阅读说明：本技术 一种胆碱类三元低共熔溶剂催化氧化脱硫的方法 (Catalytic oxidation desulfurization method for choline ternary eutectic solvent ) 是由 蒋伟 罗亚平 贾浩 李宏平 朱文帅 李华明 于 2020-06-22 设计创作，主要内容包括：本发明涉及萃取脱硫,公开了一种胆碱类三元低共熔溶剂催化氧化脱硫的方法。包括如下步骤：(1)制备低共熔溶剂：将含乙醇基的季铵盐、硼酸和有机醇混合得到低共熔溶剂,通过调节原料的加入比例,可调节该低共熔溶剂的催化氧化脱硫性能；(2)脱硫步骤：在反应瓶中按顺序将入低共熔溶剂和含硫油品,在特定反应温度下搅拌均匀后,加入双氧水,反应一段时间后,取上层油品进行硫含量检测。本发明所述的低共熔溶剂制备方法简便,脱硫效率高,油品中硫含量可降至10 ppm一下,反应在常温常压下进行,反应结束后分离方便,油品回收率高。(The invention relates to extraction desulfurization and discloses a method for catalytic oxidation desulfurization by a choline ternary eutectic solvent. The method comprises the following steps: (1) preparing a eutectic solvent: mixing quaternary ammonium salt containing ethanol group, boric acid and organic alcohol to obtain a eutectic solvent, and adjusting the addition proportion of raw materials to adjust the catalytic oxidation desulfurization performance of the eutectic solvent; (2) and (3) desulfurization: adding a eutectic solvent and a sulfur-containing oil product into a reaction bottle in sequence, stirring uniformly at a specific reaction temperature, adding hydrogen peroxide, reacting for a period of time, and taking the upper oil product to perform sulfur content detection. The preparation method of the eutectic solvent is simple and convenient, the desulfurization efficiency is high, the sulfur content in oil products can be reduced to 10ppm, the reaction is carried out at normal temperature and normal pressure, the separation is convenient after the reaction is finished, and the recovery rate of the oil products is high.)

1. A method for catalytic oxidation desulfurization of choline ternary eutectic solvent is characterized by comprising the following steps:

(1) preparing a eutectic solvent: mixing quaternary ammonium salt containing ethanol group, boric acid and organic alcohol to obtain a eutectic solvent;

(2) and (3) desulfurization: adding a eutectic solvent and a sulfur-containing oil product into a reaction bottle in sequence, stirring uniformly at a specific reaction temperature, adding hydrogen peroxide, reacting for a period of time, and taking the upper oil product to perform sulfur content detection.

2. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the quaternary ammonium salt cation containing ethanol group is R₁R₂R₃N⁺CH₂CH₂OH, R thereof₁、R₂、R₃The alkyl substituent is saturated alkane, aromatic hydrocarbon and alkane substituted by alcoholic hydroxyl; the anion is chlorine.

3. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the organic alcohol is ethylene glycol or glycerol.

4. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the mass ratio of the quaternary ammonium salt, the boric acid and the organic alcohol is 1:1:5-1:4: 5.

5. The method for the extractive desulfurization of choline eutectic solvents according to claim 1, characterized in that: the mass ratio of the sulfur-containing oil product to the eutectic solvent is 20:1 to 1: 2.

6. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the mass concentration of the hydrogen peroxide is 10-50%, and the mass ratio of the hydrogen peroxide to the sulfur element is 1:1-20: 1.

7. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the temperature of the reaction is between 0 ℃ and 80 ℃.

8. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the reaction time is 10 min-8 h.

9. The method for catalytic oxidative desulfurization of choline ternary eutectic solvents according to claim 1, characterized in that: the sulfur-containing oil product is fuel oil or semi-finished oil in the crude oil refining process.

Technical Field

The invention relates to a method for catalytic oxidation desulfurization of choline ternary eutectic solvent.

Background

The rapid development of industrial processes, especially the increase in the amount of automobiles used, leads to the combustion of petroleumThe demand of the material increases dramatically. However, a large amount of SO is generated after combustionxCan bring adverse effects to the environment and the safety of human life and property, and in order to realize the aim of sustainable development, the emission of sulfide in fuel oil is strictly controlled in various countries. At present, the industrial desulfurization technology is hydrodesulfurization, but the hydrodesulfurization needs severe reaction conditions, so that non-hydrodesulfurization is greatly sought at present, particularly oxidative desulfurization, which has mild reaction conditions, convenient operation and high removal efficiency of polycyclic sulfides. The ionic liquid as a novel solvent replaces flammable and volatile organic solvents in many fields, and is widely applied in the desulfurization direction in recent years, but the synthetic steps are relatively complex and difficult to degrade. In order to overcome the defects, the eutectic solvent of the analogue of the ionic liquid is synthesized, and compared with the ionic liquid, the eutectic solvent is lower in cost and more environment-friendly.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a method for catalytic oxidation desulfurization of choline ternary eutectic solvent; the method has mild reaction conditions and simple and convenient operation, and can effectively remove the sulfide in the oil product. The choline ternary eutectic solvent synthesized by the invention has the advantages of simple preparation process, cheap reaction raw materials, higher desulfurization performance of the obtained eutectic solvent, simple and convenient separation after the reaction is finished, and reproducibility or recycling.

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

a method for catalytic oxidation desulfurization of choline ternary eutectic solvent comprises the following steps:

(1) preparing a eutectic solvent: mixing quaternary ammonium salt containing ethanol group, boric acid and organic alcohol to obtain a eutectic solvent, and adjusting the addition proportion of raw materials to adjust the catalytic oxidation desulfurization performance of the eutectic solvent;

(2) and (3) desulfurization: adding a eutectic solvent and a sulfur-containing oil product into a reaction bottle in sequence, stirring uniformly at a specific reaction temperature, adding hydrogen peroxide, reacting for a period of time, and taking the upper oil product to perform sulfur content detection.

Preferably, in the method for catalytic oxidative desulfurization by using the choline ternary eutectic solvent, the cation of the quaternary ammonium salt containing the ethanol group is R₁R₂R₃N⁺CH₂CH₂OH, R thereof₁、R₂、R₃The alkyl substituent is saturated alkane, aromatic hydrocarbon and alkane substituted by alcoholic hydroxyl; the anion is chlorine.

Preferably, in the method for catalytic oxidative desulfurization by using the choline ternary eutectic solvent, the organic alcohol is ethylene glycol or glycerol.

Preferably, in the method for catalytic oxidative desulfurization by using the choline ternary eutectic solvent, the ratio of the amount of the quaternary ammonium salt, the boric acid and the organic alcohol is 1:1:5-1:4: 5.

Preferably, in the method for catalytic oxidative desulfurization by the choline ternary eutectic solvent, the mass ratio of the sulfur-containing oil product to the eutectic solvent is 20:1 to 1: 2.

Preferably, in the method for catalytic oxidation desulfurization by the choline ternary eutectic solvent, the mass concentration of the hydrogen peroxide is 10-50%, and the mass ratio of the hydrogen peroxide to the sulfur element is 1:1-20: 1.

Preferably, in the method for catalytic oxidative desulfurization by the choline ternary eutectic solvent, the reaction temperature is 0-80 ℃.

Preferably, in the method for catalytic oxidative desulfurization by the choline ternary eutectic solvent, the reaction time is 10 min-8 h.

Preferably, in the method for catalytic oxidative desulfurization by using the choline ternary eutectic solvent, the sulfur-containing oil product is fuel oil or semi-finished oil in the crude oil refining process.

Compared with the prior art, the invention has the following beneficial effects:

1. the choline eutectic solvent is simple and convenient to synthesize, and the utilization efficiency of reactants is 100%.

2. The quaternary ammonium salt used for synthesizing the eutectic solvent is a choline-like compound, and the hydrogen bond donor is boric acid and organic alcohol, so the eutectic solvent is green and environment-friendly, biodegradable and nontoxic.

3. The choline eutectic solvent screened by the method has high extraction efficiency, and the desulfurization performance of the eutectic solvent is enhanced.

4. The preparation method of the eutectic solvent is simple and convenient, the desulfurization efficiency is high, the sulfur content in oil products can be reduced to be below 10ppm, the reaction is carried out at normal temperature and normal pressure, the separation is convenient after the reaction is finished, and the recovery rate of the oil products is high.

Detailed Description

The present invention is described by the following examples, but the present invention is not limited to the following examples, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the invention described above and below.

Preparation of oil products: dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) were dissolved in dodecane to prepare simulated fuel oils with different sulfur contents.

Eutectic solvent No. 1 (DES1) is prepared from 1-ethanol-1-n-butyl dimethyl ammonium chloride, boric acid and ethylene glycol in a molar ratio of 1:1: 5.

Eutectic solvent No. 2 (DES2) was prepared from 1-ethanol-1-n-octyldimethylammonium chloride, boric acid, and ethylene glycol in a molar ratio of 1:3: 5.

A eutectic solvent No. 3 (DES3) is prepared from 1-ethanol-1-hexadecyl dimethyl ammonium chloride, boric acid and glycerol in a molar ratio of 1:5: 5.