阅读说明：本技术 一种燃料油脱硫剂及其制备方法 (Fuel oil desulfurizing agent and preparation method thereof ) 是由 陈波 于 2019-09-11 设计创作，主要内容包括：本发明公开了一种燃料油脱硫剂及其制备方法。所述的燃料油脱硫剂为多孔铝基金属氧化物负载富勒烯羧酸铜盐,所述的富勒烯羧酸铜盐在多孔铝基金属氧化物中的负载量为10～30wt％。所述的多孔铝基金属氧化物为SiO<Sub>2</Sub>-Al<Sub>2</Sub>O<Sub>3</Sub>-CeO<Sub>2</Sub>以摩尔比为(0.5～1):(2～3):(1～2)组成的复合物。本发明提供的燃料油脱硫剂具有高的催化活性,对硫的选择性好、脱硫深度高,将其应用于燃料油氧化脱硫工艺,脱硫率最高可达到98.7％,并且性质稳定,可回收循环使用,使用寿命长。(The invention discloses a fuel oil desulfurizer and a preparation method thereof. The fuel oil desulfurizer is a porous aluminum-based metal oxide loaded fullerene copper carboxylate, and the loading amount of the fullerene copper carboxylate in the porous aluminum-based metal oxide is 10-30 wt%. The porous aluminum-based metal oxide is SiO 2 ‑Al 2 O 3 ‑CeO 2 The compound is composed of (0.5-1) to (2-3) to (1-2) in a molar ratio. The fuel oil desulfurizer provided by the invention has high catalytic activity, good selectivity to sulfur and high desulfurization depth, can be applied to a fuel oil oxidation desulfurization process, has the highest desulfurization rate of 98.7 percent, has stable property, can be recycled, and has long service life.)

1. The fuel oil desulfurizer is characterized in that the fuel oil desulfurizer is a porous aluminum-based metal oxide loaded fullerene copper carboxylate, and the loading amount of the fullerene copper carboxylate in the porous aluminum-based metal oxide is 10-30 wt%.

2. The desulfurizing agent for fuel oil according to claim 1, wherein said porous aluminum-based metal oxide is SiO₂-Al₂O₃-CeO₂The compound is composed of (0.5-1) to (2-3) to (1-2) in a molar ratio.

3. The fuel oil desulfurizing agent according to claim 1 or 2, wherein the porous aluminum-based metal oxide has a specific surface area of 750 to 1000m²The pore volume is 1.26-1.94 cm³(ii)/g, the pore diameter is 7.5 to 20.2 nm.

4. The fuel oil desulfurizing agent according to claim 3, wherein said porous aluminum-based metal oxide is prepared by the following method:

(1) dissolving a triblock copolymer Pluronic F127 into a mixed solvent composed of absolute ethyl alcohol and glacial acetic acid according to a volume ratio of 5 (1.5-2.5), wherein the mixing ratio of the Pluronic F127 to the mixed solvent is 1g: 20-30 mL, and uniformly stirring to obtain a mixed solution A;

(2) adding a precursor mixture into the mixed solution A obtained in the step (1), stirring and dissolving to obtain a mixed solution B, wherein the mass ratio of the precursor mixture to the mixed solution A is 1: 3.5-4, the precursor mixture is formed by mixing methyl orthosilicate, aluminum nitrate nonahydrate and cerium nitrate hexahydrate, and the mixing ratio is SiO₂:Al₂O₃:CeO₂The molar ratio of (1) to (2) to (1) is calculated as (0.5-1);

(3) and (3) soaking a three-dimensional ordered macroporous-structure polystyrene template into the mixed solution B obtained in the step (2), soaking for 12-24 hours, placing the soaked polystyrene template in a drying oven at 55-65 ℃ for sol gelation for 48-72 hours to form a gel-like solid, drying the gel-like solid at 60-100 ℃, then placing the gel-like solid in a muffle furnace for calcination at 550-650 ℃ for 3-5 hours, and controlling the heating rate at 0.5-3 ℃/min during calcination to obtain the porous aluminum-based metal oxide microspheres.

5. The fuel oil desulfurizing agent according to claim 4, wherein the polystyrene template has a pore size of 470 nm.

6. The fuel oil desulfurizing agent according to claim 1, wherein the copper salt of fullerene carboxylic acid is prepared by the following method:

dissolving the fullerene carboxylic acid derivative in 75-90% by volume of ethanol water solution, slowly adding copper nitrate while stirring, continuously stirring and reacting for 1-2 h, then heating to 80-85 ℃, removing ethanol and part of water, cooling to room temperature, crystallizing, aging, filtering, and drying at 110-120 ℃ for 2-3 h to obtain the fullerene copper carboxylate.

7. The fuel oil desulfurizing agent according to claim 6, wherein the fullerene carboxylic acid derivative is a C60 carboxylic acid derivative, and the reaction molar ratio of the fullerene carboxylic acid derivative to copper nitrate is 1:3.

8. A method for preparing the desulfurizing agent for fuel oil according to any one of claims 1 to 7, comprising the steps of:

adding fullerene copper carboxylate into deionized water, performing ultrasonic dispersion to prepare a fullerene copper carboxylate solution with the mass fraction of 5-10%, adding a porous aluminum-based metal oxide into the fullerene copper carboxylate solution, loading the fullerene copper carboxylate into the porous aluminum-based metal oxide by adopting a vacuum impregnation method, so that the loading amount of the fullerene copper carboxylate in the porous aluminum-based metal oxide is 10-30 wt%, and drying at 80-100 ℃ to obtain the fuel oil desulfurizer.

9. The use of the fuel oil desulfurization agent of any one of claims 1 to 7 for oxidative desulfurization of a fuel.

Technical Field

The invention belongs to the technical field of fuel oil processing, and particularly relates to a fuel oil desulfurizer and a preparation method thereof.

Background

Sulfur in fuel oil exists mainly in the form of organic sulfides, such as mercaptans, sulfides, thiophenes and their alkyl derivatives, benzothiophenes, dibenzothiophenes and their alkyl homologs, and the like. The ease of desulfurization of fuel oils is largely determined by the type of sulfide in the oil. Thiols and thioethers are relatively easy to remove, but are more difficult to remove for valencies having aromatic ring properties, such as thiophene and its derivatives, benzothiophene, dibenzothiophene and its alkyl homologues, especially dibenzothiophene thiophenes having two alkyl substituents at the 4,6 positions.

The current fuel oil desulfurization technologies are mainly divided into two categories: hydrodesulfurization is currently used industrially mostly in hydrodesulfurization technology and non-hydrodesulfurization technology, but the technology can effectively remove sulfides such as mercaptan and thioether, but the reaction pressure is high and H is high₂Large consumption, large equipment investment, high requirement, high operation cost, difficult removal of condensed ring thiophene sulfides, reduction of gasoline octane number and the like. The catalytic oxidation desulfurization technology is one of non-hydrodesulfurization technologies, can be used for reaction at normal pressure and low temperature, has mild reaction conditions, can effectively remove thiophene sulfides, achieves the aim of deep desulfurization and the like, and has the advantages of recent yearsBecomes a hot spot of competitive research of researchers, is hopeful to replace the traditional hydrodesulfurization process, and has good application prospect.

The oxidation desulfurization technology is to oxidize thiophene sulfides in the fuel into sulfoxide and sulfone by using an oxidant, and the sulfoxide and the sulfone have stronger polarity and can be separated from the nonpolar fuel by using methods such as extraction, adsorption, distillation and the like, so that the deep desulfurization of the fuel is realized, and the aim of producing the ultralow-sulfur fuel is fulfilled. The key point of the oxidation desulfurization technology is to find a catalytic oxidation system with high activity and selectivity on sulfide in fuel oil. At present, hydrogen peroxide is used as an oxidant in a catalytic oxidation system which is researched more, heteropoly acid, organic acid, inorganic acid or ionic liquid is used as a catalyst, and the catalyst exists in a homogeneous liquid form in an oxidation desulfurization system, so that the defects that the separation of the catalyst and fuel oil is difficult to realize and the catalyst cannot be recycled exist after the reaction is finished, and the popularization of the oxidation desulfurization technology is limited.

Chinese patent application publication No. CN 104694153 a discloses a fuel oil photooxidation treatment method using cage-shaped fullerene as photosensitizer, which comprises dissolving cage-shaped fullerene (such as C60 and C70) as photosensitizer in fuel oil, introducing air or oxygen into the fuel oil under the condition of illumination, and obtaining the fuel oil after the illumination is finished, i.e. the fuel oil after photooxidation treatment. The desulfurization rate of the patent is not high, only about 80%, and the cage-shaped fullerene is directly dissolved in fuel oil, so that the separation and recovery are difficult after the use.

Disclosure of Invention

The invention aims to provide a fuel oil desulfurizer and a preparation method thereof. The desulfurizer has high catalytic activity, can be applied to the oxidation desulfurization process of fuel oil, has the highest desulfurization rate of 98.7 percent, has stable property, and can be recycled.

The technical scheme adopted by the invention is as follows:

the fuel oil desulfurizer is a copper fullerene carboxylate loaded on a porous aluminum-based metal oxide, and the loading amount of the copper fullerene carboxylate in the porous aluminum-based metal oxide is 10-30%.

Preferably, the porous aluminum-based metal oxide is SiO₂-Al₂O₃-CeO₂The compound is composed of (0.5-1) to (2-3) to (1-2) in a molar ratio. The specific surface area of the porous aluminum-based metal oxide is 750-1000 m²The pore volume is 1.26-1.94 cm³(ii)/g, the pore diameter is 7.5 to 20.2 nm.

Specifically, the porous aluminum-based metal oxide is prepared by the following method:

(1) dissolving a triblock copolymer Pluronic F127 into a mixed solvent composed of absolute ethyl alcohol and glacial acetic acid according to a volume ratio of 5 (1.5-2.5), wherein the mixing ratio of the Pluronic F127 to the mixed solvent is 1g: 20-30 mL, and uniformly stirring to obtain a mixed solution A;

(2) adding a precursor mixture into the mixed solution A obtained in the step (1), stirring and dissolving to obtain a mixed solution B, wherein the mass ratio of the precursor mixture to the mixed solution A is 1: 3.5-4, the precursor mixture is formed by mixing methyl orthosilicate, aluminum nitrate nonahydrate and cerium nitrate hexahydrate, and the mixing ratio is SiO₂:Al₂O₃:CeO₂The molar ratio of (1) to (2) to (1) is calculated as (0.5-1);

(3) and (3) soaking a three-dimensional ordered macroporous-structure polystyrene template into the mixed solution B obtained in the step (2), soaking for 12-24 hours, placing the soaked polystyrene template in a drying oven at 55-65 ℃ for sol gelation for 48-72 hours to form a gel-like solid, drying the gel-like solid at 60-100 ℃, then placing the gel-like solid in a muffle furnace for calcination at 550-650 ℃ for 3-5 hours, and controlling the heating rate at 0.5-3 ℃/min during calcination to obtain the porous aluminum-based metal oxide microspheres.

The molecular formula of the triblock copolymer Pluronic F127 is EO₁₀₆PO₇₀EO₁₀₆Wherein EO is ethylene oxide and PO is propylene oxide; average molecular weight 12600.

Preferably, the pore diameter of the polystyrene template is 470 nm.

The fullerene copper carboxylate salt is a crystalline product obtained by reacting a fullerene carboxylic acid derivative with copper nitrate. The fullerene carboxylic acid derivative is a C60 carboxylic acid derivative, and specifically, the fullerene copper carboxylate is prepared by the following method: dissolving the fullerene carboxylic acid derivative in 75-90% by volume of ethanol water solution, slowly adding copper nitrate while stirring, continuously stirring and reacting for 1-2 h, then heating to 80-85 ℃, removing ethanol and part of water, cooling to room temperature, crystallizing, aging, filtering, and drying at 110-120 ℃ for 2-3 h to obtain the fullerene copper carboxylate.

In the preparation method, the reaction molar ratio of the fullerene carboxylic acid derivative to the copper nitrate is 1:3.

The C60 carboxylic acid derivative is prepared by modifying a definite number of carboxylic acid groups on fullerene C60, and has a chemical formula of C60(C (COOH)₂)₃The preparation method is prepared by referring to the technical scheme disclosed by the Chinese patent application with the application number of 201711259691.7, and specifically comprises the following steps:

s1: addition of C60 to toluene to form 10^-3A solution in mol/L, then according to the ratio of C60: 1, 8-diazabicycloundecen-7-ene (DBU): adding DBU and diethyl bromomalonate into a toluene solution of C60 dropwise at a molar ratio of 1:3:3, stirring at room temperature for 1h for addition reaction, and separating and purifying on a silica gel column after the reaction to obtain C60 tri-addition carboxylic ester (C60(C (COOEt))₂)₃)；

S2: adding NaH into m (C60 tri-addition carboxylic ester) in a mass ratio of m (NaH) to 1:100, hydrolyzing at 70 ℃ for 8h, finally adding water for extraction, taking the lower layer aqueous solution to obtain C60 sodium carboxylate, and finally adding HCl and methanol for acidification to obtain C60 carboxylic acid derivative C60(C (COOH)₂)₃。

The invention also provides a method for preparing the fuel oil desulfurizer, which comprises the following steps: adding fullerene copper carboxylate into deionized water, performing ultrasonic dispersion to prepare a fullerene copper carboxylate solution with the mass fraction of 5-10%, adding a porous aluminum-based metal oxide into the fullerene copper carboxylate solution, loading the fullerene copper carboxylate into the porous aluminum-based metal oxide by adopting a vacuum impregnation method, so that the loading amount of the fullerene copper carboxylate in the porous aluminum-based metal oxide is 10-30 wt%, and drying at 80-100 ℃ to obtain the fuel oil desulfurizer.

Detailed Description

The following examples further illustrate the invention. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments.