阅读说明：本技术 一种燃油选择性催化氧化脱硫的方法 (Method for selective catalytic oxidation desulfurization of fuel oil ) 是由 吕树祥 黄小侨 左妙果 于 2019-10-15 设计创作，主要内容包括：本发明涉及一种燃油选择性催化氧化脱硫的方法,将钛纳米材料催化剂、氧化剂与燃油接触,在第一组分竞争耗氧的情况下选择性催化氧化脱除第二组分；所述燃油包括第一组分和第二组分；所述第一组分包括烷烃、烯烃、芳烃、环烷烃或石蜡烃中一种或多种；所述第二组分为含硫化合物,包括硫醇、硫醚、噻吩、苯并噻吩、二苯并噻吩或4,6-二甲基二苯并噻吩等带有不同烷基侧链的稠环噻吩中一种或多种。本发明制备的钛纳米材料在烷烃、烯烃、环烷烃、芳烃和石蜡烃等复杂组分竞争氧化的情况下,选择性脱除柴油、渣油、蜡油与原油中噻吩类大分子含硫化合物,燃油脱硫效率达到87.5％,在高硫含量燃油的氧化脱硫和燃油的深度脱硫等领域具有很好的应用前景。(The invention relates to a method for selective catalytic oxidation desulfurization of fuel oil, which comprises the steps of contacting a titanium nano material catalyst and an oxidant with the fuel oil, and selectively carrying out catalytic oxidation to remove a second component under the condition that a first component competes for oxygen consumption; the fuel oil comprises a first component and a second component; the first component comprises one or more of alkane, alkene, aromatic hydrocarbon, cycloalkane or paraffin hydrocarbon; the second component is a sulfur-containing compound, and comprises one or more of thiol, thioether, thiophene, benzothiophene, dibenzothiophene or 4, 6-dimethyldibenzothiophene and other fused-ring thiophenes with different alkyl side chains. The titanium nano material prepared by the invention selectively removes thiophene macromolecular sulfur-containing compounds in diesel oil, residual oil, wax oil and crude oil under the condition that complex components such as alkane, olefin, cycloparaffin, aromatic hydrocarbon and paraffin hydrocarbon compete for oxidation, the desulfurization efficiency of fuel oil reaches 87.5 percent, and the titanium nano material has good application prospect in the fields of oxidative desulfurization of fuel oil with high sulfur content, deep desulfurization of fuel oil and the like.)

1. A method for selective catalytic oxidation desulfurization of fuel oil is characterized in that a titanium nano material catalyst and an oxidant are contacted with the fuel oil, and the fuel oil is selectively catalytically oxidized to remove a second component under the condition that a first component competes for oxygen consumption;

wherein the fuel comprises a first component and a second component;

the first component comprises one or more of alkane, alkene, aromatic hydrocarbon, cycloalkane or paraffin hydrocarbon; the second component is a sulfur-containing compound, and comprises one or more of thiol, thioether, thiophene, benzothiophene, dibenzothiophene or 4, 6-dimethyldibenzothiophene and other fused-ring thiophenes with different alkyl side chains.

2. The method for the selective catalytic oxidative desulfurization of fuel oil according to claim 1, characterized by comprising the following steps:

(1) adding a titanium nano material catalyst and fuel oil into a reaction kettle;

(2) adding an oxidant, heating to 40-60 ℃, and reacting for 0.5-4 h;

(3) standing, and separating and recovering the titanium nano material catalyst.

3. The method for the selective catalytic oxidative desulfurization of fuel oil according to claim 1, wherein the titanium nanomaterial catalyst is selected from titanium nanotubes, titanium nanosheets, or titanium nanoparticles.

4. The method for the selective catalytic oxidative desulfurization of fuel oil according to claim 1 or 2, wherein the oxidizing agent is selected from hydrogen peroxide, tert-butyl hydroperoxide or cumene hydroperoxide.

5. The process for the selective catalytic oxidative desulfurization of fuel oil according to claim 1 or 2, wherein the fuel oil is selected from diesel oil, residual oil, wax oil or crude oil.

6. The method for selective catalytic oxidative desulfurization of fuel oil according to claim 1, wherein the titanium nanomaterial is contacted with the oxidant to generate an intermediate active substance with a Ti-O-H- η 1 configuration on the surface of the titanium nanomaterial.

7. The method for the selective catalytic oxidative desulfurization of fuel oil according to claim 1 or 2, characterized in that the preparation method of the titanium nanomaterial catalyst comprises the following steps: and adding 300-800mL of 0.01-1.0mol/L HCl solution into 1-3g of the prepared sodium type titanium nano material, sealing, stirring at normal temperature for 8-16h, standing, performing suction filtration, washing with deionized water until the pH value is 7, and drying to obtain the titanium nano material catalysts with different shapes.

8. The method for the selective catalytic oxidation desulfurization of the fuel oil according to claim 7, characterized in that the preparation method of the sodium type titanium nano material comprises the following steps: adding TiO2 solid powder and a sodium hydroxide solution into a crystallization kettle with a polytetrafluoroethylene lining, sealing and heating to 130-160 ℃, carrying out hydrothermal crystallization for 12-48h, then naturally cooling to room temperature, washing the obtained white solid with deionized water until the pH value is 7, and drying to obtain the sodium type titanium nano material.

Technical Field

The invention belongs to the field of fuel oil desulfurization, and particularly relates to a method for selective catalytic oxidation desulfurization of fuel oil.

Background

With the development of economy, the quantity of motor vehicles in China is increased in geometric multiples, and SOx emitted by fuel combustion is one of the important reasons for air pollution at present.

The Oxidation Desulfurization (ODS) technology has natural removal advantages for fused ring thiophene sulfides and their derivatives which are difficult to remove by hydrodesulfurization. In the prior art, a research method for oxidative desulfurization of fuel oil generally takes fixed components (alkanes such as n-hexane and n-octane or decalin) as fuel oil simulants to catalytically remove quantitative single sulfides (mostly dibenzothiophene and DBT), and under the condition that H2O2 is an oxidant, the sulfide removal efficiency is generally high, the conditions are mild, and the operation is simple.

However, the real fuel oil is a mixed species with a much more complex structure, the sulfur content of the real fuel oil is much higher than that of a fuel oil simulant, the components of the real fuel oil also comprise substances such as alkane, alkene, aromatic hydrocarbon, cyclane and the like, and the fuel oil simulant system with a single fixed component has obvious disadvantages. Recently, many studies have conducted catalytic evaluation of catalytic oxidative desulfurization systems in systems closer to real fuels, and the results are not optimistic. Researches find that most catalysts have low selectivity, and the components of fuel oil such as olefin, aromatic hydrocarbon and the like are easier to oxidize, so that the removal efficiency of sulfur-containing compounds is reduced, and the oxidation process of the competitive components not only competitively consumes the oxidant, but also causes the reduction of the fuel oil quality. Therefore, in the catalytic oxidation desulfurization technology, the problem of competitive oxidation of complex components such as olefin, cyclane and aromatic hydrocarbon in the fuel oil is solved, and the selective removal of only the thiophene sulfur-containing compounds in the fuel oil is the key for realizing industrialization of the technology.

Disclosure of Invention

The invention aims to provide a method for selective catalytic oxidation desulfurization of fuel oil, which aims to solve the problems in the background technology.

The invention relates to a method for selective catalytic oxidation desulfurization of fuel, which comprises the steps of contacting a titanium nano-material catalyst and an oxidant with the fuel, and selectively catalytically oxidizing the fuel to remove a second component under the condition that a first component competes for oxygen consumption;

the fuel oil comprises a first component and a second component;

the first component comprises one or more of alkane, alkene, aromatic hydrocarbon, cycloalkane or paraffin hydrocarbon; the second component is a sulfur-containing compound, and comprises one or more of fused thiophene with different alkyl side chains, such as mercaptan, thioether, thiophene, Benzothiophene (BT), Dibenzothiophene (DBT) or 4, 6-dimethyldibenzothiophene (4, 6-DMDBT).

Preferably, the method for the selective catalytic oxidation desulfurization of the fuel oil specifically comprises the following steps:

(1) adding a titanium nano material catalyst and fuel oil into a reaction kettle;

(2) adding an oxidant, heating to 40-60 ℃, and reacting for 0.5-4 h;

(3) standing, and separating and recovering the titanium nano material catalyst.

Preferably, the titanium nanomaterial catalyst is selected from titanium nanotubes, titanium nanoplates or titanium nanoparticles.

Preferably, the oxidizing agent is selected from hydrogen peroxide, tert-butyl hydroperoxide or cumene hydroperoxide.

Preferably, the fuel oil is selected from diesel oil, residual oil, wax oil or crude oil.

Preferably, the titanium nano material is contacted with the oxidant to generate Ti-O-O-H-eta on the surface of the titanium nano material¹Configurational intermediate actives.

Preferably, the preparation method of the titanium nanomaterial catalyst comprises the following steps: and adding 300-800mL of 0.01-1.0mol/L HCl solution into 1-3g of the prepared sodium type titanium nanomaterial, sealing, stirring at normal temperature for 8-16h, standing, performing suction filtration, washing with deionized water until the pH value is 7, and drying to obtain the titanium nanomaterial catalysts with different morphologies.

Preferably, the preparation method of the sodium type titanium nano material comprises the following steps: adding TiO into a crystallization kettle provided with a polytetrafluoroethylene lining₂And (3) sealing the solid powder and a sodium hydroxide solution, heating to 130-160 ℃, carrying out hydrothermal crystallization for 12-48h, then naturally cooling to room temperature, washing the obtained white solid with deionized water until the pH value is 7, and drying to obtain the sodium type titanium nano material.

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

1. the titanium nano material catalyst of the invention is contacted with an oxidant, and Ti-O-O-H-eta with selective oxidation activity can be generated on the surface of the titanium nano material¹The intermediate active matter with the configuration can selectively catalyze and oxidize sulfur-containing compounds in the fuel without being influenced by alkane, olefin, cycloalkane and arene in the fuel simulant, so that the problems of low desulfurization efficiency and fuel quality reduction caused by competitive oxidation of the olefin, the cycloalkane or the arene in the fuel in the prior art are solved.

2. According to the invention, the acid pickling concentration of the sodium type titanium nanotube in the acid pickling process is controlled to obtain the titanium nanomaterial catalyst mixed by the titanium nanotube, the titanium nanosheet and the titanium nanoparticles, and the catalyst has good selective catalytic oxidation removal efficiency for benzothiophene, dibenzothiophene and the like, and also has good selective catalytic oxidation removal efficiency for macromolecular sulfide-containing 4, 6-dimethyldibenzothiophene.

3. The titanium nano material catalyst has good catalytic oxidation desulfurization activity on fuel oil with high sulfur content, and the sulfur content of diesel oil is reduced from 16000ppm to 2000ppm by reacting for 2 hours at the reaction temperature of 50 ℃, and the desulfurization rate reaches 87.5 percent, so the titanium nano material catalyst has good application prospect in the field of oxidation desulfurization of fuel oil with high sulfur content.

4. The invention adopts titanium nano material as catalyst, the titanium nano material catalyst is prepared by hydrothermal synthesis, the preparation method is simple, the cost is low, the yield is high, and after the reaction is finished, the titanium nano material catalyst can be separated and recovered only by a simple filtration method.

5. The invention has the advantages of simple process and high economical efficiency without adding an extractant in the whole reaction process.

Drawings

FIG. 1 is a gas chromatogram of the oil before and after the reaction in example 5.

FIG. 2 is a gas chromatogram of the oil before and after the reaction in example 6.

FIG. 3 is a gas chromatogram of the oil before and after the reaction of example 7.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.