CN113462443B

CN113462443B - Diesel antiwear agent composition, preparation method thereof and diesel oil composition

Info

Publication number: CN113462443B
Application number: CN202010240138.4A
Authority: CN
Inventors: 蔺建民; 李宝石; 夏鑫; 李妍
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-03-30
Filing date: 2020-03-30
Publication date: 2023-07-14
Anticipated expiration: 2040-03-30
Also published as: CN113462443A

Abstract

The invention relates to a diesel antiwear agent composition, a preparation method thereof and a diesel composition, wherein the diesel antiwear agent composition at least contains an unsaturated dicarboxylic acid monoester compound. The antiwear agent is prepared by reacting C4-C8 unsaturated dianhydride or unsaturated diacid with C1-C30 alcohol or phenol. The diesel antiwear agent provided by the invention has excellent effect, is little in use amount in diesel oil, and can greatly reduce the use cost of the diesel antiwear agent.

Description

Diesel antiwear agent composition, preparation method thereof and diesel oil composition

Technical Field

The invention relates to the field of fuels, in particular to an ester diesel antiwear agent and a preparation method and a use method thereof.

Background

With the increasing attention of world countries to environmental problems, the production of high-quality clean energy has become the development direction of the modern oil refining industry, and the production standard of diesel oil is gradually increased. The clean diesel oil has the characteristics of low aromatic hydrocarbon content, high cetane number, light fraction, low sulfur and low nitrogen. Sulfur is the most harmful element that increases the pollutant content in the atmosphere, and thus the sulfur-containing compounds content in diesel fuel needs to be strictly controlled. The clean diesel oil produced at present is mainly produced by adopting a hydrogenation process, and the method reduces the content of the nitrogen-containing compound and the oxygen-containing compound in the diesel oil while removing the sulfur-containing compound in the diesel oil. It is known that the lubricity of diesel fuel is largely dependent on the content of antiwear impurities in the diesel fuel, and that polycyclic aromatic hydrocarbons, oxygen-containing impurities and nitrogen-containing impurities are very effective antiwear agents. The lower nitrogen and oxygen content causes a decrease in the lubricating properties of the diesel itself, resulting in wear and failure of the fuel pump.

Low sulfur diesel and ultra low sulfur diesel are commonly treated with lubricity additives (antiwear agents) to improve their lubricity due to their poor lubricity. The method has the advantages of low cost, flexible production, less pollution and the like, and is widely valued in industry.

The diesel antiwear agent is mainly a derivative of fatty acid, fatty acid ester, amide or salt. EP773279 discloses carboxylic esters prepared by reacting dimer acids with alcohol amines as diesel antiwear agents. EP798364 discloses the use of salts or amides prepared by reacting fatty acids with fatty amines as diesel antiwear agents. EP1209217 discloses the reaction products of C6-C50 saturated fatty acids and dicarboxylic acids with short chain oil-soluble primary, secondary and tertiary amines as diesel antiwear agents. WO9915607 discloses the reaction product of dimerised fatty acids with epoxides as diesel antiwear agents. Most of the technologies react fatty acid or fatty acid dimer with alcohol amine, amine and epoxide, wherein some of the technologies have higher cost of reaction raw materials and general antiwear effect, and the addition amount of the technology in diesel oil is larger.

The existing low-sulfur diesel antiwear agents used in industry mainly comprise an acid type and an ester type, wherein the main components of the acid type antiwear agents are long-chain unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and the like, and typical products are derived from refined tall oil fatty acids. The ester type antiwear agent is the esterification reaction product of the above fatty acid and a polyol. WO9417160A1 discloses the use of oleic acid monoglycerides as a diesel lubricity additive.

The fatty acid type antiwear agent solves the problem of diesel oil lubricity, but the problems of exceeding diesel oil acidity, increasing corrosiveness risk and the like caused by the large consumption of the diesel oil with the upgrading of the diesel oil emission standard and the deterioration of the lubricity are solved. The fatty acid ester type antiwear agent is used in small amount, but has high cost and the additive diesel oil is emulsified and muddy when meeting water.

CN109576021a discloses an improver for improving the lubricity of low-sulfur diesel oil and a preparation method thereof, which is to mix unsaturated dicarboxylic acid ester (maleic diester) and polymerization inhibitor at 150-180 ℃, gradually add tung oil biodiesel, continuously react for a certain time at 200-240 ℃ after the addition, and obtain an improver product through reduced pressure distillation after the reaction. The product needs tung oil biodiesel, the raw materials are rare and unstable, the reaction needs high temperature and is difficult to prepare, and the most critical is that the antiwear effect is very common, and more than 600mg/kg needs to be added.

CN106929112a discloses a method for improving the abrasion resistance of low-sulfur diesel, which uses the esterification reaction product of alkenyl succinic anhydride and monohydric aliphatic alcohol to improve the lubricity of diesel, but the product has high viscosity and has a general effect of improving the lubricity of ultra-low-sulfur diesel (such as diesel for vehicles reaching the national vi emission standard).

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a diesel antiwear agent with a simple structure, a preparation method thereof and a diesel oil composition containing the antiwear agent. The diesel antiwear agent provided by the invention has excellent effect, and is little in use in diesel oil, so that the use cost of the diesel antiwear agent is greatly reduced.

The inventors of the present application have unexpectedly found that the absence of long chain hydrocarbyl substituted unsaturated dicarboxylic acid monoester type compounds in low sulfur diesel can greatly improve the lubricity of the diesel by adding a small amount of the compounds, and the effect is much better than that of the fatty acid type or fatty glyceride type antiwear agents commonly used in the industry at present.

In order to achieve the above object, in a first aspect, the present invention provides a diesel antiwear agent composition comprising at least an unsaturated dicarboxylic acid monoester compound represented by structural formula 1:

wherein n is an integer from 2 to 6, wherein R is a C1-C40 hydrocarbyl group.

Preferably, n is an integer from 2 to 4, preferably R is a C1-C18 hydrocarbyl group.

The unsaturated dicarboxylic acid monoester compound refers to a monoester compound in which any carboxyl group of a C4-C8 dicarboxylic acid compound containing a carbon-carbon unsaturated double bond in the molecule is esterified.

Specifically, when n is 2, the compound represented by structural formula 1 is maleic acid monoester (maleic acid monoester), fumaric acid monoester (fumaric acid monoester); when n is 3, the compound represented by structural formula 1 is itaconic acid monoester, citraconic acid monoester (methyl maleic acid monoester), methyl fumaric acid monoester (methyl fumaric acid monoester), glutaconic acid monoester, or the like; when n is 4, the compound represented by structural formula 1 is preferably 2, 3-dimethyl maleate monoester, ethyl maleate monoester, hexenedioate monoester, or the like.

The unsaturated dicarboxylic acid monoester compound is preferably maleic acid monoester (maleic acid monoester), fumaric acid monoester (fumaric acid monoester), itaconic acid monoester, citraconic acid monoester (methyl maleic anhydride), methyl fumaric acid monoester (methyl fumaric acid monoester), 2, 3-dimethyl maleic acid monoester, glutaconic acid monoester, or the like.

The unsaturated dicarboxylic acid monoester compound further preferably has a maleic acid monoester (maleic acid monoester) and an itaconic acid monoester represented by structural formula 2, structural formula 3 or structural formula 4.

Wherein R is a C1-C30 hydrocarbon group, preferably a C1-C18 hydrocarbon group.

Specifically, R may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The aliphatic hydrocarbon can be straight-chain or branched; can be saturated aliphatic hydrocarbon or unsaturated aliphatic hydrocarbon; the unsaturated aliphatic hydrocarbon may be an aliphatic hydrocarbon containing at least one carbon-carbon double bond (olefinic bond) or at least one carbon-carbon triple bond (acetylenic bond). The alicyclic hydrocarbon may be a saturated alicyclic hydrocarbon (cycloalkane) or an unsaturated alicyclic hydrocarbon. The aromatic hydrocarbon may be a monocyclic aromatic hydrocarbon or a bicyclic or polycyclic aromatic hydrocarbon. Alicyclic hydrocarbons and aromatic hydrocarbons may also have various substituted hydrocarbon groups on the ring. Further, R is preferably a C1-C18 chain aliphatic group, a C4-C18 cyclic aliphatic group, a C7-C18 aryl-substituted hydrocarbon group or an alkyl-substituted hydrocarbon group.

When R is a saturated chain aliphatic group, R may be an n-alkyl group or an isomeric alkyl group. When R is a normal alkyl group, structural formula 2 may be selected from monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-n-butyl maleate, shan Zhengwu maleate, mono-n-hexyl maleate, shan Zhenggeng maleate, shan Zhengxin maleate, shan Zhengren maleate, shan Zhenggui maleate, mono-n-undecyl maleate, mono-n-dodecyl maleate (lauryl), mono-n-tetradecyl maleate, mono-n-hexadecyl maleate, mono-n-octadecyl maleate, and the like, preferably monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-n-butyl maleate, shan Zhengxin maleate, shan Zhengren maleate, shan Zhenggui maleate, mono-n-dodecyl maleate, and the like. The compounds of structural formulas 3 and 4 may be selected from monomethyl itaconate, monoethyl itaconate, mono-n-propyl itaconate, mono-n-butyl itaconate, shan Zhengwu itaconate, mono-n-hexyl itaconate, shan Zhenggeng itaconate, shan Zhengxin itaconate, shan Zhengren itaconate, shan Zhenggui itaconate, mono-n-undecyl itaconate, mono-n-dodecyl itaconate (lauryl ester), mono-n-tetradecyl itaconate, mono-n-hexadecyl itaconate, mono-n-stearyl itaconate and the like, preferably monomethyl itaconate, monoethyl itaconate, mono-n-propyl itaconate, mono-n-butyl itaconate, shan Zhengxin itaconate, shan Zhenggui itaconate, mono-n-dodecyl itaconate (lauryl ester) and the like.

When R is an isopolyl group, the compound of formula 2 may be selected from monoisopropyl maleate, monoisobutyl maleate, mono-sec-butyl maleate, mono-tert-butyl maleate, monoisoamyl maleate, monoisohexyl maleate, monoisooctyl maleate (mono-2-ethylhexyl maleate), monoisononyl maleate, monoisodecyl maleate, monoisoundecyl maleate, monoisododecyl maleate, monoisotridecyl maleate, monoisotetradecyl maleate, monoisopentadecyl maleate, monoisoseventeen maleate, etc., preferably monoisopropyl maleate, monoisobutyl maleate, mono-sec-butyl maleate, monoisooctyl maleate, monoisononyl maleate, monoisoisodecyl maleate, monoisoundecyl maleate, monoisotridecyl maleate, etc. The compounds of structural formulas 3, 4 may be selected from monoisopropyl itaconate, monoisobutyl itaconate, mono sec-butyl itaconate, mono tert-butyl itaconate, monoisoamyl itaconate, monoisohexyl itaconate, monoisooctyl itaconate (mono-2-ethylhexyl itaconate), monoisononyl itaconate, monoisodecyl itaconate, monoisoundecyl itaconate, monoisotridecyl itaconate, and the like, with monoisopropyl itaconate, monoisobutyl itaconate, monoisooctyl itaconate (mono-2-ethylhexyl itaconate), monoisononyl itaconate, monoisodecyl itaconate, monoisoundecyl itaconate, and the like being preferred.

When R is an unsaturated chain aliphatic hydrocarbon group, the compound represented by the structural formula 2 may be selected from monoallyl maleate, mono 3-buten-1-ol maleate, monoisopentenyl maleate, mono 3-hexen-1-ol maleate, mono 1-hepten-3-ol maleate, monomethylheptenyl maleate, mono 2-octen-1-ol maleate, mono 3-nonen-1-ol maleate, mono 2-decen-1-ol maleate, mono 7-dodecen-1-ol maleate, mono 1, 5-hexadienol maleate, mono 2, 4-nonadien-1-ol maleate, mono 2, 4-decadien-1-ol maleate, mono 9, 11-dodecenyl maleate, mono oleyl maleate and the like, preferably monoallyl maleate, mono 3-decen-1-ol maleate, mono 3-dodecen-1-ol maleate, mono 3-decenyl maleate, mono 1-oleyl maleate and the like. The compounds of structural formulas 3, 4 may be selected from monoallyl itaconate, mono2-buten-1-ol itaconate, mono3-buten-1-ol itaconate, monoisopentenyl itaconate, mono3-hexen-1-ol itaconate, mono1-hepten-3-ol itaconate, monomethylheptenyl itaconate, mono2-octen-1-ol itaconate, mono3-nonen-1-ol itaconate, mono2-decen-1-ol itaconate, mono7-dodecen-1-ol itaconate, mono1, 5-hexadienol itaconate, mono2, 4-nonen-1-ol itaconate, mono2, 4-decdien-1-ol itaconate, mono9, 11-dodecenyl itaconate, monooleyl itaconate, and the like, preferably monoallyl itaconate, mono3-buten-1-ol itaconate, mono3-decen-1-ol itaconate, mono3-nonen-1-ol itaconate, mono1-ol itaconate and the like

When R is a cyclic aliphatic group, preferred compounds are monobutyl maleate, monocyclopentyl maleate, monocyclohexyl maleate, mono-3-cyclohexene-1-methyl maleate, mono-2-cyclohexene maleate, monocyclohexyl itaconate, mono-2-cyclohexene itaconate and the like.

R may also be substituted aryl, preferred compounds are mono-p-nonylphenyl maleate, mono-p-dodecylphenyl maleate, mono-p-nonylphenyl itaconate, mono-p-dodecylphenyl itaconate.

R may also be an aliphatic group having an aromatic ring, and preferred compounds are monobenzyl maleate, monophenyl ethanol maleate, monophenyl propanol maleate, monobenzyl itaconate, monophenyl ethanol itaconate, monophenyl propanol itaconate, and the like.

The diesel antiwear agent composition of the present invention may contain a proper amount of diesel oil and/or an organic solvent, and a small amount of unreacted raw materials, and also inevitably contains some reaction by-products, such as unsaturated dicarboxylic acid diester compounds.

In a second aspect, the invention provides a preparation method of the diesel antiwear agent, wherein the antiwear agent is prepared by reacting C4-C8 unsaturated diacid anhydride or unsaturated diacid with C1-C30 alcohol or phenol.

Specific reaction conditions include: the unsaturated diacid anhydride or unsaturated diacid with C4-C8 and the alcohol or phenol with C1-C30 are reacted according to the mol ratio of 1:0.5-1.5, the reaction temperature is 50-250 ℃, the reaction time is 0.1-10 hr, and the reaction pressure can be normal pressure or can be under a certain pressure.

The unsaturated diacid anhydride or unsaturated diacid is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, methyl fumaric acid, 2, 3-dimethyl maleic anhydride. Maleic anhydride, maleic acid, itaconic anhydride are preferred.

The alcohol or phenol may be an aliphatic alcohol, alicyclic alcohol, aromatic alcohol or phenol having a carbon number of C1 to C30, preferably C1 to C18. In the case of fatty alcohols, the carbon number is from C1 to C30, preferably from C1 to C18; in the case of alicyclic alcohols, the carbon number is from C3 to C30, preferably from C4 to C18; in the case of aromatic alcohols or phenols, the carbon number is from C6 to C30, preferably from C7 to C18.

The alcohol is preferably a monohydric alcohol. Primary or secondary or tertiary alcohols; the chain fatty alcohol comprises saturated fatty alcohol and unsaturated enol, and the saturated fatty alcohol can be normal fatty alcohol or isomeric fatty alcohol. The alicyclic alcohol may be a saturated alicyclic alcohol or an unsaturated alicyclic alcohol having a double bond in the ring, and the alcoholic hydroxyl group may be attached to the ring or to the alicyclic chain having a ring.

Among them, preferred saturated fatty alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, various isomeric pentanols, n-hexanols, various isomeric hexanols, n-heptanols, various isomeric heptanols, n-octanols, various isomeric octanols (e.g., 2-ethylhexanol), n-nonanols, various isomeric nonanols (e.g., 3, 5-trimethylhexanol, 7-methyl-1-octanol), n-decanol, various isomeric decanols (e.g., 2-propylheptanol, 8-methyl-1-nonanol), various isomeric undecanol, laurinol, n-tridecanols, various isomeric tridecanols, n-tetradecanol, n-hexadecanol, n-octadecyl alcohol, and the like.

Among them, the unsaturated fatty alcohol is preferably propenol 3-buten-1-ol, isopentenol, 3-hexen-1-ol, 1-hepten-3-ol, methylheptenol, 3-nonen-1-ol, 2, 4-decadien-1-ol, oleyl alcohol and the like.

Among them, alicyclic alcohols are preferably cyclobutylalcohol, cyclopentanol, cyclohexanol, 3-cyclopenten-1-ol, 2-cyclohexenol, 3-cyclohexene-1-methanol and the like.

Among them, benzyl alcohol (benzyl alcohol), phenethyl alcohol, phenylpropanol and the like are preferable.

Wherein the phenol is selected from propylphenol, butylphenol, pentylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, etc., preferably p-nonylphenol, p-dodecylphenol.

Most preferred alcohols or phenols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, cyclohexanol, 3-cyclohexene-1-methanol, benzyl alcohol, n-octanol, isooctanol (2-ethylhexanol), isononyl alcohol (3, 5-trimethylhexanol, 7-methyl-1-octanol), n-decanol, isodecyl alcohol (2-propylheptanol, 8-methyl-1-nonanol), lauryl alcohol, oleyl alcohol, nonylphenol, and isomeric alcohols of various structures produced by polymerization of ethylene, propylene or butene, such as isomeric nonanols, isomeric undecanol, isomeric tridecanols, and the like.

The catalyst may be added or not during the reaction, and the catalyst may be acid catalyst such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, phosphoric acid, boric acid,One or more of acidic ion exchange resins, etc.; ionic liquid catalysts such as 1-butylpyridine/AlCl 4 ionic liquids and the like can be used; inorganic salt solid phase catalysts, e.g. FeCl, can be used ₃ 、AlCl ₃ Etc.; molecular sieve catalysts, such as one or more of ZSM-5, HZSM-5, al-MCM-41, and the like, may be used; heteropolyacid catalysts such as one or more of PW12/MCM-41, siW12/MCM-41, etc. may be used; can be prepared with solid superacid catalysts, such as SO ₄ ^2- /ZrO ₂ -TiO ₂ Etc.; alkali catalysts such as NaOH, KOH, sodium methoxide, solid super bases, naH, etc. may be used.

The solvent can be added or not added during the reaction, and the solvent can be hydrocarbon such as alkane and aromatic hydrocarbon, for example petroleum ether, gasoline, toluene, xylene and the like.

Because the monoesterification reaction of the anhydride is simple and easy to implement and the monoesterification yield is high, the preferred method of the invention is to react the C4-C8 unsaturated anhydride with the C1-C18 alcohol or phenol under the condition of no catalyst and no solvent, and the preferred reaction condition is that the molar ratio of the maleic anhydride or the itaconic anhydride to the C1-C18 alcohol or phenol is 1:0.8-1.3, the reaction temperature is 50-120 ℃ and the reaction time is 0.5-8 hr.

The other method is to react the C4-C8 unsaturated dicarboxylic acid with the C1-C18 alcohol or phenol in the presence of a catalyst and with or without a solvent, and the preferable reaction condition is that the molar ratio of the maleic acid or the itaconic acid to the C1-C18 alcohol or phenol is 1:0.8-1.3, the reaction temperature is 70-250 ℃, and the reaction time is 3-15 hr.

In another method, C4-C8 unsaturated dianhydride or unsaturated diacid is reacted with sufficient or excessive C1-C18 alcohol or phenol to generate unsaturated acid diester compound, and then the unsaturated acid diester compound is reacted with C4-C8 unsaturated dianhydride or unsaturated diacid in the presence of catalyst and with or without solvent to obtain unsaturated acid monoester compound. The preferable reaction condition is that the mole ratio of the maleic diester to the maleic acid or the maleic anhydride is 1:0.8-1.3, the reaction temperature is 80-200 ℃ and the reaction time is 3-15 hr.

After the reaction is finished, the product after the catalyst is removed by filtration can be used as the diesel antiwear agent composition of the invention, and the product can be separated and purified according to the standard requirements of the antiwear agent product, for example, the solvent and unreacted raw materials are removed, the solvent and the unreacted raw materials meeting the standard requirements do not influence the performance of the antiwear agent of the invention, and the components are added into diesel, so that the performance of the diesel is not adversely affected.

According to the invention, a suitable amount of diesel fuel may be added to the reaction product to obtain a diesel antiwear agent concentrate.

In a third aspect, the present invention provides a method for improving the lubricity of diesel fuel, which comprises adding the C4-C8 unsaturated dicarboxylic acid monoester compound of the present invention to low sulfur diesel fuel in an amount of 10 to 400ppm, preferably 50 to 300ppm, based on 100% by mass of diesel fuel.

In a fourth aspect, the present invention provides a diesel fuel composition comprising a low sulfur diesel fuel and a C4-C8 unsaturated dicarboxylic acid monoester compound of the present invention, wherein the content of the C4-C8 unsaturated dicarboxylic acid monoester compound is 10 to 400ppm, preferably 50 to 300ppm, based on 100% by mass of the diesel fuel.

The diesel fuel of the present invention includes various low sulfur diesel fuels. For example, the fuel can be a compression ignition type internal combustion engine fuel which is prepared by processing crude oil (petroleum) by various refining processes of a refinery such as atmospheric and vacuum pressure, catalytic cracking, catalytic reforming, coking, hydrofining, hydrocracking and the like, and the distillation range is 160-380 ℃.

The diesel fuel may also be a second generation biodiesel derived from renewable resources such as vegetable oils and animal fats, and is typically hydrotreated in a refinery, producing isomerized or non-isomerized long chain hydrocarbons by hydrogenation, which may be similar in nature and quality to petroleum-based fuel oils.

The diesel oil can also be third-generation biodiesel which is obtained by treating non-greasy biomass with high cellulose content such as wood dust, crop straw, solid waste and the like and microbial grease by adopting gasification and Fischer-Tropsch technology.

The diesel fuel may also be a coal liquefied diesel (CTL), which refers to a diesel fuel obtained by fischer-tropsch synthesis of coal, or a diesel fuel obtained by direct liquefaction of coal. The diesel fuel may be mixed diesel fuel with mixed diesel fuel comprising oxygen-containing diesel fuel blending component, which is one kind of oxygen-containing compound or mixture of oxygen-containing compounds, alcohol and ether or mixture thereof, such as alcohol, polymethoxy dimethyl ether (Polyoxymethylene dimethyl ethers, PODEn, DMMn or OME) and other diesel fuel.

The diesel fuel composition of the present invention may further contain other additives such as one or more of a phenolic antioxidant, a polymeric amine type ashless dispersant, a flow improver, a cetane improver, a metal deactivator, an antistatic agent, a preservative, an antirust agent, and a demulsifier, according to the use requirements.

The macromolecular amine type ashless dispersant comprises one or more of alkenyl succinimide and/or alkenyl succinic acid amide, mannich base type ashless dispersant, polyether amine type ashless dispersant and polyolefin amine type ashless dispersant. The flow improver is preferably a homopolymer of (meth) acrylate, and/or a polymer of ethylene and vinyl acetate. The cetane improver can be nitrate or peroxide, such as isooctyl nitrate, di-tert-butyl peroxide, and the like. The metal deactivator may be one or more of ammonium salt formed by benzotriazole and fatty amine, product obtained by Mannich reaction of benzotriazole, formaldehyde and fatty amine, schiff base and organic polycarboxylic acid.

The diesel antiwear agent has the advantages of easily available raw materials, simple and convenient production, unexpectedly superior effect to the traditional fatty acid type or fatty acid ester type antiwear agent, remarkably improved lubricity of low-sulfur diesel, greatly reduced addition amount and further reduced use cost. The unsaturated dicarboxylic acid monoester compound does not cause the risk of emulsifying turbidity of diesel oil, and the anti-emulsifying effect is equivalent to that of a fatty acid type anti-wear agent and is superior to that of a fatty glyceride type diesel oil anti-wear agent.

Drawings

FIG. 1 is a photograph of the diesel oil b as measured on a diesel lubricity tester manufactured by PCS Corp. In the United kingdom, corrected to a plaque diameter (WS 1.4) of 651 microns.

FIG. 2 is a photograph of the mill marks measured after adding 200mg/kg of monoisooctyl maleate as described in example 1 to diesel fuel b, with a corrected mill mark diameter (WS 1.4) of 208. Mu.m.

Detailed Description

The present invention will be described in detail by examples. It will be understood that the invention is capable of various modifications in various embodiments, all without departing from the scope of the invention, and that the description and illustrations herein are intended to be by way of illustration only and not to be construed as limiting the invention.

The unsaturated dicarboxylic acid monoester compound of the present invention can be produced by the above-mentioned method, or can be obtained by purchasing an existing industrial product.

Examples 1 to 7 illustrate the preparation of maleic acid monoester compounds according to the present invention.

Example 1

490g maleic anhydride (maleic anhydride, mass fraction 99.5%, manufactured by Zibo Ji Xiangteng, chemical Co., ltd.) and 650g isooctanol (2-ethylhexanol, mass fraction 99.9%, manufactured by Qilu chemical Co., ltd.) were added to a 2000mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, the molar ratio of maleic anhydride to isooctanol was about 1:1, the mixture was heated and stirred to 90℃and the unreacted isooctanol and maleic anhydride were removed by distillation under reduced pressure after 4 hours of reaction, to give 1106g monoisooctyl maleate.

Example 2

215.6g of maleic anhydride (maleic anhydride, mass fraction: 99.5%, manufactured by Shanxi-friend chemical Co., ltd.) and 372g of lauryl alcohol (mass fraction: 99.9%, coco-coco Malaysia) were charged into a 1000mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, and the mixture was heated and stirred to 95℃and reacted for 3 hours, followed by heating and distillation under reduced pressure to remove unreacted maleic anhydride, thereby obtaining 581g of monolauryl maleate.

Example 3

Into a 2000mL reactor equipped with an electric stirrer and a thermometer, 490g of maleic anhydride (maleic anhydride, mass fraction 99.5%, manufactured by Tabo Ji Xiangteng, chemical Co., ltd.) and 720g of isomeric nonanols (Exxal) were charged ^TM 9s, mass fraction 99.5%, exxon-Mobil Co.) and the molar ratio of maleic anhydride to isomeric nonanol is about 1:1, heating and stirring to 85 ℃, reacting for 5 hours, heating and distilling under reduced pressure to remove unreacted isononyl alcohol and maleic anhydride, thereby obtaining 1006g of monoisononyl maleate.

Example 4

To a 3000mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, 686g of maleic anhydride (maleic anhydride, mass fraction 99.5%, manufactured by Shanxi-you chemical Co., ltd.) and 1452g of nonylphenol (mass fraction 99.5%) were added, and the mixture was heated and stirred to 95℃at a molar ratio of maleic anhydride to isooctanol of about 1.1:1, and reacted for 5.5 hours to obtain 2133g of mono-p-nonylphenyl maleate.

Example 5

490g maleic anhydride (maleic anhydride, mass fraction 99.5%, manufactured by Mitsubishi chemical corporation of Japan) and 540g benzyl alcohol (benzyl alcohol, mass fraction 99.5%, manufactured by Shandong Russian group Co., ltd.) were charged into a 2000mL reactor equipped with an electric stirrer and a thermometer, and the mixture was heated and stirred to 100℃and reacted for 4.5 hours, followed by heating and distillation under reduced pressure to remove unreacted benzyl alcohol and maleic anhydride, whereby 996g of monobenzyl maleate was obtained.

Example 6

147g of anhydride (maleic anhydride, mass fraction: 99.5%, aba Ding Shiji) and 180g of cyclohexanol (mass fraction: 98%, aba Ding Shiji) were charged into a 500mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, the molar ratio of maleic anhydride to cyclohexanol was about 1.1:1, and after the reaction was carried out at 80℃for 6 hours with stirring by heating, unreacted cyclohexanol was distilled off under reduced pressure to obtain 296g of monocyclohexyl maleate.

Example 7

147g of maleic anhydride (maleic anhydride, mass fraction: 99.5%, aba Ding Shiji) and 152g of 3-cyclohexene-1-methanol (mass fraction: 99.5%, manufactured by TCI reagent Co.) were charged into a 500mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, and the molar ratio of maleic anhydride to 3-cyclohexene-1-methanol was about 1:0.9, and the mixture was heated and stirred to 90℃to react for 3.5 hours to obtain mono-3-cyclohexene-1-methyl maleate.

Example 8 is commercially available monobutyl maleate (TCI reagent Co.) with a mass fraction of 97%.

Example 9 is commercially available monobutyl fumarate (TCI agent Co.) at 97% mass fraction.

Example 10 is commercially available monomethyl maleate (TCI reagent company), 95% by mass.

Example 11 was commercially available monoethyl maleate (company a. A Ding Shiji) with a mass fraction of 97%.

Examples 12 to 17 illustrate the preparation of itaconic acid monoester compounds according to the present invention.

Example 12

In a 2000mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, 560g of itaconic anhydride (mass fraction: 98% manufactured by optical biochemistry Co., ltd. In Zhejiang) and 650g of isooctanol (2-ethylhexanol, mass fraction: 99.9% manufactured by optical biochemistry Co., ltd. In China) were added, the molar ratio of itaconic anhydride to isooctanol was about 1:1, the mixture was heated and stirred to 95℃and reacted for 4 hours, and unreacted isooctanol and itaconic anhydride were removed by distillation under reduced pressure to obtain 1193g of monoisooctyl itaconate.

Example 13

In a 1000mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser tube, 260g of itaconic acid (mass fraction: 99.6%, manufactured by Zhejiang optical Biochemical Co., ltd.), 446g of lauryl alcohol (mass fraction: 99.9%, malaysia cocoanut) and 7g of p-toluenesulfonic acid were added, the molar ratio of itaconic acid to lauryl alcohol was about 1.1:2, the mixture was heated and stirred to 165℃and reacted for 6 hours, the unreacted raw materials were removed by distillation under reduced pressure, and 611g of monolauryl itaconate was obtained by distillation.

Example 14

Into a 2000mL reactor equipped with an electric stirrer and a thermometer, 571g of itaconic anhydride (98% by mass, manufactured by optical Biochemical Co., ltd.) and 792g of isomeric nonanols (Exxal) ^TM 9s, mass fraction of 99.5%, exxon-Mobil Co.) the molar ratio of itaconic anhydride to isomeric nonanol was about 1:1.1, heating and stirring to 90℃for 5 hours, and then heating and distilling under reduced pressure to remove unreacted isononyl alcohol and itaconic anhydride, thereby obtaining 1286g of monoisononyl itaconate.

Example 15

In a 500mL reactor equipped with an electric stirrer, a thermometer and a reflux condenser, 56g of itaconic anhydride (mass fraction: 97% manufactured by Aba Ding Shiji Co.) and 121g of nonylphenol (mass fraction: 99.5%) were charged, and the molar ratio of itaconic anhydride to nonylphenol was about 1.1:1, and the mixture was heated to 100℃with stirring, and reacted for 5.5 hours to obtain 171g of a mixture mainly composed of mono-p-nonylphenyl itaconate.

Example 16

490g of itaconic anhydride (mass fraction: 95% produced by TCI group, japan) and 540g of benzyl alcohol (benzyl alcohol, mass fraction: 99.5% produced by Shandong Ruxi group Co., ltd.) were charged in a 2000mL reactor equipped with an electric stirrer and a thermometer, and the molar ratio of itaconic anhydride to benzyl alcohol was about 1:1, and after heating and stirring to 100℃for 4.5 hours, the unreacted benzyl alcohol and itaconic anhydride were heated and distilled off under reduced pressure to obtain 996g of monobenzyl itaconate.

Example 17

147 anhydride (97% by mass, ara Ding Shiji) and 180g cyclohexanol (98% by mass, ara Ding Shiji) were added to a 500mL electric stirrer, thermometer and reflux cold energy tube reactor, the molar ratio of itaconic anhydride to cyclohexanol was about 1.1:1, and after heating and stirring to 80℃for 6 hours, unreacted cyclohexanol was distilled off under reduced pressure to give 296g of cyclohexyl itaconate.

Example 18 is commercially available monobutyl itaconate with a mass fraction of 99.5%.

Example 19 the same reaction was carried out using citraconic anhydride instead of maleic anhydride in example 1 to obtain monoisooctyl citraconate (monoisooctyl methylmaleate).

Comparative example 1

According to the technical scheme described in CN106929112A, dodecenyl succinic acid monomethyl ester is prepared as an antiwear agent.

Comparative example 2

The commercial diisooctyl maleate is used as an antiwear agent.

Comparative example 3

An antiwear agent commonly used in industry, namely an antiwear agent available from Afton corporation under the brand name HiTEC 4140, was used.

Comparative example 4

An ester type antiwear agent, which is commonly used in industry, is used, which is Infinium R655, available from Runner-Ind company.

Test example 1

The test examples are the use effects of the diesel antiwear agents in examples and comparative examples in diesel (antiwear agent is mixed with diesel a and diesel b, respectively, diesel a is from the middle petrochemical Yanshan division company, diesel b is from the middle petrochemical high-bridge division company, and physicochemical properties of diesel a and diesel b are shown in table 1).

Lubricity of diesel fuel the wear scar diameter (Wear Scar Diameter, WSD) at 60℃was measured according to SH/T0765 on a High frequency reciprocating tester (High-Frequency Reciprocating Rig, HFRR, british PCS instruments Co.) and the reported result WS1.4 was obtained by correcting for the effects of temperature and humidity.

The mill spot diameters WS1.4 of the diesel fuel before and after dosing are shown in tables 2 and 3. Among them, the smaller the wear scar diameter is, the better the diesel lubricity is. At present, most of the world diesel standards such as European standard EN 590, chinese vehicle diesel standard GB 19147 and vehicle diesel Beijing local standard DB 11/239 are qualified by taking the grinding mark diameter smaller than 460 mu m (60 ℃) as the basis of qualified diesel lubricity.

TABLE 1

TABLE 2

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TABLE 3 Table 3

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As can be seen from tables 2 and 3, the alcohol compound has no antiwear effect, and does not improve the lubricity of diesel oil in the diesel oil, for example, the lubricity of diesel oil is not substantially improved after isooctanol or lauryl alcohol is added, whereas the lubricity of diesel oil is surprisingly greatly improved after the unsaturated dicarboxylic acid monoester type compound of the present invention is added.

For the low sulfur diesel fuel shown in Table 2, the unsaturated dicarboxylic acid monoester compound of the present invention can greatly improve the lubricity of diesel fuel even at a very small addition amount, for example, examples 1 and 2 can reduce the lubricity plaque diameter of diesel fuel a from 564 μm to 211 μm and 205 μm at an addition amount of 150mg/kg, whereas the dodecenylsuccinic acid monoester shown in comparative example 1 is reduced to 389 μm, and the unsaturated dicarboxylic acid diester compound shown in comparative example 2 has no effect of improving the lubricity of diesel fuel; even the fatty acid type (comparative example 3) or fatty acid ester type (comparative example 4) diesel antiwear agent currently in common use in industry can only reduce the plaque diameter of diesel a to 427 and 394 microns at 150mg/kg, the unsaturated dicarboxylic acid monoester compound of the present invention has an unparalleled antiwear effect. When the dosage is further reduced to 80mg/kg, the unsaturated dicarboxylic monoester compound can also enable the lubricity of the diesel oil a to meet the standard requirement of the diesel oil, and the comparative example has poor antiwear effect when the dosage is added, and can not meet the requirement of not more than 460 microns of the standard requirement of the diesel oil.

For the ultra low sulfur diesel fuel shown in Table 3, the unsaturated dicarboxylic acid monoester compound of the present invention surprisingly improves the lubricity of the diesel fuel at very small addition levels, such as examples 1 and 2 being able to reduce the lubricity plaque diameter of diesel fuel b from 651 microns to 208 microns and 206 microns at addition levels of 200mg/kg, which is surprising.

The dodecenylsuccinic monoester shown in comparative example 1 was added in an amount of 200mg/kg to reduce the lubricating plaque diameter of diesel oil b from 651 micrometers to 389 micrometers, and the fatty acid type (comparative example 3) or fatty acid ester type (comparative example 4) diesel oil antiwear agent was also capable of reducing the plaque diameter of diesel oil b only to 432 micrometers and 387 micrometers at 200 mg/kg. When the dosage is further reduced to 120mg/kg, the unsaturated dicarboxylic acid monoester compound can also enable the lubricity of the diesel oil b to meet the standard requirement of the diesel oil, while when the dosage is 120mg/kg, the comparative examples 1, 3 and 4 enable the abrasive spot diameter of the diesel oil b to be reduced to 471 micrometers, 519 micrometers and 482 micrometers, the abrasion resistance effect is poor, and the specification of the diesel oil standard requirement of not more than 460 micrometers can not be met.

It can also be seen from test example 1 that the preferred maleic acid monoesters and itaconic acid monoesters have better effect of improving the diesel lubricity. Fumaric acid monoesters of the trans-structure and methyl maleic acid monoesters with branches are less effective.

Test example 2

The test examples are used for illustrating the anti-emulsifying property of the examples and the comparative examples, and the dosage is 300mg/kg.

Test method 1: 100g of diesel oil sample is put into a transparent glass bottle with scales, 1g of water is added, after magnetic stirring is carried out for 10 minutes at a rotating speed of 500rpm, the diesel oil sample is kept stand for 30 minutes at 30 ℃ in a dark place to observe the clear condition of the diesel oil, and the clear condition is compared with the diesel oil sample without additives.

Test method 2: according to the diesel antiwear agent demulsification test method of annex C in the specification of diesel antiwear agent technical requirement of China petrochemical group company, Q/SHCG 57-2017, test diesel oil and phosphate buffer solution are put into a clean glass measuring cylinder with a plug, shake is carried out for 2min according to the requirement, after standing for 15min, the volume of a water layer is observed, the light transmittance of an upper layer oil sample is measured by an ultraviolet spectrometer, and the ultraviolet spectrometer used in the test is the UV-2600 type manufactured by Shimadzu corporation. The test results are shown in Table 4.

TABLE 4 Table 4

As can be seen from Table 4, the test of method 1 shows that the diesel oil sample after adding the unsaturated dicarboxylic acid monoester compound of the invention is clear and transparent after adding moisture, and the sample is slightly turbid after adding the same dosage of the fatty acid ester type antiwear agent; the test of the method 2 shows that after the unsaturated dicarboxylic acid monoester compound is added, the water layer volume of the diesel oil sample is more than 18mL, which is equivalent to that of blank diesel oil, the light transmittance of the oil layer is not less than 90%, and the light transmittance of the sample added with the fatty acid ester antiwear agent of the comparative example 4 is only 75%. Test example 2 shows that the unsaturated dicarboxylic acid monoester compound provided by the invention does not cause the risk of emulsifying turbidity of diesel oil, and the anti-emulsifying effect is equivalent to that of a fatty acid type anti-wear agent and is superior to that of a fatty acid glyceride type diesel oil anti-wear agent.

Claims

1. The diesel oil composition at least comprises diesel oil and a diesel oil antiwear agent composition, wherein the diesel oil antiwear agent composition at least comprises unsaturated dicarboxylic acid monoester compounds, and the content of the unsaturated dicarboxylic acid monoester compounds is 10-400 ppm based on the mass of the diesel oil of 100%; the unsaturated dicarboxylic acid monoester compound is one or more selected from maleic acid monoester, fumaric acid monoester, itaconic acid monoester, citraconic acid monoester, methyl fumaric acid monoester, 2, 3-dimethyl maleic acid monoester and glutaconic acid monoester, wherein the ester group contains C1-C40 alkyl.

2. The composition according to claim 1, wherein the ester group of the unsaturated dicarboxylic acid monoester compound contains a C1 to C18 hydrocarbon group.

3. The composition according to claim 1 or 2, wherein the ester group of the unsaturated dicarboxylic acid monoester compound contains a C1-C18 chain aliphatic group, a C4-C18 cyclic aliphatic group, and a C7-C18 aryl-substituted hydrocarbon group or a hydrocarbon-substituted aryl group.

4. The composition of claim 1 wherein the unsaturated dicarboxylic acid monoester compound is selected from the group consisting of monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-n-butyl maleate, shan Zhengxin maleate, shan Zhengren maleate, shan Zhenggui maleate, mono-n-dodecyl maleate, monomethyl itaconate, monoethyl itaconate, mono-n-propyl itaconate, mono-n-butyl itaconate, shan Zhengxin itaconate, shan Zhenggui itaconate, mono-n-dodecyl itaconate, monoisopropyl maleate, monoisobutyl maleate, monosec-butyl maleate, monoisooctyl maleate, monoisononyl maleate, monoisodecyl maleate, monoisopropyl itaconate, monoisobutyl itaconate, monoisononyl itaconate, monoisodecyl itaconate, mono3-hexen-1-ol itaconate, monooleyl itaconate, monohexyl maleate, monononylbenzyl itaconate, monobenzyl itaconate.

5. The composition according to claim 1, wherein the unsaturated dicarboxylic acid monoester compound is contained in an amount of 50 to 300ppm.

6. A method for improving the lubricity of diesel oil comprises the steps of adding an unsaturated dicarboxylic acid monoester compound to diesel oil in an amount of 10-400 ppm based on the mass of the diesel oil as 100%; the unsaturated dicarboxylic acid monoester compound is one or more selected from maleic acid monoester, fumaric acid monoester, itaconic acid monoester, citraconic acid monoester, methyl fumaric acid monoester, 2, 3-dimethyl maleic acid monoester and glutaconic acid monoester, wherein the ester group contains C1-C40 alkyl.

7. The method according to claim 6, wherein the ester group of the unsaturated dicarboxylic acid monoester compound contains a C1-C18 hydrocarbon group.

8. The method according to claim 6, wherein the ester group of the unsaturated dicarboxylic acid monoester compound contains a C1-C18 chain aliphatic group, a C4-C18 cyclic aliphatic group, and a C7-C18 aryl-substituted hydrocarbon group or a hydrocarbon-substituted aryl group.

9. The method of claim 6, wherein the unsaturated dicarboxylic acid monoester compound is selected from the group consisting of monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-n-butyl maleate, shan Zhengxin maleate, shan Zhengren maleate, shan Zhenggui maleate, mono-n-dodecyl maleate, monomethyl itaconate, monoethyl itaconate, mono-n-propyl itaconate, mono-n-butyl itaconate, shan Zhengxin itaconate, shan Zhenggui itaconate, mono-n-dodecyl itaconate, monoisopropyl maleate, monoisobutyl maleate, monosec-butyl maleate, monoisooctyl maleate, monoisononyl maleate, monoisodecyl maleate, monoisopropyl itaconate, monoisobutyl itaconate, monomonoisooctyl itaconate, monoisononyl itaconate, monoisodecyl itaconate, mono3-hexen-1-ol itaconate, monohexen-1-ol itaconate, monohexyl itaconate, monononylmonononylmaleate, monobenzyl itaconate.

10. The method according to claim 6, wherein the unsaturated dicarboxylic acid monoester compound is added in an amount of 50 to 300ppm.