阅读说明：本技术 一种燃料添加剂、其制备方法及燃料组合物 (Fuel additive, preparation method thereof and fuel composition ) 是由 夏鑫 蔺建民 李宝石 李妍 于 2020-06-28 设计创作，主要内容包括：本发明涉及一种燃料添加剂,其中至少含有结构式I所示的化合物：其中,R-(1)可以是氢、含或不含双键的烃基,R-(2)为含或不含双键的烃基,R-(1)和R-(2)的总碳数1～30,R-(3)为氢或C-(1)-C-(20)的烃基,R-(4)为C-(1)～C-(30)的烃基或不存在。本发明添加剂以羟基脂肪酸(酯)为原料,与二羧酸或其酸酐进行酯化反应得到,所生成的燃料添加剂具有令人惊讶的显著抗磨效果。(The invention relates to a fuel additive, which at least contains a compound shown in a structural formula I: wherein R is 1 Can be hydrogen, hydrocarbon radicals with or without double bonds, R 2 Is a hydrocarbon radical with or without double bonds, R 1 And R 2 Total carbon number of 1 to 30, R 3 Is hydrogen or C 1 ‑C 20 A hydrocarbon group of R 4 Is C 1 ～C 30 Or is absent. The additive is obtained by taking hydroxy fatty acid (ester) as a raw material and carrying out esterification reaction with dicarboxylic acid or anhydride thereof, and the generated fuel additive has a surprisingly remarkable anti-wear effect.)

1. A fuel additive comprising at least a compound of formula I:

wherein R is₁Is hydrogen, a hydrocarbon radical with or without double bonds, R₂Is a hydrocarbon radical with or without double bonds, R₁And R₂Total carbon number of 1 to 30, R₃Is hydrogen or C₁～C₂₀A hydrocarbon group of R₄Is C₁～C₃₀Or is absent.

2. The additive of claim 1, wherein R₁、R₂The total number of carbon atoms of (a) is 8 to 24, more preferably 16 to 22, and the total number of double bonds is 0 to 5, preferably 0 to 3.

3. The additive of claim 1, wherein R₃Is hydrogen or C₁～C₁₀Is preferably hydrogen or C₁～C₄Most preferably hydrogen, methyl or ethyl.

4. The additive of claim 1, wherein R₄Is C₁～C₂₀Is preferably C₂～C₁₆Alkylene, alkenylene, alkyl-substituted alkylene, alkyl-substituted alkenylene, alkenyl-substituted alkylene, alkenyl-substituted alkenylene.

5. The additive of claim 1, wherein R₄Is ethylene, vinylene, methylene ethylene, methyl ethylene, dodecyl ethylene or dodecenyl ethylene.

6. A method of preparing a fuel additive comprising: raw materials containing hydroxy fatty acid and/or hydroxy fatty acid ester and dicarboxylic acid and/or anhydride thereof are subjected to esterification reaction to generate the compound shown in the structural formula I.

7. The process according to claim 6, wherein the hydroxy fatty acid or hydroxy fatty acid ester is reacted with the dicarboxylic acid or anhydride thereof at a molar ratio of 1:0.1 to 10, preferably 1:0.5 to 5.

8. The process according to claim 6, wherein the esterification reaction temperature is in the range of 30 to 300 ℃, preferably 50 to 250 ℃, and more preferably 70 to 180 ℃.

9. The process according to claim 6, wherein the hydroxy fatty acid or hydroxy fatty acid ester has a fatty carbon chain having C as the carbon number₁～C₃₀Preferably C₈～C₂₄Most preferably C₁₆～C₂₂。

10. The method according to claim 6, wherein the number of unsaturated carbon-carbon double bonds in the aliphatic carbon chain of the hydroxy fatty acid or hydroxy fatty acid ester is 0 to 5, preferably 0 to 3.

11. The method according to claim 6, wherein the hydroxy fatty acid ester has an ester group carbon number of C₁～C₁₀Preferably C₁～C₄。

12. The method according to claim 6, wherein the hydroxy fatty acid is one or more selected from ricinoleic acid, 12-hydroxy-stearic acid, and 12-hydroxy-9, 15-octadecadienoic acid.

13. The method according to claim 6, wherein the hydroxy fatty acid ester is one or more selected from the group consisting of methyl ricinoleate, ethyl ricinoleate, methyl 12-hydroxy-9, 15-octadecadienoate, and castor oil biodiesel.

14. The method according to claim 6, wherein the castor oil biodiesel has a methyl ricinoleate content of more than 80% by weight, preferably a methyl ricinoleate content of more than 90% by weight.

15. The process according to claim 6, wherein the dicarboxylic acid or anhydride thereof is selected from the group consisting of C₂～C₃₀Preferably C₄～C₂₄Most preferably C₄～C₁₈A saturated or unsaturated dicarboxylic acid or an anhydride thereof.

16. The process according to claim 6, wherein the dicarboxylic acid or anhydride thereof is selected from the group consisting of unsubstituted C₄～C₈And a saturated or unsaturated dicarboxylic acid or anhydride thereof, and a copolymer of 1 to 2 carbon atoms₁～C₁₆Alkyl or alkenyl substituted C₄～C₈A saturated or unsaturated dicarboxylic acid or an anhydride thereof.

17. The method according to claim 6, wherein the dicarboxylic acid is one or more selected from succinic acid, methylsuccinic acid, decenylsuccinic acid, dodecenylsuccinic acid, maleic acid, fumaric acid, cis-methylbutenedioic acid, trans-methylbutenedioic acid, itaconic acid, and 2-butene-1, 4-dicarboxylic acid.

18. The method according to claim 6, wherein the acid anhydride is one or more selected from the group consisting of maleic anhydride, citraconic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, methyl succinic anhydride, dimethyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, and the like.

19. A fuel composition comprising a base fuel and a fuel additive as claimed in any one of claims 1 to 5.

20. The composition of claim 19, wherein the sulfur content of the base fuel is less than 500 mg-kg^-1The addition amount of the fuel additive in the base fuel is 10-500 mg/kg^-1Preferably 50 to 300 mg/kg^-1。

21. The composition of claim 19, wherein the base fuel is selected from the group consisting of diesel fuel, heavy fuel, industrial fuel, biofuel, aviation fuel, gasoline fuel, kerosene fuel, ethanol fuel, and mixtures thereof.

Technical Field

The invention relates to the field of fuels, in particular to a fuel additive, a preparation method thereof and a fuel composition.

Background

With the continuous upgrading of the quality of oil products, the problem of poor lubricating property of low-sulfur diesel oil is highlighted, mainly because in the refining process of the diesel oil, sulfide is removed, and simultaneously aromatic heterocyclic compounds with stronger polarity, nitrogen-containing polar compounds, acidic substances and other effective anti-wear components are removed, so that the lubricating property of the diesel oil is poor. This is accompanied by problems such as insufficient engine power, poor fuel atomization, excessive wear of precision parts, and failure of the fuel pump.

The addition of an antiwear agent to low sulfur diesel is a widely adopted method to improve the lubricity of diesel at present. The currently used diesel lubricity additives are mainly some polar compounds, such as alcohols, ethers, fatty acids and esters thereof, amine compounds, and the like. The compounds are generally oily agents with polar groups such as hydroxyl, carboxyl or ester groups, and the active polar substances are adsorbed on the surface of the friction metal under the boundary lubrication condition to form a firmer chemical adsorption film, so that the direct contact of the metal is reduced, the oxidation corrosion abrasion, the chemical corrosion abrasion, the adhesion abrasion and the scratch between the friction surfaces in an oil pump and an oil injector are prevented, and the boundary lubrication and the abrasion reduction are realized. The amount of the additive varies depending on the type, concentration and type of the diesel oil, and is generally 50 to 300. mu.g/g.

Patent EP1209217B1 discloses C₆～C₅₀The reaction product of saturated fatty acid and dicarboxylic acid and short-chain oil-soluble primary, secondary and tertiary amines is used as diesel antiwear agent, but the addition amount is large, and the solubility and stability in base diesel are poor.

Patent EP0605857B1(CA2112732C) discloses the use of fatty acid esters such as rapeseed oil, sunflower oil, castor oil, etc. as diesel antiwear agents directly, which have the advantages of readily available raw materials, relatively low price, etc., but relatively poor use effect, and are inconvenient for practical use due to their high viscosity.

Patent US2009/0056203a1 discloses a fatty acid type low sulfur diesel antiwear agent, but this fatty acid type antiwear agent is susceptible to interact with high base number dispersants in diesel to generate calcium and magnesium salts, which cause fuel filter screen plugging and may also cause metal corrosion.

The patent CN109576021A discloses an improver for improving the lubricity of low-sulfur diesel oil and a preparation method thereof, unsaturated dicarboxylic acid ester and a polymerization inhibitor are mixed at 150-180 ℃, tung oil biodiesel is gradually added, then the reaction is continued at 200-240 ℃, and a diesel oil antiwear agent product is obtained through reduced pressure distillation after the reaction.

Patent CN104031701B discloses a low-sulfur diesel antiwear agent, which is compounded by at least one ester oily component, at least one amide oily component and at least one low-sulfur solvent component, such as dodecyl salicylic acid glyceride, dodecyl salicylic acid ethylenediamine amide and D60 solvent oil; or compounding the ricinoleic acid glyceride, the ricinoleic acid ethylenediamine amide and the D60 solvent oil, and the like. The antiwear agent is non-toxic and free of heavy metal, and can improve the lubricating property of low-sulfur diesel oil. However, the preparation process of the antiwear agent compound is complex and difficult to operate, and the preparation cost of the product is high due to the limited raw material sources.

The patent CN106118767B discloses an antiwear agent for bio-based diesel fuel, which is prepared by taking biomass castor oil as a raw material, preparing castor oil fatty acid through saponification and acidification treatment, then reacting the castor oil fatty acid with diethanol amine to prepare a lubricating base material with an oleic acid alcohol amide structure, and then preparing nano cerium oxide through an oil-water interface method, wherein the nano cerium oxide is doped and dispersed in the base material to prepare the antiwear agent, but the preparation process of the antiwear agent is complex.

The patent CN105936837B discloses a full-ester environment-friendly diesel antiwear agent and a preparation method thereof, wherein resorcinol is taken as a basic raw material to react with acetic anhydride and ethylene oxide, potassium hydroxide is added, a reduced pressure method is adopted to obtain a resorcinol ester solution, then the resorcinol ester solution reacts with ricinoleic acid, methanol and toluene, ethanol is added, and then the mixture is washed and filtered to obtain the full-ester environment-friendly diesel antiwear agent. The antiwear agent does not contain limiting elements such as sulfur, chlorine and the like, and is an environment-friendly antiwear agent. But the synthesis process is complex and the experimental parameters are difficult to control.

Patent CN103289763A discloses a low-sulfur diesel antiwear agent, which is composed of triethanolamine, toluene, ricinoleic acid, glycerol, polyethylene glycol and an antioxidant, but the antiwear agent is more complex in composition and general in antiwear performance.

Disclosure of Invention

In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a fuel additive with significant antiwear effect and anti-rust function.

The invention also provides a preparation method of the fuel additive.

The invention also provides a fuel composition containing the additive.

In a first aspect, a fuel additive comprising at least a compound represented by structural formula I:

wherein R is₁Can be hydrogen, hydrocarbon radicals with or without double bonds, R₂Is a hydrocarbon radical with or without double bonds, R₁And R₂Has a total carbon number of 1 to 30, R₃Is hydrogen or C₁～C₂₀A hydrocarbon group of R₄May or may not be present. When R is₄When present, R₄Is C₁～C₃₀A hydrocarbon group of (1).

Preferably, R₁、R₂The total number of carbon atoms of (A) is 8 to 24, more preferably 16 to 22, and the total number of double bonds is 0 to 5, preferably 0 to 3, for example R₁And R₂May each be independently selected from alkyl, alkenyl, dienyl, and the like.

Preferably, R₃Is hydrogen or C₁～C₁₀More preferably R₃Is hydrogen or C₁～C₄The hydrocarbyl group of (2) such as alkyl group and alkenyl group may specifically be methyl group, ethyl group, n-propyl group, propenyl group, n-butyl group, isobutyl group, butenyl group, etc., and most preferably hydrogen, methyl group, ethyl group.

Preferably, R₄Is C₁～C₂₀The hydrocarbon group of (3) may be an alkylene group or an alkenylene group, an alkyl-substituted alkylene group, an alkyl-substituted alkenylene group, an alkenyl-substituted alkylene group or an alkenyl-substituted alkenylene group, and may be a normal alkyl group, an isomeric alkyl group, a normal alkenyl group or an isomeric alkenyl group, more preferably C₂～C₁₆Alkylene of (A)Alkyl or alkenyl substituted alkylenes, alkyl or alkenyl substituted alkenylenes such as ethylene, vinylene, methylene ethylene, methylethylene, dodecenylethylene, and the like.

In a second aspect, the present invention provides a process for preparing a fuel additive comprising the formula I: raw materials containing hydroxy fatty acid and/or hydroxy fatty acid ester and dicarboxylic acid and/or anhydride thereof are subjected to esterification reaction to generate the compound shown in the structural formula I.

Wherein, the hydroxy fatty acid or hydroxy fatty acid ester and the dicarboxylic acid or anhydride thereof can be reacted according to a molar ratio of 1: 0.1-10, preferably the molar ratio is 1: 0.5-5, more preferably the molar ratio is 1: 0.5-3, such as 1:1, 1:2, and the like.

Wherein, the esterification reaction temperature can be in the range of 30-300 ℃, preferably 50-250 ℃, and more preferably 70-180 ℃. The esterification reaction time is generally 0.5 to 30 hours, preferably 2 to 20 hours, and more preferably 4 to 10 hours.

According to the process of the present invention, the reaction system may or may not be added with a solvent. The solvent can be toluene, xylene, ethylbenzene, petroleum ether, mineral spirits, cyclohexane, n-octane, or mixtures thereof.

According to the method of the present invention, a catalyst may be used in the reaction system without using a catalyst. The catalyst may be an acid catalyst such as sulfuric acid, p-toluenesulfonic acid, phosphoric acid, boric acid, and the like; ionic liquid catalysts may be used, such as 1-butylpyridine/AlCl₄Ionic liquids and the like; inorganic salt solid phase catalysts, e.g. FeCl, may be used₃、AlCl₃Etc.; molecular sieve catalysts such as ZSM-5, HZSM-5, Al-MCM-41, etc.; with heteropolyacid catalysts, e.g. PW₁₂/MCM-41、SiW₁₂/MCM-41, etc.; solid super acidic catalysts, e.g. SO, may be used₄ ^2-/ZrO₂-TiO₂Etc.; alkali catalysts such as NaOH, KOH, sodium methoxide, solid superbase, NaH, etc. may be used.

According to the method of the present invention, when the additive is prepared using dicarboxylic acid as a raw material, it is preferable to use a catalyst in order to improve the progress of the esterification reaction and to improve the yield; when the additive is prepared starting from an acid anhydride, it is preferred not to use a catalyst.

For the sake of simplicity of description, the "hydroxy fatty acid and/or hydroxy fatty acid ester" is simply referred to as "hydroxy fatty acid (ester)" in the following description.

The carbon number of the fatty carbon chain in the hydroxy fatty acid (ester) is C₁～C₃₀Preferably C₈～C₂₄Most preferably C₁₆～C₂₂The aliphatic carbon chain may be a straight chain hydrocarbon or an isomeric hydrocarbon. The number of unsaturated carbon-carbon double bonds in the aliphatic carbon chain is 0 to 5, preferably 0 to 3. The double bonds may be at any position of the carbon chain, and if 2 or more carbon-carbon double bonds are present, the relative positions of the unsaturated carbon-carbon double bonds are random, and may be a conjugated structure or a non-conjugated structure, for example.

The hydroxyl in the hydroxy fatty acid (ester) can be positioned at any position of a fatty carbon chain, such as alpha position, beta position and the like.

The carbon number of the ester group of the hydroxy fatty acid ester can be C₁～C₁₀Preferably C₁～C₄For example, it may be one or more of hydroxy fatty acid methyl ester, hydroxy fatty acid ethyl ester, hydroxy fatty acid n-propyl ester, hydroxy fatty acid isopropyl ester, hydroxy fatty acid n-butyl ester, hydroxy fatty acid isobutyl ester, hydroxy fatty acid butenyl ester, hydroxy fatty acid n-octyl ester, etc., preferably one or more of hydroxy fatty acid methyl ester and hydroxy fatty acid ethyl ester.

The hydroxy fatty acid ester can be an esterification product of hydroxy fatty acid and fatty alcohol, and can also be an ester exchange product of triglyceride and fatty alcohol. Wherein the fatty alcohol is C₁～C₁₀Saturated or unsaturated fatty alcohols of, preferably C₁～C₄The saturated fatty alcohol of (2) may be a normal saturated fatty alcohol or an isomeric saturated fatty alcohol.

The preferred hydroxy fatty acid ester may specifically be one or more of a methyl ester compound of a hydroxy fatty acid, an ethyl ester compound of a hydroxy fatty acid, an n-propyl ester compound of a hydroxy fatty acid, an isopropyl ester compound of a hydroxy fatty acid, an n-butyl ester compound of a hydroxy fatty acid, an isobutyl ester compound of a hydroxy fatty acid, and the like.

The hydroxy fatty acid (ester) may be specifically selected from one or more of the compounds listed in table 1, but is not limited to the listed compounds:

table 1 fatty acid (ester) compounds

Among the above-mentioned hydroxy fatty acid compounds, one or more of ricinoleic acid, hydroxystearic acid, hydroxyoctadecadienoic acid and the like are most preferable.

Among the above-mentioned hydroxy fatty acid ester compounds, one or more of methyl ricinoleate, methyl transricinoleate, ethyl ricinoleate, methyl hydroxyoctadecadienoate and the like are most preferable.

Another preferred example of the hydroxy fatty acid ester compound includes castor oil biodiesel, the main chemical composition of which is methyl ricinoleate. The castor oil biodiesel produced by raw materials with high content of methyl ricinoleate can be preferably selected, and the saturated fatty acid methyl ester in the castor oil biodiesel can be removed by reduced pressure distillation and low temperature freezing crystallization to obtain the castor oil biodiesel with high content of methyl ricinoleate.

The castor oil biodiesel is castor oil biodiesel with the content of methyl ricinoleate more than 60 wt%, preferably castor oil biodiesel with the content of methyl ricinoleate more than 80 wt%, further preferably castor oil biodiesel with the content of methyl ricinoleate more than 90 wt%, and more preferably castor oil biodiesel with the content of methyl ricinoleate more than 95 wt%.

The dicarboxylic acid or anhydride thereof is selected from C₂～C₃₀Preferably C₄～C₂₄Further preferably C₄～C₁₈The saturated or unsaturated dicarboxylic acid or anhydride thereof may be unsubstituted dicarboxylic acid or anhydride thereof, or one or more of dicarboxylic acids or anhydrides thereof having alkyl or alkenyl substituents, most preferably unsubstituted C₄～C₈And a saturated or unsaturated dicarboxylic acid or anhydride thereof, and a copolymer of 1 to 2 carbon atoms₁～C₁₆Alkyl or alkenyl substituted C₄～C₈A saturated or unsaturated dicarboxylic acid or an anhydride thereof.

The saturated dicarboxylic acid may be specifically selected from one or more of the following compounds: can be oxalic acid, malonic acid, succinic acid (succinic acid), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, etc.; and may be selected from methyl malonic acid, methyl succinic acid, dimethyl succinic acid, diethyl succinic acid, propyl succinic acid, amyl succinic acid, isopropyl succinic acid, hexyl succinic acid, heptyl succinic acid, octyl succinic acid, nonyl succinic acid, decyl succinic acid, undecyl succinic acid, dodecyl succinic acid, tridecyl succinic acid, tetradecyl succinic acid, pentadecyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, and the like.

The saturated dicarboxylic acid is most preferably one or more of succinic acid, methylsuccinic acid, dimethylsuccinic acid, octylsuccinic acid and dodecylsuccinic acid.

The unsaturated dicarboxylic acid may be specifically selected from one or more of the following compounds, including but not limited to: maleic acid (maleic acid), fumaric acid (fumaric acid), cis-methylbutenedioic acid (citraconic acid), trans-methylbutenedioic acid (mesaconic acid), dimethylmaleic acid, itaconic acid (methylenesuccinic acid, itaconic acid), glutaconic acid, trans-3-hexenedioic acid, butynedioic acid, 2-butene-1, 4-dicarboxylic acid, hexadiene diacid, heptenedioic diacid, octenedioic diacid, nonene diacid, decene diacid, undecene diacid, dodecene diacid, tridecene diacid, tetradecene diacid, pentadecene diacid, hexadecene diacid, heptadecene diacid, octadecene diacid, eicosene diacid, etc.; it may be selected from pentenylsuccinic acid, hexadienylsuccinic acid, heptylsuccinic acid, octenylsuccinic acid, nonenylsuccinic acid, decenylsuccinic acid, dodecenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, octadecenylsuccinic acid, docosenylsuccinic acid, etc.

The unsaturated dicarboxylic acid is preferably: maleic acid (maleic acid), fumaric acid (fumaric acid), cis-methyl butenedioic acid (citraconic acid), trans-methyl butenedioic acid (mesaconic acid), dimethyl maleic acid, itaconic acid (methylenesuccinic acid ), 2-butene-1, 4-dicarboxylic acid, decenylsuccinic acid, dodecenylsuccinic acid.

The saturated anhydride may be selected from one or more of the following compounds, including but not limited to: can be succinic anhydride (succinic anhydride), oxalic anhydride, glutaric anhydride, adipic anhydride, etc.; methyl glutaric anhydride, methyl succinic anhydride, dimethyl succinic anhydride, ethyl succinic anhydride, propyl succinic anhydride, butyl succinic anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, tridecyl succinic anhydride, tetradecyl succinic anhydride, pentadecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, methylpentadecyl succinic anhydride, ethyltetradecyl succinic anhydride, dimethyl tetradecyl succinic anhydride, hexyl dodecyl succinic anhydride, heptyl undecyl succinic anhydride, 1-octyl-2-decyl succinic anhydride, or the like;

the unsaturated anhydride may be selected from maleic anhydride (maleic anhydride), 2, 3-dimethylmaleic anhydride, citraconic anhydride, itaconic anhydride, glutaconic anhydride, and the like.

The unsaturated anhydride may also be selected from (2-methyl-2-propene) based succinic anhydride, vinyl succinic anhydride, propenyl succinic anhydride, butenyl succinic anhydride, triisobutenyl succinic anhydride, pentenyl succinic anhydride, 3-methyl-hexenyl succinic anhydride, heptenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, eicosadienyl succinic anhydride, methyl heptadecenyl succinic anhydride, octyl decenyl succinic anhydride, and the like.

The anhydride is most preferably one or more of maleic anhydride, citraconic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, methyl succinic anhydride, dimethyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, nonenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, and the like.

In a third aspect, the present invention provides a fuel composition comprising a base fuel and a fuel additive according to the present invention. The sulfur content of the base fuel is less than 500mg kg^-1The amount of the fuel additive to be added to the base fuel is generally 10 to 500 mg/kg^-1Preferably 50 to 300 mg/kg^-1。

The basic fuel can be distillate of crude oil (petroleum) processed by various refining processes of an oil refinery, such as atmospheric and vacuum distillation, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking and the like, or fuel for spark ignition internal combustion engines, fuel for compression ignition internal combustion engines and turbine fuel which are blended to meet national standards. Such as diesel fuel, heavy fuel, industrial fuel, renewable fuel (biofuel), aviation fuel, gasoline fuel, kerosene fuel, ethanol fuel, and the like, and mixtures thereof.

The diesel fuel can be first generation biodiesel, second generation biodiesel, third generation biodiesel, diesel fuel obtained by Fischer-Tropsch synthesis, or diesel fuel obtained by direct coal liquefaction.

The gasoline fuel can be vehicle gasoline and aviation gasoline. The gasoline fuel can be straight-run gasoline, thermal cracked gasoline, catalytic cracked gasoline, reformed gasoline, coker gasoline, congruence gasoline, hydrocracking gasoline, pyrolysis gasoline, alkylated gasoline, synthetic gasoline, etc. according to different preparation processes.

The aviation fuel can be aviation gasoline, aviation kerosene and the like.

Including but not limited to marine fuels.

The fuel oil lubricity additive provided by the invention can be used as a single agent, and can also be compounded with other fuel oil additives for use. The fuel oil composition may further contain other additives such as a flow improver, a cetane number improver, a detergent dispersant, a metal deactivator, a preservative and the like according to use requirements.

The invention takes hydroxy fatty acid (ester) as raw material to carry out esterification reaction with dicarboxylic acid or anhydride thereof, thus generating the fuel additive with surprisingly remarkable anti-wear effect.

Compared with the prior art, the invention has the following advantages:

(1) the fuel additive has good stability, good compatibility with the basic fuel, small addition amount in the basic fuel and surprising antiwear effect;

(2) the fuel additive has no antagonistic effect with other fuel additives;

(3) the fuel additive has simple preparation process, low production cost and clean production process;

(4) the fuel additive has certain anti-corrosion performance.

Drawings

FIG. 1 is a mass spectrum of the additive product prepared in example 1, namely: is a succinic acid ester ricinoleic acid methyl ester product prepared by using ricinoleic acid methyl ester and succinic anhydride as raw materials, and m/z is 435.83 which is a mass spectrum addition peak of sodium ions of the succinic acid ester ricinoleic acid methyl ester prepared in example 1.

FIG. 2 is a mass spectrum of the additive product prepared in example 6, namely: is a succinate-based ricinoleic acid product prepared from ricinoleic acid and succinic anhydride as raw materials, and m/z 421.502 is the mass spectrum addition peak of sodium ions of the succinate-based ricinoleic acid prepared in example 6.

FIG. 3 is a mass spectrum of the additive product prepared in example 11, namely: is a methyl maleate ricinoleate product prepared from methyl ricinoleate and maleic anhydride, and m/z 433.25 is the mass spectrum addition peak of sodium ions of the methyl maleate ricinoleate prepared in example 11.

FIG. 4 is an infrared spectrum of the additive product prepared in example 11, i.e.: is a maleic acid ester based methyl ricinoleate product prepared by taking methyl ricinoleate and maleic anhydride as raw materials, wherein the mass is 1727cm^-1Strong peak of (A) represents CH₂Stretching vibration peak of carbonyl group having CH-COOH structure, 1166cm^-1The sharp absorption peak of (A) represents an absorption peak of an ester ether bond of 3000cm^-1～2700cm^-1The region represents the stretching vibration peak of methyl and methylene, 978cm^-1The peak represents the stretching vibration peak of the trans-carbon double bond.

FIG. 5 is a mass spectrum of the antiwear agent product prepared in example 19, namely: is a maleate-based ricinoleic acid product prepared from ricinoleic acid and maleic anhydride, and m/z 419.59 is the mass spectrum addition peak of the sodium ion of the maleate-based ricinoleic acid prepared in example 19.

FIG. 6 is an infrared spectrum of the antiwear agent product prepared in example 19, namely: is a maleic acid ester ricinoleic acid product prepared by taking ricinoleic acid and maleic anhydride as raw materials, wherein the length of the product is 3450-3150 cm^-1The area represents hydroxyl and is 2800-3000 cm^-1The region represents methyl and methylene, 1736cm^-1Represents the stretching vibration peak of ester carbonyl group, 722cm^-1The sharp absorption peak of (2) represents 4 or more methylene deformation oscillation peaks.

FIG. 7 is a plot of HFRR wear scar area for base diesel A, corrected for scar wear diameter (WS1.4) value of 640 μm.

FIG. 8 is a HFRR wear plaque after the antiwear product prepared in example 1 was added to a base diesel fuel at an addition level of 200. mu.g/g, and the corrected scar diameter (WS1.4) value was 217 μm.

FIG. 9 HFRR wear marks after the antiwear product prepared in example 12 was added to A base diesel fuel at an addition level of 200. mu.g/g, and the corrected scar diameter (WS1.4) value was 181. mu.m.

FIG. 10 HFRR wear marks after the antiwear product prepared in example 18 was added to a base diesel fuel A at an addition level of 200. mu.g/g, and the corrected scar diameter (WS1.4) value was 408. mu.m.

Detailed Description

The technical solutions of the present invention are further described below with reference to specific embodiments, which should not be construed as limiting the present invention in any way.

The invention can use castor oil biodiesel as raw material, so that the castor oil biodiesel obtained by any mode can be used in the invention. In the present invention, since castor oil biodiesel is generally a mixed fatty acid methyl ester mainly composed of methyl ricinoleate, the molecular weight thereof can be regarded as the same as that of methyl ricinoleate (molecular weight of 312.5g/mol) for the sake of calculating the charge ratio.

Examples 1-5 are provided to illustrate the synthesis of fuel additive products by reacting hydroxy fatty acid esters with saturated dicarboxylic acids or anhydrides.

Example 1

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biochemical technology Co., Ltd.) and 128.5g of succinic anhydride (99% by mass, Shanghai Arlatin Biochemical technology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube (the molar ratio of methyl ricinoleate to succinic anhydride was about 1: 0.8). Nitrogen was introduced, and the mixture was slowly heated to 80 ℃ with stirring, and reacted under reflux for 4 hours.

As shown in equation 1.

624.1g of methyl succinate ricinoleate were obtained in a yield of about 71.3%.

Example 2

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biotechnology Co., Ltd.) and 245.7g of succinic acid (99.5% by mass, Shanghai Arlatin Biotechnology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen introduction tube (the molar ratio of methyl ricinoleate to succinic acid was about 1: 1.3). Nitrogen gas is introduced, the mixture is slowly heated to 120 ℃ while stirring, and the reflux reaction is carried out for 10 hours. Excess succinic acid was removed by distillation under reduced pressure to give 739.9g of succinylated methyl ricinoleate with a yield of about 76.7%.

Example 3

The castor oil biodiesel is obtained according to the preparation method of the castor oil biodiesel provided in example 1 of patent CN 101974372A. 1000g of castor oil biodiesel (the composition of fatty acid ester of castor oil biodiesel is shown in Table 2) and 801.5g of succinic anhydride (succinic anhydride, 99% by mass, available from Shanghai Arlatin Biochemical technology Co., Ltd.) were charged into a 3000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen inlet tube, the molar ratio of castor oil biodiesel (the molecular weight of which is the same as that of methyl ricinoleate, and is 312.5g/mol) to succinic anhydride was about 1:2.5, nitrogen was introduced, the mixture was heated under stirring to 100 ℃ and subjected to reflux reaction for 8 hours, and excess succinic anhydride was removed by distillation under reduced pressure to obtain about 1706.1g of a product, with a yield of about 92.8%.

TABLE 2 fatty acid ester composition of castor oil biodiesel

Fatty acid methyl ester type	Fatty acid methyl ester content (% by weight)
		Ricinoleic acid methyl ester	86
Oleic acid methyl ester	4.1
		Palmitic acid methyl ester	1.3
Stearic acid methyl ester	1.5
		Linoleic acid methyl ester	5.3
Total methyl ester	98.2

Example 4

500g of methyl ricinoleate (75% by mass, Shanghai Arragana Biochemical Co., Ltd.) and 328.7g of glutaric anhydride (98% by mass, Shanghai Merlan Biochemical Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube (the molar ratio of methyl ricinoleate to glutaric anhydride was about 1: 1.8). Nitrogen is introduced, the mixture is slowly heated to 180 ℃ while stirring, and the reflux reaction is carried out for 2 hours. 822.4g of glutarate-based methyl ricinoleate were obtained, and the yield was about 85.7%.

Example 5

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biochemical technology Co., Ltd.) and 383.4g of 2-methylsuccinic anhydride (98% by mass, Shanghai Merlin Biochemical technology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube (the molar ratio of methyl ricinoleate to 2-methylsuccinic anhydride was about 1: 2.1). Nitrogen gas is introduced, the mixture is slowly heated to 200 ℃ while stirring, and the reflux reaction is carried out for 5 hours. 877.1g of methyl 2-methylsuccinate-based ricinoleate were obtained in a yield of about 83.4%.

Examples 6-10 are provided to illustrate the synthesis of antiwear agents by reacting hydroxy fatty acids with saturated dicarboxylic acids or anhydrides.

Example 6

500g of ricinoleic acid (95 mass%, Shanghai Michelin Biochemical technology Co., Ltd.) and 100.6g of succinic anhydride (99 mass% succinic anhydride, Shanghai Aladdin Biochemical technology Co., Ltd.) were put into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen introduction tube, and nitrogen was introduced for 5 to 10 minutes. The molar ratio of ricinoleic acid to succinic anhydride is about 1:0.6, the temperature is raised to 50 ℃ by heating and stirring, and the reflux reaction is carried out for 28 hours, as shown in the reaction formula 2.

594.4g of succinate-based ricinoleic acid was obtained in a yield of about 73.1%.

Example 7

500g of ricinoleic acid (95 mass%, Shanghai Michelin Biochemical technology Co., Ltd.) and 322.0g of 2, 2-dimethylsuccinic anhydride (98 mass%, Shanghai Aladdin Biochemical technology Co., Ltd.) were put into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes. The molar ratio of the ricinoleic acid to the 2, 2-dimethylsuccinic anhydride is about 1:1.5, the temperature is raised to 200 ℃ by heating and stirring, and the reflux reaction is carried out for 7 hours, so that about 816.9g of the 2, 2-dimethylsuccinate ricinoleic acid product is obtained, and the yield is about 89.7%.

Example 8

500g of ricinoleic acid (95 mass percent, Shanghai Michelin Biochemical technology Co., Ltd.) and 774.6g of glutaric acid (99 mass percent, Shanghai Michelin Biochemical technology Co., Ltd.) were added to a 2000mL reactor, the reactor was equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen inlet tube, and nitrogen was introduced for 5-10 minutes. The molar ratio of ricinoleic acid to glutaric acid was about 1:3.5, and about 13g of p-toluenesulfonic acid (99% by mass, Shanghai Michelin Biochemical technology Co., Ltd.) was added as a catalyst in an amount of about 1% by mass of the total mass of the reactants. Heating and stirring to 240 ℃, refluxing for 8 hours, cooling to room temperature, and removing p-toluenesulfonic acid to obtain about 1269.1g of glutarate-based ricinoleic acid product with the yield of about 87.2%.

Example 9

500g of 12-hydroxystearic acid (85% by mass, Shanghai Michelin Biochemical technology Co., Ltd.) and 1332.2g of succinic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were put into a 3000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and nitrogen was introduced for 5 to 10 minutes. The molar ratio of 12-hydroxystearic acid to succinic anhydride is about 1:8, the mixture is heated and stirred to 150 ℃, and the reflux reaction is carried out for 10 hours until about 1829.9g of succinate stearic acid product is obtained, and the yield is about 73.7%.

Example 10

500g of 10-hydroxy-decanoic acid (96% by mass, Shanghai Michelin Biochemical technology Co., Ltd.) and 398.7g of succinic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were added to a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen inlet tube, nitrogen was introduced for 5-10 minutes, the molar ratio of 10-hydroxy-decanoic acid to succinic anhydride was about 1:1.5, the mixture was heated, stirred and heated to 100 ℃ and refluxed for 16 hours. After cooling to room temperature, excess succinic anhydride was removed by distillation under reduced pressure to give about 894.3g of succinylated decanoic acid product in about 79.4% yield.

Examples 11-18 illustrate the synthesis of antiwear agent products from the reaction of hydroxy fatty acid esters with unsaturated dicarboxylic acids or anhydrides.

Example 11

500g of methyl ricinoleate (75% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) and 156.9g of maleic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were added to a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen introduction tube, the molar ratio of methyl ricinoleate to maleic anhydride was about 1:1, nitrogen was introduced for 5-10 minutes, the temperature was raised to 100 ℃ by heating and stirring, and the reflux reaction was carried out for 4 hours, as shown in reaction formula 3.

649.6g of methyl maleate ricinoleate were obtained in a yield of about 75.1%.

Example 12

500g of methyl ricinoleate (75% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) and 392.4g of maleic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the molar ratio of methyl ricinoleate to maleic anhydride was about 1: 2.5. And introducing nitrogen for 5-10 minutes, heating and stirring to raise the temperature to 80 ℃, carrying out reflux reaction for 10 hours, and removing excessive maleic anhydride through reduced pressure distillation to obtain the maleic ester ricinoleic acid methyl ester. 887.1g of product was obtained with a yield of about 89.1%.

Example 13

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biochemical technology Co., Ltd.) and 148.6g of maleic acid (maleic acid, 99% by mass, Shanghai Merlin Biochemical technology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the molar ratio of methyl ricinoleate to maleic acid was about 1: 0.8. And introducing nitrogen for 5-10 minutes, heating, stirring, heating to 320 ℃, and performing reflux reaction for 3 hours to obtain the maleic ester ricinoleic acid methyl ester. 642.3g of product was obtained with a yield of about 82.1%.

Example 14

Castor oil biodiesel was obtained in a 3000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, according to the method for producing castor oil biodiesel provided in example 1 of patent CN 101974372A. Adding 1000g of castor oil biodiesel (the composition of fatty acid ester of the castor oil biodiesel is shown in table 3), 1098.8g of maleic anhydride (maleic anhydride, the mass fraction of which is 99%, Shanghai Aladdin Biotechnology Co., Ltd.), wherein the molar ratio of the castor oil biodiesel (the molecular weight of which is 312.5g/mol) to the maleic anhydride is about 1:3.5, introducing nitrogen for 5-10 minutes, heating and stirring to 120 ℃, carrying out reflux reaction for 6 hours, and removing excessive maleic anhydride by reduced pressure distillation to obtain about 2091.1g of product, wherein the yield is about 97.3%.

TABLE 3 fatty acid ester composition of castor oil biodiesel

Fatty acid methyl ester type	Fatty acid methyl ester content (% by weight)
		Ricinoleic acid methyl ester	79.78
Oleic acid methyl ester	11.48
		Palmitic acid methyl ester	1.74
Hexadecenoic acid methyl ester	1.42
		Stearic acid methyl ester	1.82
Total methyl ester	96.24

Example 15

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biochemical technology Co., Ltd.) and 269.5g of cis-methylbutenedioic anhydride (98% by mass, Shanghai Merling Biochemical technology Co., Ltd.) were added to a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, the molar ratio of methyl ricinoleate to citraconic anhydride was about 1:1.5, nitrogen gas was introduced for 5 to 10 minutes, the mixture was heated and stirred to 220 ℃ and subjected to reflux reaction for 18 hours, and excess citraconic anhydride was removed by distillation under reduced pressure to obtain a conate methyl ricinoleate. 765.1g of product was obtained with a yield of about 91.6%.

Example 16

500g of methyl ricinoleate (75% by mass, Shanghai Alantin Biochemical technology Co., Ltd.) and 624.5g of cis-methylbutenedioic acid (98% by mass, Shanghai Alantin Biochemical technology Co., Ltd.) were added to a 2000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction pipe, the molar ratio of methyl ricinoleate to citraconic acid was about 1:3, nitrogen gas was introduced for 5 to 10 minutes, the mixture was heated and stirred to 160 ℃ and subjected to reflux reaction for 22 hours, and excess citraconic acid was removed by distillation under reduced pressure to obtain citraconyl methyl ricinoleate. The product 1119.3g is obtained with a yield of about 86.7%.

Example 17

500g of methyl ricinoleate (75 mass percent, Shanghai Aladdin Biochemical technology Co., Ltd.) and 233.5g of itaconic anhydride (95 mass percent, Shanghai Aladdin Biochemical technology Co., Ltd.) were added into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, the molar ratio of methyl ricinoleate to itaconic anhydride was about 1:1.3, nitrogen was introduced for 5-10 minutes, the mixture was heated and stirred to 120 ℃, a reflux reaction was carried out for 12 hours, and excess itaconic anhydride was removed by vacuum distillation to obtain itaconate methyl ricinoleate. 828.3g of product was obtained with a yield of about 88.7%.

Example 18

500g of methyl ricinoleate (75% by mass, Shanghai Arlatin Biochemical Co., Ltd.) and 1065.7g of dodecenyl succinic anhydride (95% by mass, Shanghai Arlatin Biochemical Co., Ltd.) were charged into a 2000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube (the molar ratio of methyl ricinoleate to dodecenyl succinic anhydride was about 1: 2.5). And introducing nitrogen for 5-10 minutes, heating and stirring to raise the temperature to 140 ℃, carrying out reflux reaction for 10 hours, and carrying out reduced pressure distillation to remove excessive dodecenyl succinic anhydride to obtain dodecenyl succinate-based methyl ricinoleate, wherein 1557.9g of the product is obtained, and the yield is about 89.6%.

Examples 19-23 are provided to illustrate the synthesis of antiwear agent products obtained by reacting hydroxy fatty acids with unsaturated dicarboxylic acids or anhydrides.

Example 19

500g of ricinoleic acid (95 mass percent, Shanghai Michelin Biochemical technology Co., Ltd.) and 131.5g of maleic anhydride (99 mass percent, Shanghai Aladdin Biochemical technology Co., Ltd.) were added to a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser tube and a nitrogen introduction tube, the molar ratio of ricinoleic acid to maleic anhydride was about 1:0.8, nitrogen was introduced for 5 to 10 minutes, the mixture was heated and stirred to 80 ℃ and subjected to reflux reaction for 10 hours, as shown in reaction formula 4.

625.4g of maleate-based ricinoleic acid was obtained with a yield of about 75.9%.

Example 20

500g of ricinoleic acid (95 mass%, Shanghai Michelin Biochemical Co., Ltd.) and 316.9g of 2, 3-dimethylmaleic anhydride (98 mass%, Shanghai Arlatin Biochemical Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction pipe, and the molar ratio of ricinoleic acid to 2, 3-dimethylmaleic anhydride was about 1: 1.5. And introducing nitrogen for 5-10 minutes, heating, stirring, heating to 150 ℃, and carrying out reflux reaction for 8 hours to obtain about 809.7g of the 2, 3-dimethyl maleate ricinoleic acid product, wherein the yield is about 81.7%.

Example 21

500g of 12-hydroxystearic acid (85% by mass, Shanghai Michelin Biochemical technology Co., Ltd.) and 293.8g of maleic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, and the molar ratio of 12-hydroxystearic acid to maleic anhydride was about 1: 1.8. And introducing nitrogen for 5-10 minutes, heating, stirring, heating to 200 ℃, and carrying out reflux reaction for 1 hour to obtain about 787.6g of a maleate stearic acid product, wherein the yield is about 85.4%.

Example 22

500g of 10-hydroxy-decanoic acid (96% by mass, Shanghai Michelin Biochemical technology Co., Ltd.) and 78.3g of maleic anhydride (99% by mass, Shanghai Aladdin Biochemical technology Co., Ltd.) were placed in a 1000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and the molar ratio of 10-hydroxy-decanoic acid to maleic anhydride was about 1: 0.3. And introducing nitrogen for 5-10 minutes, heating, stirring, heating to 180 ℃, and carrying out reflux reaction for 4 hours to obtain about 884.7g of maleate-base decanoic acid product, wherein the yield is about 92.4%.

Example 23

500g of ricinoleic acid (95% by mass, Shanghai Michell Biotech Co., Ltd.) and 714.7g of dodecenylsuccinic acid (98% by mass, Nanjing Bomiel Biotech Co., Ltd.) were charged into a 2000mL reactor equipped with an electric stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube (the molar ratio of ricinoleic acid to dodecenylsuccinic acid was about 1:1.5), and about 12.2g of p-toluenesulfonic acid (99% by mass, Shanghai Michell Biotech Co., Ltd.) was added as a catalyst in an amount of about 1% by mass based on the total mass of the reactants. And introducing nitrogen for 5-10 minutes, heating, stirring, heating to 280 ℃, carrying out reflux reaction for 10 hours, cooling to room temperature, removing p-toluenesulfonic acid, and carrying out reduced pressure distillation to remove excessive dodecenylsuccinic acid to obtain dodecenylsuccinic ester-based ricinoleic acid, wherein 1208.9g of the product is obtained, and the yield is about 84.6%.

Comparative example

Comparative example 1 methyl ricinoleate (75% by mass) reagent from Shanghai Arlatin Biotechnology Co., Ltd was used as a diesel antiwear agent.

Comparative example 2 an ester type diesel antiwear agent Infineum R655 from Runki Co.

Comparative example 3 ricinoleic acid (95% by mass) reagent from makelin biochemical technology ltd, shanghai was used as a diesel antiwear agent.

Comparative example 4 a product of Hitec 4140, a fatty acid type diesel antiwear agent from jafton, usa, was used.

EXAMPLE 24 lubricity test

In this example, the lubricity of diesel fuel was measured in accordance with the method described in ISO12156-1 (ASTM D6079) on a High-Frequency Reciprocating Rig (HFRR) (manufactured by PCS instruments, UK) at 60 ℃ in a Wear Diameter (WSD), and the reported result WS1.4 was obtained by correcting the influence of temperature and humidity, and the evaluation test conditions of the HFRR tester are shown in Table 4.

Table 4 evaluation test conditions

Parameter(s)	Numerical value
		Liquid volume/mL	2.0±0.2
Temperature of the liquid/. degree.C	60±2
		frequency/Hz	50±1
Length of stroke/mm	1.0±0.02
		Test time/min	75

The sulfur content of the low-sulfur diesel oil used in the lubricating property test is 6mg kg^-1、11mg·kg^-1The specific properties of the hydrorefined diesel oil having respective worn-out spot diameters of 640 μm and 545 μm are shown in Table 5.

TABLE 5 physicochemical properties of diesel fuel

HFRR method (ISO 12156-1) trace diameter WS1.4 of diesel before and after addition of additives is shown in tables 6 and 7, wherein the smaller the trace diameter, the better the lubricity of the diesel. At present, most of diesel oil standards in the world, such as European standard EN 590 and China automotive diesel oil standard GB/T19147, use the trace grinding diameter less than 460 μm (60 ℃) as the basis of the qualified diesel oil lubricity standard.

TABLE 6 evaluation results of lubricity of Diesel oil A

From the lubricity evaluation data in Table 6, it can be seen that the product additive of example 1 was added to the base diesel fuel at 100 mg-kg^-1When the lubricating property index of the base diesel oil is reduced from 640 mu m to 388 mu m, the base diesel oil can be used as the lubricating agentThe lubricating performance of the base diesel oil is obviously improved; 200 mg/kg of the solution is added^-1When the lubricating property index of the base diesel oil is reduced from 640 mu m to 217 mu m, even example 11 can be reduced to 205 mu m, and the lubricating property of the base diesel oil shows surprisingly excellent antiwear performance which is far better than the antiwear effect of a commercial antiwear agent.

TABLE 7 evaluation results of lubricity of Diesel oil B

It can be seen from tables 6 and 7 that methyl ricinoleate has little effect when used as diesel antiwear agent, and the addition of the same amount or even smaller amount of the product of the present invention can greatly improve the lubricating property of low sulfur diesel oil, and is obviously superior to the antiwear property of the products of the antiwear agents on the market, especially the examples 1, 2,3, 11, 12, 13 and 19 of the present invention show surprisingly excellent antiwear property.

Example 25 tarnish testing

This example shows the rust inhibitive effect of the additive products prepared in some of the examples and the additives of comparative examples 1 and 2 added to diesel fuel in an amount of 200 mg/kg, as shown in tables 8 and 9^-1The test method is GB/T11143.

TABLE 8 improvement of diesel A rust performance by additives

Oil sample	Dosage/mg/kg-1	Performance of
			Blank diesel oil A	0	100% corrosion in 4 hours
Blank Diesel A + example 1	200	No corrosion in 12 hours
			Blank Diesel A + example 2	200	No corrosion in 12 hours
Blank Diesel A + example 3	200	No corrosion in 12 hours
			Blank Diesel A + example 10	200	8 hours 10% corrosion
Blank Diesel A + example 11	200	No corrosion in 12 hours
			Blank diesel A + example 12	200	No corrosion in 12 hours
Blank Diesel A + example 13	200	No corrosion in 12 hours
			Blank Diesel A + example 19	200	No corrosion in 12 hours
Blank Diesel A + comparative example 1	200	Corrosion of 15% in 4 hours
			Blank Diesel A + comparative example 2	200	20% corrosion in 4 hours

TABLE 9 improvement of additive on diesel B Corrosion Performance

As can be seen from tables 8 and 9, the additive provided by the invention has a great improvement effect on the rust of diesel oil, and the effect is obviously better than that of castor oil fatty acid methyl ester (comparative example 1) and that of a comparative example antiwear agent (comparative example 2).

The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.