阅读说明：本技术 二苯并噻吩类化合物催化氧化生成2-(2-羟基苯基)-苯亚磺酸及其盐的氧化脱硫方法 (Oxidative desulfurization method for generating 2- (2-hydroxyphenyl) -benzene sulfinic acid and salt thereof by catalytic oxidation of dibenzothiophene compound ) 是由 周新锐 景嘉伟 石文君 于 2019-07-26 设计创作，主要内容包括：本发明涉及一种用于仿生催化氧化脱硫的方法,尤其涉及一种二苯并噻吩化合物的氧化脱硫的方法。本发明的方法以二苯并噻吩类化合物在过氧化物氧化剂、烃类溶液、磷酸盐水溶液以及金属酞菁或金属卟啉存在下,经过光催化氧化反应生成2-(2-羟基苯基)-苯亚磺酸及其盐,该类化合物极易溶于水中,与原油相体系脱离,从而实现了脱硫。本发明方法生成的亚磺酸类物质直接溶于水溶液中与原油相体系脱离,无需后处理步骤,直接达到油相脱硫的目的,脱硫率最高可接近100％。本发明方法有效解决了现有氧化脱硫后处理困难,如砜和亚砜类仍然溶于油相,不能通过萃取达到分离,吸附分离设备要求高,油相烃类损失大等问题。(the invention relates to a method for biomimetic catalytic oxidative desulfurization, in particular to a method for oxidative desulfurization of a dibenzothiophene compound. The method of the invention uses dibenzothiophene compounds to generate 2- (2-hydroxyphenyl) -benzene sulfinic acid and salts thereof through photocatalytic oxidation reaction in the presence of peroxide oxidant, hydrocarbon solution, phosphate aqueous solution and metal phthalocyanine or metalloporphyrin, and the compounds are very easy to dissolve in water and separate from a crude oil phase system, thereby realizing desulfurization. The sulfinic acid substances generated by the method are directly dissolved in the aqueous solution and separated from a crude oil phase system, the post-treatment step is not needed, the aim of oil phase desulfurization is directly fulfilled, and the desulfurization rate can be close to 100% at most. The method effectively solves the problems that the existing oxidation desulfurization post-treatment is difficult, such as sulfone and sulfoxide are still dissolved in the oil phase, separation cannot be achieved through extraction, the requirement on adsorption separation equipment is high, the loss of oil phase hydrocarbons is large, and the like.)

1. a method for desulfurizing dibenzothiophene compounds is characterized in that the method comprises the steps of carrying out catalytic oxidation reaction on the dibenzothiophene compounds in an oil-water two-phase to generate 2- (2-hydroxyphenyl) -benzene sulfinic acid and salts thereof;

The dibenzothiophene compound is dissolved in hydrocarbon solution for reaction, and the hydrocarbon solution is C_6-20a hydrocarbon organic;

the reaction solution of the catalytic oxidation reaction is a phosphate buffer aqueous solution;

The catalyst for the catalytic oxidation reaction is metal phthalocyanine or metal porphyrin;

the oxidant for catalyzing the oxidation reaction is peroxide, and the peroxide is a compound of a general formula (III):

the conditions of the catalytic oxidation reaction are as follows: illumination with the wavelength of 200-600 nm and the reaction temperature of 10-40 ℃;

the molar ratio of the peroxide to the dibenzothiophene compound is 1: 1-18: 1;

The dosage of the metal phthalocyanine or the metal porphyrin is 1 to 10 percent of the weight of the reactant.

2. The process for desulfurizing dibenzothiophene according to claim 1, wherein said reaction temperature is 30 ℃.

3. The method for desulfurizing dibenzothiophene compounds according to claim 1, wherein the wavelength is 200-400 nm.

4. The method for desulfurizing dibenzothiophene compounds according to claim 1, wherein the molar ratio of the peroxide to the dibenzothiophene compounds is 4:1 to 9: 1.

5. The desulfurization method of dibenzothiophene compounds according to claim 1, wherein the amount of said metal phthalocyanine or metalloporphyrin is 2% -8% of the weight of the reactants.

6. The method for desulfurizing dibenzothiophene according to claim 1, wherein said hydrocarbon solution is decalin.

7. The method for desulfurizing a dibenzothiophene compound according to claim 1, wherein the concentration of said aqueous phosphate buffer solution is 1 to 3 mol/L.

8. The method for desulfurizing a dibenzothiophene compound according to claim 1, wherein said dibenzothiophene compound is represented by the general formula (VI);

Wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂Each independently selected from H, or C_rH_2r+1Wherein r is an integer of 1 to 5.

9. the desulfurization method of dibenzothiophene compound according to claim 1, wherein said metallophthalocyanine is a compound of formula (I), said metalloporphyrin is a compound of formula (ii);

Wherein M is independently selected from Fe, Mn, Ru, Co, Ni and V;

R₁、R₂And R₃each independently selected from Cl, F, NO₂、SO₃H、H、C_nH_2n+1Wherein: n is an integer of 1 to 5;

Y₁、Y₂、Y₃、Y₄each independently selected from C_mH_mWherein m is 0 or 2.

Technical Field

The invention relates to a method for biomimetic catalytic oxidative desulfurization, in particular to an oxidative desulfurization method for generating 2- (2-hydroxy) -benzene sulfinic acid and salts thereof by catalytic oxidation of a dibenzothiophene compound.

Background

Sulfur-containing compounds have a great influence on the quality and properties of petroleum productsThe long-term use of gasoline and diesel oil products with high sulfur content can cause great mechanical damage to the machine. The exhaust of fuel automobile exhaust, such as SOx, can cause serious atmospheric pollution, which is also a direct cause of acid rain. The sulfur oxides can destroy the active center of the three-way catalyst, thereby causing permanent poisoning of the catalyst and seriously reducing the processing capacity of the automobile exhaust. Sulfur oxides are also a significant cause of corrosion in automotive engines^[1]。

Hydrodesulfurization of hydrocarbons^[2]The sulfur-containing compound in the petroleum reacts with hydrogen under the catalysis of the catalyst to be converted into hydrogen sulfide and hydrocarbon substances, so that the desulfurization effect is achieved. Hydrodesulfurization has better removal effect on sulfur-containing compounds such as mercaptan, thioether and the like in petroleum components, and is a method for producing low-sulfur petroleum products. However, the catalytic hydrogenation process itself has some disadvantages, for example, dibenzothiophene compounds are difficult to remove by hydrogenation due to large steric hindrance effect; in addition, the process has high requirements on equipment, a large amount of hydrogen needs to be consumed, and the production cost is increased.

In recent years, researchers have developed a number of non-hydrodesulfurization processes, such as adsorption desulfurization^[3]and extractive desulfurization^[4]Oxidative desulfurization^[5]Biological desulfurization^[6]Complex desulfurization^[7]And the different desulfurization processes have some obvious advantages, such as lower cost and equipment investment, simpler construction requirements, convenience for popularization and use and the like. Oxidative Desulfurization (ODS)^[8-11]the method is a popular research in the future, the desulfurization mode is carried out at normal temperature and normal pressure, the reaction condition is mild, the cost is greatly reduced, and oxidative desulfurization has good removing effect on thiophene substances and derivatives thereof which are difficult to remove by hydrogenation in oil products, so the method becomes a process choice with great application prospect in the future. Oxidative desulfurization suffers from the disadvantage that dibenzothiophene oxidation products (sulfoxides and sulfones) are not sufficiently polar, resulting in inefficient subsequent adsorption and extractive removal.

Bionic catalytic desulfurization technology^[12]The basis of (a) is to simulate the structural characteristics of the biological enzymeThe catalyst is prepared, and the condition that the catalytic reaction condition of the enzyme is similar is adopted, so that the desulfurization effect superior to that of the traditional reaction process is achieved. Compounds such as metalloporphyrins can be used to mimic cytochrome P-450^[13]And chlorophyll enzyme catalyst to remove dibenzothiophene sulfide under mild condition. CN201410548393X reports a photolysis method of dibenzothiophene, the product is dibenzothiophene sulfinic acid lactone oil-soluble substances, the polarity of the product obtained by the method is increased compared with that of the prior dibenzothiophene oxidation product, the oil phase desulfurization efficiency is improved, but the product cannot be separated by liquid separation, only an adsorption separation mode is used, and the subsequent treatment still has problems.

Disclosure of Invention

In order to solve the problems in the prior art, the invention aims to provide a one-step deep oxidation desulfurization method for oxidizing dibenzothiophene compounds into 2- (2-hydroxyphenyl) -benzene sulfinic acid and salts thereof by oxidation-extraction separation in oil-water two phases through metal phthalocyanine or metalloporphyrin.

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

The reaction principle of the invention is as follows:

A method for desulfurizing dibenzothiophene compounds comprises the steps of carrying out catalytic oxidation reaction on the dibenzothiophene compounds to generate 2- (2-hydroxyphenyl) -benzene sulfinic acid and salts thereof;

The dibenzothiophene compound is dissolved in hydrocarbon solution for reaction, and the hydrocarbon solution is C_6-20A hydrocarbon organic;

The reaction solution of the catalytic oxidation reaction is a phosphate buffer aqueous solution;

The catalyst for the catalytic oxidation reaction is metal phthalocyanine or metal porphyrin;

The oxidant for catalyzing the oxidation reaction is peroxide, and the peroxide is a compound of a general formula (III):

The conditions of the catalytic oxidation reaction are as follows: illumination with the wavelength of 200-600 nm and the reaction temperature of 10-40 ℃;

The molar ratio of the peroxide to the dibenzothiophene compound is 1: 1-18: 1;

The dosage of the metal phthalocyanine or the metal porphyrin is 1 to 10 percent of the weight of the reactant.

In the method for desulfurizing the dibenzothiophene compound, the reaction temperature is preferably 30 ℃.

The method for desulfurizing dibenzothiophene compounds preferably has a wavelength of 200 to 400 nm.

In the method for desulfurizing a dibenzothiophene compound, the molar ratio of the peroxide to the dibenzothiophene compound is preferably 4:1 to 9: 1.

in the method for desulfurizing dibenzothiophene compounds, the metal phthalocyanine or metal porphyrin is preferably used in an amount of 2-8% by weight of the reactants.

In the method for desulfurizing a dibenzothiophene compound, the hydrocarbon solution is preferably decalin.

in the method for desulfurizing a dibenzothiophene compound, the concentration of the phosphate buffer aqueous solution is preferably 1 to 3 mol/L.

in the technical scheme, the dibenzothiophene compound is represented by a general formula (VI);

Wherein R is₇、R₈、R₉、R₁₀、R₁₁And R₁₂each independently selected from H, or C_rH_2r+1Wherein r is an integer of 1 to 5.

in the technical scheme, the metal phthalocyanine is a compound of a general formula (I), and the metal porphyrin is a compound of a general formula (II);

Wherein M is independently selected from Fe, Mn, Ru, Co, Ni and V;

R₁、R₂and R₃Each independently selected from Cl, F, NO₂、SO₃H、H、C_nH_2n+1Wherein: n is an integer of 1 to 5;

Y₁、Y₂、Y₃、Y₄Each independently selected from C_mH_mWherein m is 0 or 2.

the metal phthalocyanine of formula (I) or the metal porphyrin of formula (II) can be purchased or prepared by conventional preparation methods in the field.

in the technical scheme, the reaction is carried out under the monitoring of liquid chromatography, the yield of the product sulfinic acid is obtained by comparing the areas of a raw material peak and a product peak, the light-irradiation catalysis time can be adjusted according to the yield of the sulfinic acid generated by the reaction, the reaction is continued when the yield is in an ascending trend in the reaction process, and the reaction can be ended when the yield is in a stable trend; under the reaction conditions, the reaction can reach good desulfurization rate within 3-20 hours.

The invention has the beneficial effects that: according to the method, under the similar biological desulfurization conditions of mild temperature, normal pressure, illumination and oil-water two-phase, the dibenzothiophene substances are oxidized by a biomimetic catalyst through one-step reaction to obtain the 2- (2-hydroxyphenyl) -benzene sulfinic acid and the salts thereof, the substances are directly dissolved in an aqueous solution to be separated from a crude oil phase system, a post-treatment step is not needed, the aim of oil-phase desulfurization is directly fulfilled, and the highest desulfurization rate can approach 100%. The method effectively solves the problems that the existing oxidation desulfurization post-treatment is difficult, such as sulfone and sulfoxide are still dissolved in the oil phase, separation cannot be achieved through extraction, the requirement on adsorption separation equipment is high, the loss of oil phase hydrocarbons is large, and the like.

Drawings

FIG. 1 nuclear magnetic spectrum of the products of examples 2 to 6 of the present invention.

Detailed Description

The invention is further illustrated but is not in any way limited by the following specific examples. In the following examples, unless otherwise specified, the experimental methods used were all conventional methods, and materials, reagents and the like used were all available from biological or chemical companies.

The method comprises the following steps: mixing hydrocarbon solution containing dibenzothiophene compounds with phosphate aqueous solution, catalyzing by metal phthalocyanine or metalloporphyrin, and obtaining water-soluble 2- (2-hydroxyphenyl) -benzene sulfinic acid and salt thereof under the irradiation of light with specific wavelength at a certain temperature in the presence of peroxide oxidant.