阅读说明：本技术 一种醇基清洁燃油用缓蚀润滑剂及其制备方法 (Corrosion inhibition lubricant for alcohol-based clean fuel oil and preparation method thereof ) 是由 汤颖 杨颖� 周瑞 马超 王进 于 2019-11-19 设计创作，主要内容包括：本发明公开了一种醇基清洁燃油用缓蚀润滑剂及其制备方法。将2-羟基苯并咪唑分散于甲醇或者乙醇中,搅拌下加入碱,再加入双卤代烷和碘化钾,加热反应；冷却至室温,加入碱,再加入长链卤代烷,加热反应,冷却至室温,过滤出不溶物,即得甲醇/乙醇汽柴油用缓蚀润滑剂。使用温度下,本发明制备的缓蚀润滑剂用量为10-500mg/L时,对铜片的缓蚀率在90％以上,摩擦系数降低30％以上。本发明方法简便,产品不需要进行纯化即可作为添加剂使用,产品具有良好的缓蚀作用。(The invention discloses a corrosion inhibition lubricant for alcohol-based clean fuel and a preparation method thereof. Dispersing 2-hydroxybenzimidazole in methanol or ethanol, adding alkali while stirring, adding double alkyl halides and potassium iodide, and heating for reaction; cooling to room temperature, adding alkali, adding long-chain alkyl halide, heating for reaction, cooling to room temperature, and filtering out insoluble substances to obtain the corrosion inhibition lubricant for methanol/ethanol gasoline and diesel oil. At the use temperature, when the dosage of the corrosion inhibition lubricant prepared by the invention is 10-500mg/L, the corrosion inhibition rate on the copper sheet is more than 90%, and the friction coefficient is reduced by more than 30%. The method is simple and convenient, the product can be used as an additive without purification, and the product has good corrosion inhibition effect.)

1. The preparation method of the corrosion inhibition lubricant for the alcohol-based clean fuel oil is characterized by comprising the following steps of:

firstly, dispersing 2-hydroxybenzimidazole in 5-20 times of methanol or ethanol by mass in a container;

secondly, adding alkali A into the container in a mass ratio of 1:1-1.1 to the 2-hydroxybenzimidazole substance under stirring;

thirdly, adding the dihalogenated alkane and the 2-hydroxybenzimidazole substance into the container in a mass ratio of 1:2-2.2, and adding the potassium iodide accounting for 1-5% of the 2-hydroxybenzimidazole substance;

fourthly, heating the solution in the container to 40-78 ℃ under stirring, and reacting for 1-6 hours;

fifthly, cooling to room temperature, and adding alkali B into the solution, wherein the amount ratio of the alkali B to the 2-hydroxybenzimidazole substance is 1: 1-1.1;

sixthly, adding long-chain alkyl halide with the amount ratio of 2-hydroxybenzimidazole substance being 1:1-1.5 into the container under stirring;

seventhly, heating the solution to 40-78 ℃ under stirring, and reacting for 1-6 hours;

and eighthly, cooling to room temperature, and filtering out insoluble substances to obtain the corrosion inhibition lubricant for the methanol/ethanol clean fuel oil.

2. The preparation method of the corrosion inhibition lubricant for the alcohol-based clean fuel oil according to claim 1, wherein in the first step, the 2-hydroxybenzimidazole, the methanol and the ethanol are products with purity of industrial grade and above.

3. The method for preparing the corrosion-inhibiting lubricant for the alcohol-based clean fuel oil as claimed in claim 1, wherein the alkali A in the second step is sodium hydroxide or potassium hydroxide with the purity of industrial grade or above.

4. The method for preparing the corrosion-inhibiting lubricant for the alcohol-based clean fuel oil as claimed in claim 1, wherein the bis-alkyl halide in the third step is selected from industrial grade and above 1, 2-dichloroethane, 1, 3-dichloroethane, 1, 4-dichloroethane, 1, 2-dibromoethane, 1, 3-dibromoethane, methyl ethyl ketone, ethyl methyl ketone, ethyl,

One or more than one mixture of 1, 4-dibromoethane, and the potassium iodide is a product with the purity of industrial grade and above.

5. The preparation method of the corrosion inhibition lubricant for the alcohol-based clean fuel oil as claimed in claim 1, wherein the alkali B in the fifth step is sodium hydroxide or potassium hydroxide with purity of industrial grade or above.

6. The method for preparing the corrosion inhibition lubricant for the alcohol-based clean fuel as claimed in claim 1, wherein the long-chain alkyl halide in the sixth step is one or more than one selected from chloro-n-octane, chloro-dodecane, chloro-hexadecane, chloro-octadecane, bromo-n-octane, bromo-dodecane, bromo-hexadecane and bromo-octadecane with industrial grade or higher purity.

7. The corrosion inhibition lubricant for alcohol-based clean fuel oil, which is obtained by the preparation method according to any one of claims 1 to 6.

8. The corrosion inhibiting lubricant for alcohol-based clean fuel according to claim 7, characterized in that the corrosion inhibiting lubricant comprises a compound of the following structural formula:

wherein R is an alkyl connecting arm with 2-4 carbons, and R' is a long-chain alkyl with 8-18 carbons.

Technical Field

The invention relates to the technical field of additives for clean fuel oil, in particular to a corrosion inhibition lubricant for alcohol-based clean fuel oil and a preparation method thereof.

Background

With the proposal of energy conservation, environmental protection and low carbon economy, the vehicle alternative fuel is widely concerned. At present, gasoline and diesel oil mixed with methanol/ethanol are also put on the market in addition to gasoline and diesel oil produced by traditional petroleum refining. Methanol and ethanol have properties similar to gasoline in many respects and are therefore considered to be the most promising new energy source for replacing gasoline in internal combustion engines, particularly spark ignition engines. At present, methanol gasoline or ethanol gasoline is popularized and used in a plurality of provinces and cities such as Shanxi, Henan and the like in China. However, there is a problem of corrosiveness in the use of methanol gasoline or ethanol gasoline. Formaldehyde, formic acid, a large amount of water vapor, unburned methanol and the like generated in the methanol combustion reaction process are corrosive to the metal surface, so that corrosion and abrasion can be caused to an engine fuel system, and the method becomes one of key problems restricting the development of methanol fuel. The existence of water in the ethanol gasoline activates the problems of acid corrosion and electrochemical corrosion of metals. When no water is contained in gasoline, the acidic corrosion is very weak, mainly the corrosion of metals caused by active sulfides. And the existence of water in the ethanol gasoline can cause the ionization of acid, so that the acid corrosion of the active metal is intensified, and other corrosion behaviors are activated. In addition, the corrosion inhibitor is used as an additive of the lubricating oil, and plays an important role in the storage and use processes of the finished lubricating oil. Particularly water-based lubricating materials, lubricating materials that contact non-ferrous metal parts, and lubricating materials that operate at high temperatures and chemical conditions. The existing methanol/ethanol gasoline and diesel oil corrosion inhibition lubricants are all monomolecular heterocyclic compounds, play a role in protection by adsorbing and forming a film on the surface of metal, and the coupled heterocyclic compounds are more beneficial to adsorbing and forming a film on the surface of metal, so that the corrosion inhibition efficiency can be greatly improved.

The 2-hydroxybenzimidazole has three hetero atoms, has strong adsorption capacity, can be strongly adsorbed on the metal surface to form a protective film to play a corrosion inhibition role, but has large polarity, higher solubility in methanol and ethanol and difficult dissolution in gasoline and diesel oil, so the 2-hydroxybenzimidazole is difficult to be directly used as a gasoline and diesel oil additive. Thus, long chain alkyl groups can be introduced into the molecule to enhance its oil solubility.

Disclosure of Invention

The invention aims to solve the problems of lubricity and corrosivity in methanol/ethanol gasoline and diesel oil, and provides a corrosion-inhibiting lubricant for alcohol-based clean fuel oil and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of a corrosion inhibition lubricant for alcohol-based clean fuel oil comprises the following steps:

firstly, dispersing 2-hydroxybenzimidazole in 5-20 times of methanol or ethanol in mass in a container, wherein the 2-hydroxybenzimidazole, the methanol and the ethanol are industrial-grade and above-purity products;

secondly, adding alkali A into the container in a mass ratio of 1:1-1.1 to the 2-hydroxybenzimidazole substance under stirring, wherein the alkali A is sodium hydroxide or potassium hydroxide with the purity of industrial grade or above;

thirdly, adding a bishaloalkane and potassium iodide, wherein the amount ratio of the bishaloalkane to the 2-hydroxybenzimidazole substance is 1:2-2.2, the bishaloalkane is one or a mixture of more than one of industrial-grade 1, 2-dichloroethane, 1, 3-dichloroethane, 1, 4-dichloroethane, 1, 2-dibromoethane, 1, 3-dibromoethane and 1, 4-dibromoethane, and the potassium iodide accounts for 1-5% of the amount of the 2-hydroxybenzimidazole substance, and the potassium iodide is a product with industrial-grade purity or more;

fourthly, heating the solution in the container to 40-78 ℃ under stirring, and reacting for 1-6 hours;

fifthly, cooling to room temperature, and adding alkali B into the solution, wherein the alkali B is sodium hydroxide or potassium hydroxide with the purity of industrial grade or above, and the amount ratio of the alkali B to the 2-hydroxybenzimidazole substance is 1: 1-1.1;

sixthly, adding long-chain alkyl halide with the mass ratio of 1:1-1.5 to the 2-hydroxybenzimidazole substance into the container under stirring, wherein the long-chain alkyl halide is one or a mixture of more than one of industrial-grade chloro-n-octane, chloro-dodecane, chloro-hexadecane, chloro-octadecane, bromo-n-octane, bromo-dodecane, bromo-hexadecane and bromo-octadecane;

seventhly, heating the solution to 40-78 ℃ under stirring, and reacting for 1-6 hours;

and eighthly, cooling to room temperature, and filtering out insoluble substances to obtain the corrosion inhibition lubricant for the methanol/ethanol clean fuel oil.

The invention adopts the technical scheme, and the technical idea is as follows: the 2-hydroxybenzimidazole has three hetero atoms, has strong adsorption capacity, can be strongly adsorbed on the metal surface to form a protective film to play a corrosion inhibition role, but has large polarity, higher solubility in methanol and ethanol and difficult dissolution in gasoline and diesel oil, so the 2-hydroxybenzimidazole is difficult to be directly used as a gasoline and diesel oil additive. The molecule has an active reaction group of an amino group and a hydroxyl group, can be linked through a double halogenated hydrocarbon to form a gemini type functional reagent, increases the solubility of the molecule in gasoline and diesel oil, and further introduces a long-chain alkyl group to the molecule to obtain a molecule with the following structure (wherein R is an alkyl connecting arm with 2-4 carbons, and R' is a long-chain alkyl with 8-18 carbons), enhances the oil solubility of the molecule, so that on the basis of adsorption film formation, a low-polarity protective film is formed, the contact between a corrosion medium and metal is inhibited, the corrosion resistance is improved, and an oil film is formed between the metals to play a role in lubrication and improve the lubricity.

The method is simple and convenient, the product can be used as an additive without purification, can be completely dissolved when being added into gasoline and diesel oil, and has better corrosion inhibition effect. According to the method specified by a lubricant extreme pressure performance test method (four-ball method) (GB/T12583-1998), the diameter of a wear scar is measured, and according to the corrosion inhibition performance of a petroleum product copper sheet corrosion test method (GB-T5096-1985), under the use temperature, when the dosage of the corrosion inhibition lubricant for the methanol/ethanol clean fuel prepared by the invention is 10-500mg/L, the corrosion inhibition rate on the copper sheet is more than 90%, and the friction coefficient is reduced by more than 30%.

Detailed Description

The invention is further illustrated by the following examples. It should be understood that the method described in the examples is only for illustrating the present invention and not for limiting the present invention, and that simple modifications of the preparation method of the present invention based on the concept of the present invention are within the scope of the claimed invention.