oxygen content of methoxypropane affects the combustion performance of diesel fuel and has no effect on reducing exhaust gas emissions. Therefore, this method cannot be called an effective means for improving diesel oil.
  • JP-A-H09-165586 that the addition of a carbonate compound to diesel fuel reduces the minute particles in the exhaust gas. Granules, but do not contribute to the improvement of other properties of diesel such as cetane number, so this method also lacks practicality.
  • An object of the present invention is to provide a fuel additive composition for a vehicle and an application thereof, in order to overcome the above disadvantages of the prior art described above.
  • the present invention provides a fuel additive composition for a vehicle, the vehicle fuel additive composition comprising:
  • n is an integer from 2 to 4, and R 1 is a C 1 -C 6 alkyl group;
  • n is an integer from 2 to 4, and R 2 and R 3 are each independently C 1 -C 6 alkyl,
  • composition further comprises component C, said component C being selected from at least one of the following compounds:
  • R 4 and R 5 are each independently C 1 -C 6 alkyl
  • q and u are each independently an integer of from 2 to 4, and R 6 and R 7 are each independently C 1 -C 6 alkyl;
  • s and t are each independently an integer of from 2 to 4, and R 8 and R 9 are each independently C 1 -C 6 alkyl.
  • the invention also provides the use of the additive composition of the invention in a vehicle fuel.
  • the fuel additive composition for vehicle of the present invention has the characteristics of reducing exhaust gas emissions, improving cetane number, improving combustibility, reducing fine particles in exhaust gas of automobiles, and being excellent in compatibility with fuel.
  • the present invention relates to a fuel additive composition for a vehicle, the fuel additive composition for a vehicle comprising:
  • n is an integer from 2 to 4, and R 1 is a C 1 -C 6 alkyl group;
  • n is an integer from 2 to 4, and R 2 and R 3 are each independently C 1 -C 6 alkyl,
  • composition further comprises component C, said component C being at least one of the following compounds:
  • R 4 and R 5 are each independently C 1 -C 6 alkyl
  • q and u are each independently an integer of from 2 to 4, and R 6 and R 7 are each independently C 1 -C 6 alkyl;
  • s and t are each independently an integer of from 2 to 4, and R 8 and R 9 are each independently C 1 -C 6 alkyl.
  • the C 1 -C 6 alkyl group is a linear or branched alkyl group, and examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl Base, pentyl and hexyl and isomers thereof.
  • the present invention has no particular requirement for the amount of each component in the composition, preferably, the volume ratio of the compound of the formula (I) to the compound of the formula (II) may be from 1 to 4: 4-1; It is 1-3:3-1.
  • the volume ratio of component C to the total amount of the compound of formula (I) and the compound of formula (II) is from 0.05 to 1:1, preferably from 0.1 to 0.5:1.
  • the present invention has no particular requirement for the ratio of the amounts of the components in the component C, and can be adjusted according to the actual application.
  • R 1 is a C 2 -C 4 alkyl group, and n is an integer of 2-3.
  • An example of the compound (I) may be at least one of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, or ethylene glycol monoethyl ether, and the like, and is preferably ethylene glycol monomethyl ether.
  • the oxygen mass ratio of ethylene glycol monomethyl ether is 47.3%, and adding it to diesel fuel can increase the average oxygen content of the fuel and increase the combustibility of the fuel.
  • the hydroxyl group of ethylene glycol monomethyl ether forms a hydrogen bond with the molecules of trace water in the oil, and its own freezing point (-85 ° C) is low, thus reducing the freezing point of water in the fuel, and preventing freezing. Effect.
  • ethylene glycol monoalkyl ether has poor compatibility with diesel oil and low cetane number. It should not be added separately.
  • m is preferably an integer of 2-3
  • R 2 is a C 1 -C 4 alkyl group
  • R 3 is a C 1 -C 3 alkyl group.
  • An example of the compound (II) may be propylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-tert-butoxy-2-ethoxyethane or 1-tert-butoxy At least one of benzyl-2-methoxyethane; preferably ethylene glycol dimethyl ether and/or 1-tert-butoxy-2-methoxyethane.
  • the flash point (-2 ° C) of ethylene glycol dimethyl ether is low, and the addition to diesel fuel can improve the ignitability of the fuel and increase the cetane number.
  • the oxygen content ratio (35.6%) of ethylene glycol dimethyl ether is low, so it is not suitable to be used alone.
  • the mixed use of the compound (I) and the compound (II) in the fuel additive composition for vehicles of the present invention can make up for the respective disadvantages and has a certain effect on improving the performance of the diesel fuel, but the compound (I), the compound (II) and the diesel oil, etc.
  • the compatibility of the fuel is not good, and the composition ratio of the additive and the amount added to the fuel are restricted, which affects the performance of each component.
  • the fuel additive composition of the present invention further comprises at least one of the following components.
  • (C-1) in the fuel additive composition for vehicles of the present invention is a compound of the following formula:
  • R 4 and R 5 are each independently C 1 -C 6 alkyl; preferably p is an integer from 2 to 3, R 4 is C 1 -C 3 alkyl, and R 5 is C 1 - C 3 alkyl; further preferably p is an integer of 2-3, R 4 is C 1 -C 2 alkyl, and R 5 is C 1 -C 2 alkyl.
  • An example of the compound of the compound (C-1) may be at least one of propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, ethylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate; preferably B Glycol methyl ether acetate and/or ethylene glycol ethyl ether acetate are further preferably ethylene glycol methyl ether acetate.
  • the compound (C-2) in the fuel additive for vehicles of the present invention is a compound of the following formula:
  • q and u are each independently an integer of from 2 to 4, and R 6 and R 7 are each independently a C 1 -C 6 alkyl group.
  • q and u are each independently an integer from 2 to 3
  • R 6 and R 7 are each independently C 1 -C 3 alkyl.
  • An example of the compound (C-2) may be: di(2-ethoxyethyl) carbonate, bis(2-methoxyethyl) carbonate (Cas. No. 626-84-6) At least one of bis(3-methoxypropyl) carbonate or bis(3-ethoxypropyl) carbonate is preferably bis(2-methoxyethyl) carbonate.
  • the formula (V) of the compound (C-3) in the fuel additive composition for vehicles of the present invention is:
  • s and t are each independently an integer of from 2 to 4, and R 8 and R 9 are each independently C 1 -C 6 alkyl.
  • s and t are each independently an integer from 2 to 3
  • R 8 is a C 1 -C 3 alkyl group
  • R 9 is a C 1 -C 4 alkyl group.
  • Examples of the compound of the formula (V) may be dipropylene glycol monobutyl ether carboxylate, dipropylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether carboxylate, diethylene glycol monobutyl ether carboxylate, diethylene glycol Alcohol monobutyl ether acetate (Cas. No. 124-17-4), diethylene glycol monomethyl ether acetate or diethylene glycol monomethyl ether acetate (Cas. NO. 629-38-9) At least one of them is preferably diethylene glycol monobutyl ether acetate and/or diethylene glycol monomethyl ether acetate.
  • the compound (C-1), the compound (C-2), and the compound (C-3) are widely used as excellent solvents, and their viscosity is small, and they are added as an auxiliary component to the above.
  • the interaction between the molecules of each component can be reduced, the atomization quality of the fuel can be easily improved, and the variation range of the compound ratio can be increased, thereby improving the vehicle for the present invention.
  • the combined effect of the fuel additive composition is widely used as excellent solvents, and their viscosity is small, and they are added as an auxiliary component to the above.
  • Compound (I) such as ethylene glycol monomethyl ether as main component and compound (II) such as ethylene glycol dimethyl ether and auxiliary compounds (C-1), (C-2) and (C-3)
  • the mixture of at least one of the compositions will compensate for the shortcomings of the various ingredients added separately, forming a practical fuel additive.
  • the fuel of the mixed additive and the diesel fuel has high oxygen content, high flammability, and large cetane number. It is not easy to freeze and reduce exhaust gas discharge.
  • the volume ratio of the main component compound I to the compound II in the additive composition of the present invention is preferably from 4/1 to 1/4.
  • the volume ratio of the compound I to the compound II is more than 4/1, the content of the compound II in the fuel is too small, and the low flash point characteristic of the compound II is difficult to exert; when the volume ratio of the compound I to the compound II is less than 1/4, the compound The content of I in the fuel is too small, the high oxygen content of the compound I is not easy to exert, and the combustion performance of the obtained fuel is not good, which is not beneficial for the improvement of exhaust gas emissions.
  • the volume content of the compound I and the compound II is not more than 95% of the total volume of the additive composition, and the volume content of the component C (ie, at least one of the compound III, the compound IV, and the compound V) is not less than the total volume of the additive composition. 5%.
  • the volume content of the component C is less than 5% of the total volume of the additive composition, the effect of improving the compatibility between the components is not large, the uniformity of the obtained mixed fuel is poor, and the atomization quality is not good.
  • a general chemical product which is commercially available can be used as the compound contained in the fuel additive composition for vehicles of the present invention.
  • the mixture of ethylene glycol monomethyl ether and ethylene glycol dimethyl ether obtained by reacting ethylene glycol with methanol can also be directly used as a main component of the fuel additive composition of the present invention, and the market is added according to the effective distribution ratio of the fuel additive composition.
  • the raw material of ethylene glycol can be selected from coal as the starting material of coal to ethylene glycol, which will be more in line with China's national conditions, the cheaper fuel additives are easier to popularize.
  • a small amount of dioxane (Cas. No.
  • ethylene glycol dimethyl ether oligomer may be entrained in a mixture of ethylene glycol monomethyl ether and ethylene glycol dimethyl ether due to fluctuations in reaction conditions.
  • the oligomer of methyl ether also does not affect the effect of the fuel additive.
  • the oligomer of ethylene glycol dimethyl ether can also play a role in cleaning the diesel engine while increasing the cetane number of the diesel.
  • the vehicle fuel additive composition comprises:
  • R 1 is C 2 -C 4 alkyl, and n is an integer of 2-3;
  • n is an integer of 2-3
  • R 2 is C 1 -C 4 alkyl
  • R 3 is C 1 -C 3 alkyl
  • composition further comprises component C, said component C being at least one of the following compounds:
  • R 4 is C 1 -C 3 alkyl
  • R 5 is C 1 -C 3 alkyl
  • q and u are each independently an integer of 2-3, and R 6 and R 7 are each independently C 1 -C 3 alkyl;
  • R 8 is a C 1 -C 3 alkyl group
  • R 9 is a C 1 -C 4 alkyl group.
  • the vehicle fuel additive composition comprises:
  • (A) at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether;
  • (B) is selected from the group consisting of propylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-tert-butoxy-2-ethoxyethane or 1-tert-butoxy-2 At least one of -methoxyethane;
  • (C-1) at least one selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, ethylene glycol methyl ether acetate, or ethylene glycol ethyl ether acetate; and/or
  • (C-2) is selected from the group consisting of di(2-ethoxyethyl) carbonate, bis(2-methoxyethyl) carbonate, bis(3-methoxypropyl) carbonate or carbonic acid (3) At least one of -ethoxypropyl) esters; and/or
  • (C-3) is selected from the group consisting of dipropylene glycol butyl ether carboxylate, dipropylene glycol butyl ether acetate, dipropylene glycol monomethyl ether carboxylate, diethylene glycol butyl ether carboxylate, diethylene glycol butyl ether acetate, At least one of diethylene glycol monomethyl ether carboxylate or diethylene glycol monomethyl ether acetate.
  • the vehicle fuel additive composition comprises:
  • the amounts conventionally used herein (the units of the following numbers are: g/L, that is, the weight of other additives described below in a unit volume of vehicle fuel) Contains at least one, but usually some or all of the additives listed below:
  • Sulfur compounds such as terpene ( ⁇ -pinene), resin oil or low molecular weight polybutene with sulfur, dialkyl sulfide, dialkyl trisulfide, polysulfide, diaryl sulfide, modified sulfur Alcohol, mercaptobenzimidazoles, mercaptotriazines, thiophene derivatives, xanthates, zinc dialkyl dithiocarbamate, thiodiols, thioaldehydes, dibenzyl disulfides, alkanes Reaction product of a phenol sulfide, a dialkyl phenol sulfide or a sulfur-containing carboxylic acid
  • Phosphorus compounds such as triaryl phosphite, trialkyl phosphite, dialkyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate or piperazine phosphonate
  • Sulfur-phosphorus compounds such as zinc dialkyl dithiophosphate (dialkyl dithiophosphate metal salts are also used as corrosion inhibitors and high pressure additives in lubricating oils) or phosphorus pentasulfide and terpene ( ⁇ -pinene) , dipentene), a reaction product of polybutene, an olefin or an unsaturated ester
  • a phenol derivative such as sterically hindered mono-, di- or trisphenol, sterically hindered polycyclic phenol, polyalkylphenol, 2,6-di-tert-butyl-4-methylphenol or methylene-4, 4'-bis(2,6-di-tert-butylphenol) (phenol derivatives are usually used in combination with thio or amine based antioxidants)
  • Amines such as arylamines such as diphenylamine, phenyl- ⁇ -naphthylamine or 4,4'-tetramethyldiaminodiphenylmethane
  • Metal deactivators in a narrower sense such as N-salicylidene ethylamine, N,N'-disalicylidene ethylenediamine, N,N'-disalicylidene-1,2-propanediamine, Triethylenediamine, ethylenediaminetetraacetic acid, phosphoric acid, citric acid, glycolic acid, lecithin, thiadiazole, imidazole or pyrazole derivatives
  • Viscosity index improver such as polyisobutylene having a molecular weight of usually 10 000 to 45,000, polymethacrylate having a molecular weight of usually 15 000 to 100 000, and a molecular weight of usually 80 000-100 000 Homopolymers and copolymers of 1,3-diolefins such as butadiene or isoprene, 1,3-diene-styrene copolymers having a molecular weight of usually from 80 000 to 100 000, usually having a molecular weight of 60 000 - 120 000 esterified form of maleic anhydride-styrene polymer, usually having a molecular weight of from 200 000 to 500 000, a star polymer having a block structure by means of a unit composed of a conjugated diene and an aromatic monomer a polyalkylstyrene having a molecular weight of usually 80 000 to 150 000, a polyolefin or a
  • Pour point depressant such as bicyclic aromatic hydrocarbons such as naphthalenes with different long chain alkyl groups, having 12-18 carbon atoms in the alcohol group, a degree of branching of 10- 30 mol% of polymethacrylate with an average molecular weight of 5000-500 000, a copolymer of a long-chain alkyl phenol and a dialkyl aryl phthalate or a different olefin
  • Detergent (HD additive) (0.2-4 g/L), such as calcium naphthenate, lead naphthenate, zinc naphthenate and manganese naphthenate, calcium dichloride stearate, calcium phenyl stearate , chlorophenyl stearate, sulfonated product of alkyl arene such as dodecylbenzene, petroleum sulfonate, sodium sulfonate, calcium sulfonate, sulfonium sulfonate or magnesium sulfonate, neutral, basic and Overbased sulfonates, phenates and carboxylates, salicylates, metal salts of alkylphenols and alkylphenol sulfides, phosphates, thiophosphates or alkenyl phosphate derivatives
  • Ashless dispersant such as Mannich condensate of alkylphenol, formaldehyde and polyalkylene polyamine, reaction product of polyisobutenyl succinic anhydride with polyhydroxy compound or polyamine, alkyl methacrylate a copolymer of a base ester with diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylpyridine or 2-hydroxyethyl methacrylate or a vinyl acetate-fumarate copolymer
  • High pressure additive for example chlorine content 40-70% by weight
  • dialkyl hydrogen phosphite triaryl phosphite
  • aryl phosphate such as tricresyl phosphate, dialkyl phosphate
  • Trialkyl esters such as tributyl phosphate, trialkyl phosphine, pyrophosphate, nitro arene, aminophenol derivatives of naphthenic acid, carbamate, dithiocarbamic acid derivatives, substituted 1,2 , 3-triazoles, mixtures of benzotriazoles and alkyl succinic anhydrides or alkyl maleic anhydride, 1,2,4-thiadiazole polymers, morpholinobenzothiadiazole disulfide, chlorine Alkenyl sulfides, sulfurized olefins, chlorinated chlorona
  • Friction modifier (0.05-1 g/L), especially a polar oil-soluble compound that produces a thin layer on the friction surface by adsorption, such as fatty alcohols, fatty acid amides, fatty acid salts, fatty acid alkyl esters or fatty acid glycerides
  • Defoaming additive 0.0001-0.2g/L
  • liquid polysiloxanes such as polydimethylsiloxane or polyethylene glycol ethers and sulfides
  • Demulsifiers such as dinonylnaphthalene sulfonate in the form of alkali metal and alkaline earth metal salts
  • Corrosion inhibitors also known as metal deactivators (0.01-2), such as tertiary amines and their salts, imino esters, amide oximes, diaminomethanes, saturated or unsaturated fatty acids with alkanolamines Derivatives, alkylamines, sarcosine, imidazolines, alkylbenzotriazoles, dimercaptothiadiazole derivatives, diaryl phosphates, phosphorothioates, n-C 8 -C 18 alkanes Neutral salt of a primary or tertiary alkylamine with a dialkyl phosphate having a branched C 5 -C 12 alkyl group, a neutral or basic alkaline earth metal sulfonate, zinc naphthenate, mono- and di Alkyl aryl sulfonate, bismuthylnaphthalene sulfonate, lanolin, heavy metal salt of naphthenic acid,
  • Emulsifier (0.01-1 g/L), such as long chain unsaturated natural carboxylic acid, naphthenic acid, synthetic carboxylic acid, sulfonamide, N-oleyl sarcosine, alkanesulfonamidoacetic acid, dodecyl Benzene sulfonate, long chain alkylated ammonium salt such as dimethyldodecylbenzylammonium chloride, imidazole Salt, alkyl-, alkyl aryl-, acyl-, alkylamino- and acylamino polyethylene glycol or long chain acylated mono- and diethanolamine
  • Odour improver (0.001-0.2 g/L).
  • a composition is preferred in which the other additives in the component (A), the component (B) and the component (C) are used in an amount of 20 g/L or less, preferably 15 g/L or less.
  • the invention also provides for the use of an additive composition in a vehicle fuel, the additive composition comprising
  • n is an integer from 2 to 4, and R 1 is a C 1 -C 6 alkyl group;
  • n is an integer from 2 to 4, and R 2 and R 3 are each independently C 1 -C 6 alkyl,
  • composition further comprises component C, said component C being selected from at least one of the following compounds:
  • R 4 and R 5 are each independently C 1 -C 6 alkyl
  • q and u are each independently an integer of from 2 to 4, and R 6 and R 7 are each independently C 1 -C 6 alkyl;
  • s and t are each independently an integer of from 2 to 4, and R 8 and R 9 are each independently C 1 -C 6 alkyl.
  • the vehicle fuel additive composition provided by the present invention is simple to prepare, and it is only necessary to uniformly mix the components constituting the additive composition. These components can be mixed directly.
  • the vehicle fuel additive composition of the invention is used in an amount of usually from 0.001 to 30% by volume, preferably from 0.01 to 20% by volume, especially from 0.05 to 10% by volume, in particular from 0.1 to 5% by volume, based on the total amount of the vehicle fuel. .
  • the experimental method is as follows.
  • the fuel used was the diesel products supplied by Sinopec Shijiazhuang Refinery Branch.
  • a vehicle fuel additive composition was prepared by mixing each compound in the volume ratio shown in Table 1. Based on the total volume of the fuel for the vehicle, it is added to the No. 0 diesel oil at a ratio of 20% by volume. The experimental results are shown in Table 1.
  • C-2 bis(2-methoxyethyl) carbonate (Cas. No. 626-84-6)
  • B-2 1-tert-butoxy-2-methoxyethane (Cas. No. 66728-50-5)
  • C-3-1 Diethylene glycol monobutyl ether acetate (Cas. No. 124-17-4)

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Abstract

一种车用燃料添加剂组合物及用途，该组合物包含：(A)式(I)化合物，其中n为2-4的整数，R1为C1-C6烷基；(B)式(II)化合物，其中m为2-4的整数，R2和R3各自独立地为C1-C6烷基， C选自式(III)- (V)化合物中的至少一种：(C-1)式(III)化合物，其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；(C-2)式(IV)化合物，其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基；和(C-3)式(V)化合物，其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。该组合物具有降低废气排放、改进十六烷值、提高燃烧性、降低汽车排放废气中的微粒子、与燃料相溶性优异等特点。

Description

车用燃料添加剂组合物及其用途 技术领域
本发明涉及车用燃料添加剂组合物及其用途。
背景技术
柴油发动机因有较高的热效率和较低的燃油消耗率而得到广泛的应用和发展，但柴油发动机有较高的NOx和碳烟排放，对环境危害大。PM2.5系指空气中直径小于等于2.5微米的细颗粒物，它能较长时间悬浮于空气中，其在空气中浓度越高，就代表空气污染越严重。据调查和统计PM2.5的部分成因是由柴油发动机的排放废气造成的，所以如何减少柴油发动机有害物质的排放对我国的经济发展和国民健康都具有深远影响。
通过向柴油中添加含氧添加剂来改善柴油发动机废气排放的研究已在许多单位和机构里展开。已开发出的含氧燃料添加剂有醇类、醚类及酯类等物质。例如：陆克久等，柴油机燃料用乙二醇二甲醚-柴油混合燃料的排放试验研究，车用发动机，No.2，75-77，2009中记述了向柴油中添加乙二醇二甲醚来降低尾气排放的方法，随着乙二醇二甲醚含量的增加，混合燃料的烟度呈递减趋势。但由于乙二醇二甲醚含氧量不高，混合燃料的燃烧性能有所降低，单独添加乙二醇二甲醚的方法缺乏实用性。李丽梅等，新配方乙二醇单乙醚含氧燃料对柴油机燃烧和排放的影响，燃烧科学与技术，Vol.14，No.2，152-156，2008中记述了乙二醇单乙醚与乙二醇二甲醚组成的燃料添加剂，该添加剂加入柴油中可降低CO及碳烟排放，但对NOx及HC的排放效果不佳。加之乙二醇单乙醚产量低，所以本方法还无法得到实际推广。JP特开平11-148086中记述了乙二醇二甲醚与1,3-二甲氧基丙烷组成的燃料添加剂，该添加剂加入柴油中可提高柴油的十六烷值，但1,3-二甲氧基丙烷含氧量低，会影响柴油的燃烧性能，对降低废气排放量也无任何效果，所以该方法还不能称作改善柴油的有效手段。JP-特开平9-165586中记述了向柴油中添加碳酸酯类化合物会降低废气中的微小颗 粒，但对柴油的其他特性如十六烷值的改进无任何贡献，所以此方法也缺乏实用性。
到目前为止的公开文献和技术资料中，既经济又能有效改进柴油综合特性的实用性添加剂还未出现，开发此类新型添加剂可谓迫在眉睫、大势所趋。
发明内容
本发明的目的是为了克服上述现有技术的上述缺点，提供一种车用燃料添加剂组合物及其应用。
本发明提供了一种车用燃料添加剂组合物，所述车用燃料添加剂组合物包含：
(A)式(I)化合物
Figure PCTCN2015079766-appb-000001
其中n为2-4的整数，R1为C1-C6烷基；
(B)式(II)化合物
Figure PCTCN2015079766-appb-000002
其中m为2-4的整数，R2和R3各自独立地为C1-C6烷基，
其中该组合物还含有组分C，所述组分C选自以下化合物中的至少一种：
(C-1)式(III)化合物
Figure PCTCN2015079766-appb-000003
其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；
(C-2)式(Ⅳ)化合物：
Figure PCTCN2015079766-appb-000004
其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基；和
(C-3)式(Ⅴ)化合物：
Figure PCTCN2015079766-appb-000005
其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。
本发明还提供了本发明的添加剂组合物在车用燃料中的用途。
本发明的车用燃料添加剂组合物具有降低废气排放、改进十六烷值、提高燃烧性、降低汽车排放废气中的微粒子、与燃料相溶性优异等特点。
具体实施方式
本发明涉及一种车用燃料添加剂组合物，所述车用燃料添加剂组合物包含：
(A)式(I)化合物
Figure PCTCN2015079766-appb-000006
其中n为2-4的整数，R1为C1-C6烷基；
(B)式(II)化合物
Figure PCTCN2015079766-appb-000007
其中m为2-4的整数，R2和R3各自独立地为C1-C6烷基，
其中该组合物还含有组分C，所述组分C为以下化合物中的至少一种：
(C-1)式(III)化合物
Figure PCTCN2015079766-appb-000008
其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；
(C-2)式(Ⅳ)化合物：
Figure PCTCN2015079766-appb-000009
其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基；和
(C-3)式(Ⅴ)化合物：
Figure PCTCN2015079766-appb-000010
其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。
本发明中，C1-C6烷基为线性或支化的烷基，实例是甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基和己基及其异构体。
根据本发明，尽管本发明对于组合物中各组分的用量没有特别要求，优选地，所述式(I)化合物与式(II)化合物的体积比可以为1-4：4-1；优选为1-3：3-1。组分C与所述式(I)化合物和式(II)化合物总量的体积比为0.05-1：1，优选为0.1-0.5:1。本发明对于组分C中各种组分之间的用量比没有特别要求，可以根据实际应用进行调整即可。
根据本发明，式(I)化合物中优选R1为C2-C4烷基，n为2-3的整数。
化合物(I)的实例可以为丙二醇单甲醚、丙二醇单乙醚、乙二醇单甲醚、或乙二醇单乙醚等中的至少一种，优选为乙二醇单甲醚。乙二醇单甲醚的含氧质量比为47.3％，将其添加至柴油中可提高燃料的平均含氧量，增加燃料的燃烧性。另外，乙二醇单甲醚的羟基与油中微量水的分子间形成氢键缔合，加之本身的冰点(-85℃)很低，因而降低了燃料中水的结冰点，有防冻结的效果。但乙二醇单烷基醚与柴油的相溶性差，且十六烷值低，所 以不宜单独添加使用。
本发明中，式(Ⅱ)化合物中优选m为2-3的整数，R2为C1-C4烷基，R3为C1-C3烷基。
化合物(II)的实例可以为丙二醇二甲醚、丙二醇二乙醚、乙二醇二甲醚、乙二醇二乙醚、1-叔丁氧基-2-乙氧基乙烷或1-叔丁氧基-2-甲氧基乙烷中的至少一种；优选为乙二醇二甲醚和/或1-叔丁氧基-2-甲氧基乙烷。乙二醇二甲醚的闪点(-2℃)低，添加至柴油中可提高燃料的发火性，增加十六烷值。但乙二醇二甲醚的含氧质量比(35.6％)较低，所以也不宜单独添加使用。
本发明车用燃料添加剂组合物中化合物(I)与化合物(II)的混合使用虽然能弥补各自的缺点，对改善柴油的性能有一定效果，但化合物(I)和化合物(II)与柴油等燃料的相溶性不佳，添加剂的组成比与向燃料中添加的量都会受到制约，影响了各成分性能的发挥。为此，本发明的燃料添加剂组合物还包含以下组分中的至少一种。
本发明车用燃料添加剂组合物中(C-1)为以下通式化合物：
Figure PCTCN2015079766-appb-000011
其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；优选p为2-3的整数，R4为C1-C3烷基，R5为C1-C3烷基；进一步优选p为2-3的整数，R4为C1-C2烷基，R5为C1-C2烷基。
化合物(C-1)的化合物的实例可以为丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、乙二醇甲醚乙酸酯或乙二醇乙醚乙酸酯中的至少一种；优选为乙二醇甲醚乙酸酯和/或乙二醇乙醚乙酸酯，进一步优选为乙二醇甲醚乙酸酯。
本发明车用燃料添加剂中化合物(C-2)为以下通式化合物：
Figure PCTCN2015079766-appb-000012
其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基。优选q和u各自独立地为2-3的整数，R6和R7各自独立地为C1-C3 烷基。
化合物(C-2)的实例可以为：碳酸二(2-乙氧基乙基)酯、碳酸二(2-甲氧基乙基)酯(Cas.No.626-84-6)
Figure PCTCN2015079766-appb-000013
碳酸二(3-甲氧基丙基)酯或碳酸二(3-乙氧基丙基)酯中的至少一种，优选为碳酸二(2-甲氧基乙基)酯。
本发明车用燃料添加剂组合物中化合物(C-3)的通式(Ⅴ)为：
Figure PCTCN2015079766-appb-000014
其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。优选s和t各自独立地为2-3的整数，R8为C1-C3烷基，R9为C1-C4烷基。
通式(Ⅴ)化合物的实例可以为二丙二醇单丁醚甲酸酯、二丙二醇单丁醚醋酸酯、二丙二醇单甲醚甲酸酯、二乙二醇单丁醚甲酸酯、二乙二醇单丁醚醋酸酯(Cas.No.124-17-4)、二乙二醇单甲醚甲酸酯或二乙二醇单甲醚醋酸酯(Cas.NO.629-38-9)中的至少一种，优选为二乙二醇单丁醚醋酸酯和/或二乙二醇单甲醚醋酸酯。
本发明车用燃料添加剂组合物中化合物(C-1)、化合物(C-2)、化合物(C-3)因均为优良溶剂而被广泛使用，它们粘度小，作为辅助成分添加到前述作为主成分的化合物(I)和化合物(II)的混合物中，能减少各成分分子间的相互作用，易于提高燃料的雾化质量，并能增大化合物比的变化范围，从而提高本发明车用燃料添加剂组合物的综合效果。
作为主成分的乙二醇单甲醚等化合物(I)和乙二醇二甲醚等化合物(II)与辅助成分的化合物(C-1)、(C-2)和(C-3)中的至少一种组成的混合物会弥补各种成分单独添加时的缺点，形成一种有实用效果的燃料混合添加剂。该混合添加剂与柴油组成的燃料具有含氧量高、燃烧性强、十六烷值大、 不易冻结、降低废气排出等特点。
本发明添加剂组合物中的主成分化合物I与化合物II的体积比介于4/1～1/4之间为宜。化合物I与化合物II的体积比大于4/1时，化合物II在燃料中的含量过少，化合物II的低闪点特性很难发挥；化合物I与化合物II的体积比小于1/4时，化合物I在燃料中的含量太少，化合物I的高含氧特性不易发挥，所得燃料的燃烧性能不佳，对废气排放的改善无益。化合物I与化合物II合计的体积含量不超过添加剂组合物总体积的95％，组分C(即化合物Ⅲ、化合物Ⅳ、化合物Ⅴ中的至少一种)的体积含量不少于添加剂组合物总体积的5％。组分C的体积含量小于添加剂组合物总体积的5％时，提高各成分间相溶性的作用不大，所得混合燃料的均匀性差，雾化质量不好。
本发明车用燃料添加剂组合物中的所含化合物可以使用市场上流通的一般化工产品。乙二醇与甲醇反应获得的乙二醇单甲醚与乙二醇二甲醚混合物也可以直接作为本发明燃料添加剂组合物的主要成分来使用，根据燃料添加剂组合物的有效成分配比添加市场流通的一般化工产品来调制燃料添加剂。原料的乙二醇可以选用从煤炭为出发原料的煤制乙二醇，这样会更符合我国国情，所得廉价的燃料添加剂更易于普及推广。煤制乙二醇中有时会残留少量二恶烷(Cas.No.123-91-1)，并带到最终的燃料添加剂之中，燃料添加剂中的少量二恶烷残留并不会影响燃料的性能，对柴油发动机还会有洗净的效果。另外，乙二醇与甲醇反应时，因反应条件变动，有时会在乙二醇单甲醚与乙二醇二甲醚混合物中夹带少量乙二醇二甲醚的低聚物，乙二醇二甲醚的低聚物同样不会影响燃料添加剂的效果，乙二醇二甲醚的低聚物在增加柴油十六烷值的同时，也能起到清洗柴油发动机的作用。
在一种优选实施方案中，所述车用燃料添加剂组合物包含：
(A)式(I)化合物
Figure PCTCN2015079766-appb-000015
其中R1为C2-C4烷基，n为2-3的整数；
(B)式(II)化合物
Figure PCTCN2015079766-appb-000016
其中m为2-3的整数，R2为C1-C4烷基，R3为C1-C3烷基，
其中该组合物还含有组分C，所述组分C为以下化合物中的至少一种：
(C-1)式(III)化合物
Figure PCTCN2015079766-appb-000017
其中p为2-3的整数，R4为C1-C3烷基，R5为C1-C3烷基；
(C-2)式(Ⅳ)化合物：
Figure PCTCN2015079766-appb-000018
其中q和u各自独立地为2-3的整数，R6和R7各自独立地为C1-C3烷基；和
(C-3)式(Ⅴ)化合物：
Figure PCTCN2015079766-appb-000019
其中s和t各自独立地为2-3的整数，R8为C1-C3烷基，R9为C1-C4烷基。
在一种进一步优选实施方案中，所述车用燃料添加剂组合物包含：
(A)选自丙二醇单甲醚、丙二醇单乙醚、乙二醇单甲醚或乙二醇单乙醚中的至少一种；
(B)选自丙二醇二甲醚、丙二醇二乙醚、乙二醇二甲醚、乙二醇二乙醚、1-叔丁氧基-2-乙氧基乙烷或1-叔丁氧基-2-甲氧基乙烷中的至少一种；以及
(C-1)选自丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、乙二醇甲醚乙酸酯或乙二醇乙醚乙酸酯中的至少一种；和/或
(C-2)选自碳酸二(2-乙氧基乙基)酯、碳酸二(2-甲氧基乙基)酯、碳酸二(3-甲氧基丙基)酯或碳酸二(3-乙氧基丙基)酯中的至少一种；和/或
(C-3)选自二丙二醇丁醚甲酸酯、二丙二醇丁醚醋酸酯、二丙二醇单甲醚甲酸酯、二乙二醇丁醚甲酸酯、二乙二醇丁醚醋酸酯、二乙二醇单甲醚甲酸酯或二乙二醇单甲醚醋酸酯中的至少一种。
在一种最优选实施方案中，所述车用燃料添加剂组合物包含：
(A)乙二醇单甲醚；
(B)乙二醇二甲醚和/或1-叔丁氧基-2-甲氧基乙烷；以及
(C-1)乙二醇甲醚乙酸酯；和/或
(C-2)碳酸二(2-甲氧基乙基)酯；和/或
(C-3)二乙二醇丁醚醋酸酯和/或二乙二醇单甲醚醋酸酯。
除了本发明的通式(I)-(V)化合物外，还以常用于此的量(以下数字的单位为：g/L，即表示其他下述添加剂在单位体积车用燃料中的重量)包含至少一种，但通常是一些或全部下文所列添加剂：
·抗氧化剂(0.1-5g/L)：
硫化合物，例如萜烯(α-蒎烯)、树脂油或低分子量聚丁烯与硫、二烷基硫醚、二烷基三硫化物、多硫化物、二芳基硫醚、改性硫醇、巯基苯并咪唑类、巯基三嗪类、噻吩衍生物、黄原酸盐、二硫代氨基甲酸二烷基酯锌、硫代二醇、硫代醛、二苄基二硫化物、烷基酚硫化物、二烷基酚硫化物或含硫羧酸的反应产物
磷化合物，例如亚磷酸三芳基酯、亚磷酸三烷基酯、3,5-二叔丁基-4-羟基苄基膦酸二烷基酯或膦酸哌嗪化物
硫-磷化合物，例如二硫代磷酸二烷基酯锌(二硫代磷酸二烷基酯金属盐在润滑油中也用作腐蚀抑制剂和高压添加剂)或五硫化二磷与萜烯(α-蒎烯、双戊烯)，聚丁烯，烯烃或不饱和酯的反应产物
苯酚衍生物，例如空间位阻单-、双-或三酚，空间位阻多环酚，多烷基酚，2,6-二叔丁基-4-甲基苯酚或亚甲基-4,4’-二(2,6-二叔丁基苯酚)(苯酚衍生物通常与硫基或胺基抗氧化剂组合使用)
胺类，例如芳基胺如二苯基胺、苯基-α-萘胺或4,4’-四甲基二氨基二苯基甲烷
更窄意义上的金属去活化剂，例如N-亚水杨基乙基胺、N,N’-二亚水杨基乙二胺、N,N’-二亚水杨基-1,2-丙二胺、三亚乙基二胺、乙二胺四乙酸、磷酸、柠檬酸、乙醇酸、卵磷脂、噻二唑、咪唑或吡唑衍生物
·粘度指数改进剂(0.05-10g/L)，例如分子量通常为10 000-45 000的聚异丁烯，分子量通常为15 000-100 000的聚甲基丙烯酸酯，分子量通常为80 000-100 000的1,3-二烯烃如丁二烯或异戊二烯的均聚物和共聚物，分子量通常为80 000-100 000的1,3-二烯烃-苯乙烯共聚物，分子量通常为60 000-120 000的酯化形式的马来酸酐-苯乙烯聚合物，分子量通常为200 000-500 000的借助由共轭二烯烃和芳族单体构成的单元而具有嵌段状结构的星形聚合物，分子量通常为80 000-150 000的聚烷基苯乙烯，分子量通常为60 000-140 000的由乙烯和丙烯构成的聚烯烃或苯乙烯-环戊二烯-降冰片烯三元共聚物
·倾点下降剂(冷流改进剂)(0.03-1g/L)，例如双环芳烃如具有不同长链烷基的萘，在醇基中具有12-18个碳原子、支化度为10-30mol％且平均分子量为5000-500 000的聚甲基丙烯酸酯，长链烷基酚和邻苯二甲酸二烷基芳基酯或不同烯烃的共聚物
·去垢剂(HD添加剂)(0.2-4g/L)，例如环烷酸钙，环烷酸铅，环烷酸锌和环烷酸锰，二氯硬脂酸钙，苯基硬脂酸钙，氯苯基硬脂酸钙，烷基芳烃如十二烷基苯的磺化产物，石油磺酸盐，磺酸钠，磺酸钙，磺酸钡或磺酸镁，中性、碱性和高碱性磺酸盐，酚盐和羧酸盐，水杨酸盐，烷基酚和烷基酚硫化物的金属盐，磷酸盐，硫代磷酸盐或链烯基磷酸衍生物
·无灰分散剂(0.5-10g/L)，例如烷基酚、甲醛和多亚烷基多胺的Mannich缩合物，聚异丁烯基琥珀酸酐与多羟基化合物或多胺的反应产物，甲基丙烯酸烷基酯与甲基丙烯酸二乙氨基乙酯、N-乙烯基吡咯烷酮、N-乙烯基吡啶或甲基丙烯酸2-羟基乙酯的共聚物或乙酸乙烯酯-富马酸酯共聚物
·高压添加剂(极端压力添加剂)(0.2-2.5g/L)，例如氯含量为40-70重量％ 的氯化石蜡，氯化脂肪酸(尤其具有三氯甲基端基)，亚磷酸氢二烷基酯，亚磷酸三芳基酯，磷酸芳基酯如磷酸三甲苯酯，磷酸二烷基酯，磷酸三烷基酯如磷酸三丁酯，三烷基膦，焦磷酸酯，硝基芳烃，环烷酸的氨基酚衍生物，氨基甲酸酯，二硫代氨基甲酸衍生物，取代的1,2,3-三唑类，苯并三唑和烷基琥珀酸酐或烷基马来酸酐的混合物，1,2,4-噻二唑聚合物，吗啉代苯并噻二唑二硫化物，氯代烷基硫化物，硫化烯烃，硫化氯代萘类，硫代碳酸氯代烷基酯，有机硫化物和多硫化物如二(4-氯苄基)二硫化物和四氯二苯基硫醚，三氯丙烯醛缩硫醛或尤其是二硫代磷酸二烷基酯锌(ZDDP)
·摩擦改性剂(0.05-1g/L)，尤其是在摩擦表面通过吸附产生薄层的极性油溶性化合物，例如脂肪醇、脂肪酰胺、脂肪酸盐、脂肪酸烷基酯或脂肪酸甘油酯
·消泡添加剂(0.0001-0.2g/L)，例如液体聚硅氧烷如聚二甲基硅氧烷或聚乙二醇醚和硫化物
·破乳剂(0.1-1g/L)，例如碱金属和碱土金属盐形式的二壬基萘磺酸盐
·腐蚀抑制剂(也已知为金属去活化剂)(0.01-2)，例如叔胺及其盐，亚氨基酯，酰胺肟，二氨基甲烷类，饱和或不饱和脂肪酸与链烷醇胺的衍生物，烷基胺，肌氨酸，咪唑啉类，烷基苯并三唑类，二巯基噻二唑衍生物，磷酸二芳基酯，硫代磷酸酯，正-C8-C18烷基伯胺或环烷基胺与具有支化C5-C12烷基的磷酸二烷基酯的中性盐，中性或碱性碱土金属磺酸盐，环烷酸锌，单-和二烷基芳基磺酸盐，二壬基萘磺酸钡，羊毛脂，环烷酸的重金属盐，二羧酸，不饱和脂肪酸，羟基脂肪酸，脂肪酸酯，季戊四醇单油酸酯和脱水山梨醇单油酸酯，O-硬脂酰链烷醇胺，聚异丁烯基琥珀酸衍生物或二硫代磷酸二烷基酯锌和二硫代氨基甲酸二烷基酯锌
·乳化剂(0.01-1g/L)，例如长链不饱和天然羧酸，环烷酸，合成羧酸，磺酰胺，N-油基肌氨酸，链烷磺酰胺基乙酸，十二烷基苯磺酸盐，长链烷基化铵盐如二甲基十二烷基苄基氯化铵，咪唑
Figure PCTCN2015079766-appb-000020
盐，烷基-、烷基 芳基-、酰基-、烷基氨基-和酰基氨基聚乙二醇或长链酰化单-和二乙醇胺
·染料和荧光添加剂(0.001-0.2g/L)
·防腐剂(0.001-0.5g/L)
·气味改进剂(0.001-0.2g/L)。
优选如下组合物，其中在组分(A)、组分(B)和组分(C)中其他添加剂的用量为20g/L以下，优选为15g/L以下。
本发明还提供添加剂组合物在车用燃料中的用途，该添加剂组合物包含
(A)式(I)化合物
Figure PCTCN2015079766-appb-000021
其中n为2-4的整数，R1为C1-C6烷基；
(B)式(II)化合物
Figure PCTCN2015079766-appb-000022
其中m为2-4的整数，R2和R3各自独立地为C1-C6烷基，
其中该组合物还含有组分C，所述组分C选自以下化合物中的至少一种：
(C-1)式(III)化合物
Figure PCTCN2015079766-appb-000023
其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；
(C-2)式(Ⅳ)化合物：
Figure PCTCN2015079766-appb-000024
其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基；和
(C-3)式(Ⅴ)化合物：
Figure PCTCN2015079766-appb-000025
其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。
本发明提供的车用燃料添加剂组合物的制备简单，只需将组成添加剂组合物的各组分混合均匀即可。这些组分可以直接混合。
本发明的车用燃料添加剂组合物基于车用燃料的总量以通常为0.001-30体积％，优选0.01-20体积％，尤其是0.05-10体积％，特别是0.1-5体积％的量使用。
本发明参考下列非限制性实施例详细说明。
实施例
实验方法如下
使用柴油版捷达车进行道路行车实验。先将试验车辆油箱中的余油抽干净，并清洁油箱、油滤，然后加满上述的燃料进行油耗及尾气排放污染物的测试。百公里耗油量＝(实际耗油量/实际行驶里程数)×100。十六烷值、S(μg/g)、多环芳烃(质量％)分别按照标准GB/T386、SH/T0689、SH/T0606来进行测试。实验结果参见表1。
实施例1-12
以下测试中，所用燃料为中石化石家庄炼化分公司提供的柴油产品。
按照表1所示的体积比混合各化合物制备得到车用燃料添加剂组合物。并以车用燃料的总体积为基准，按体积含量20％的比例加入到0号柴油中。实验结果参见表1。
比较例1-5
使用无添加剂的0号柴油，与实施例1同样的方法进行道路行车实验。实验结果参见表1。
表1
Figure PCTCN2015079766-appb-000026
表1中的化合物记号说明：
A:乙二醇单甲醚(Cas.No.109-86-4)
B-1:乙二醇二甲醚(Cas.No.110-71-4)
C-1:乙二醇甲醚乙酸酯(Cas.No.110-49-6)
C-2:碳酸二(2-甲氧基乙基)酯(Cas.No.626-84-6)
B-2:1-叔丁氧基-2-甲氧基乙烷(Cas.No.66728-50-5)
C-3-1:二乙二醇单丁醚醋酸酯(Cas.No.124-17-4)
C-3-2:二乙二醇单甲醚醋酸酯(Cas.No.629-38-9)
从表1中实施例1～12的结果不难看出使用本发明的车用燃料添加剂组合物，在保持汽车动力的同时，S、多环芳烃等的尾气排放污染物均有不 同程度的降低，对废气由来的环境问题有很大改善效果。另外，使用本发明的车用燃料添加剂组合物后，汽车百公里耗油量也有所降低，究其原因可能为本发明的组合物提高了燃料的雾化效果及燃烧效率，从而降低了发动机的耗油量。

Claims (16)

  1. 一种车用燃料添加剂组合物，所述车用燃料添加剂组合物包含：
    (A)式(I)化合物
    Figure PCTCN2015079766-appb-100001
    其中n为2-4的整数，R1为C1-C6烷基；
    (B)式(II)化合物
    Figure PCTCN2015079766-appb-100002
    其中m为2-4的整数，R2和R3各自独立地为C1-C6烷基，
    其中该组合物还含有组分C，所述组分C选自以下化合物中的至少一种：
    (C-1)式(III)化合物
    Figure PCTCN2015079766-appb-100003
    其中p为2-4的整数，R4和R5各自独立地为C1-C6烷基；
    (C-2)式(Ⅳ)化合物：
    Figure PCTCN2015079766-appb-100004
    其中q和u各自独立地为2-4的整数，R6和R7各自独立地为C1-C6烷基；和
    (C-3)式(Ⅴ)化合物：
    Figure PCTCN2015079766-appb-100005
    其中s和t各自独立地为2-4的整数，R8和R9各自独立地为C1-C6烷基。
  2. 根据权利要求1的车用燃料添加剂组合物，所述式(I)化合物与所述式(II)化合物的体积比为1-4：4-1；优选为1-3：3-1；组分C与所述式(I)化合物和式(II)化合物总量的体积比为0.05-1：1，优选为0.1-0.5：1。
  3. 根据权利要求1或2的车用燃料添加剂组合物，其中在式(I)中R1为C2-C4的烷基，n为2-3的整数。
  4. 根据权利要求1-3中任一项的车用燃料添加剂组合物，其中式(I)化合物选自丙二醇单甲醚、丙二醇单乙醚、乙二醇单甲醚或乙二醇单乙醚中的至少一种；优选为乙二醇单甲醚。
  5. 根据权利要求1-4中任一项的车用燃料添加剂组合物，其中在式(II)中m为2-3的整数，R2为C1-C4烷基，R3为C1-C3烷基。
  6. 根据权利要求1-5中任一项的车用燃料添加剂组合物，其中式(II)化合物选自乙二醇二甲醚、乙二醇二乙醚、1-叔丁氧基-2-乙氧基乙烷、1-叔丁氧基-2-甲氧基乙烷、丙二醇二甲醚或丙二醇二乙醚中的至少一种；优选为乙二醇二甲醚和/或1-叔丁氧基-2-甲氧基乙烷。
  7. 根据权利要求1-6中任一项的车用燃料添加剂组合物，其中在式(III)中p为2-3的整数，R4为C1-C3烷基，R5为C1-C3烷基。
  8. 根据权利要求1-7中任一项的车用燃料添加剂组合物，其中式(III)化合物选自丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、乙二醇甲醚乙酸酯 或乙二醇乙醚乙酸酯中的至少一种；优选为乙二醇甲醚乙酸酯。
  9. 根据权利要求1-8中任一项的车用燃料添加剂组合物，其中在式(Ⅳ)中q和u为2-3的整数，R6和R7各自独立地为C1-C3烷基。
  10. 根据权利要求1-9中任一项的车用燃料添加剂组合物，其中式(Ⅳ)化合物选自碳酸二(2-乙氧基乙基)酯、碳酸二(2-甲氧基乙基)酯、碳酸二(3-甲氧基丙基)酯或碳酸二(3-乙氧基丙基)酯中的至少一种；优选为碳酸二(2-甲氧基乙基)酯。
  11. 根据权利要求1-10中任一项的车用燃料添加剂组合物，其中在式(Ⅴ)中s和t各自独立地为2-3的整数，R8为C1-C3烷基，R9为C1-C4烷基。
  12. 根据权利要求1-11中任一项的车用燃料添加剂组合物，其中式(Ⅴ)化合物选自二丙二醇单丁醚甲酸酯、二丙二醇单丁醚醋酸酯、二丙二醇单甲醚甲酸酯、二乙二醇单丁醚甲酸酯、二乙二醇单丁醚醋酸酯、二乙二醇单甲醚甲酸酯或二乙二醇单甲醚醋酸酯中的至少一种，优选为二乙二醇单丁醚醋酸酯和/或二乙二醇单甲醚醋酸酯。
  13. 根据权利要求1-12中任一项的车用燃料添加剂组合物，其中所述车用燃料添加剂组合物包含：
    (A)式(I)化合物
    Figure PCTCN2015079766-appb-100006
    其中R1为C2-C4烷基，n为2-3的整数；
    (B)式(II)化合物
    Figure PCTCN2015079766-appb-100007
    其中m为2-3的整数，R2为C1-C4烷基，R3为C1-C3烷基，
    其中该组合物还含有组分C，所述组分C为以下化合物中的至少一种：
    (C-1)式(III)化合物
    Figure PCTCN2015079766-appb-100008
    其中p为2-3的整数，R4为C1-C3烷基，R5为C1-C3烷基；
    (C-2)式(Ⅳ)化合物：
    Figure PCTCN2015079766-appb-100009
    其中q和u各自独立地为2-3的整数，R6和R7各自独立地为C1-C3烷基；和
    (C-3)式(Ⅴ)化合物：
    Figure PCTCN2015079766-appb-100010
    其中s和t各自独立地为2-3的整数，R8为C1-C3烷基，R9为C1-C4烷基。
  14. 根据权利要求1-13中任一项的车用燃料添加剂组合物，其中所述车用燃料添加剂组合物包含：
    (A)选自丙二醇单甲醚、丙二醇单乙醚、乙二醇单甲醚或乙二醇单乙醚中的至少一种；
    (B)选自丙二醇二甲醚、丙二醇二乙醚、乙二醇二甲醚、乙二醇二乙醚、1-叔丁氧基-2-乙氧基乙烷或1-叔丁氧基-2-甲氧基乙烷中的至少一种；以及
    (C-1)选自丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、乙二醇甲醚乙酸酯或 乙二醇乙醚乙酸酯中的至少一种；和/或
    (C-2)选自碳酸二(2-乙氧基乙基)酯、碳酸二(2-甲氧基乙基)酯、碳酸二(3-甲氧基丙基)酯或碳酸二(3-乙氧基丙基)酯中的至少一种；和/或
    (C-3)选自二丙二醇丁醚甲酸酯、二丙二醇丁醚醋酸酯、二丙二醇单甲醚甲酸酯、二乙二醇丁醚甲酸酯、二乙二醇丁醚醋酸酯、二乙二醇单甲醚甲酸酯或二乙二醇单甲醚醋酸酯中的至少一种。
  15. 根据权利要求1-14中任一项的车用燃料添加剂组合物，所述车用燃料添加剂组合物包含：
    (A)乙二醇单甲醚；
    (B)乙二醇二甲醚和/或1-叔丁氧基-2-甲氧基乙烷；以及
    (C-1)乙二醇甲醚乙酸酯；和/或
    (C-2)碳酸二(2-甲氧基乙基)酯；和/或
    (C-3)二乙二醇丁醚醋酸酯和/或二乙二醇单甲醚醋酸酯。
  16. 根据权利要求1-15中任一项的组合物在车用燃料中的用途。
PCT/CN2015/079766 2015-05-26 2015-05-26 车用燃料添加剂组合物及其用途 WO2016187798A1 (zh)

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