CN-121972225-A - Fe/Cu-BTC-BA catalyst, preparation method and desulfurization application

Abstract

The invention provides a Fe/Cu-BTC-BA catalyst, a preparation method and application thereof, and relates to the technical field of metal organic framework materials. The preparation method comprises the steps of mixing an iron source, a copper source, trimesic acid, benzoic acid and hexadecyl trimethyl ammonium bromide with a solvent, performing solvothermal reaction at 120-140 ℃ for 20-28 h, and filtering, washing and drying to obtain the target catalyst. By constructing Fe-Cu double active sites and combining double ligands, cu 2+ is induced to be converted into Cu + , the Lewis acidity and hydrogen sulfide adsorption activation capacity are enhanced, the framework stability is improved, and the pore channel structure is optimized. The catalyst has the advantages of high specific surface area, high sulfur capacity up to 7.8%, high desulfurization rate and stable structure, and is suitable for catalytic desulfurization of sulfur-containing gas.

Inventors

• WANG NA
• BAO SULING
• YAN JING
• WANG XING

Assignees

• 天津新翔油气技术有限公司
• 内蒙古新翔油气技术有限公司

Dates

Publication Date

20260505

Application Date

20260126

Claims (10)

1. 1. The preparation method of the Fe/Cu-BTC-BA catalyst is characterized by comprising the following steps of: Mixing an iron source, a copper source, trimesic acid, benzoic acid and hexadecyl trimethyl ammonium bromide with a solvent, and performing solvothermal reaction to obtain the Fe/Cu-BTC-BA catalyst.
2. 2. The method of preparing of claim 1, wherein the iron source comprises at least one of ferric chloride hexahydrate or ferric nitrate nonahydrate.
3. 3. The method of making according to claim 2, wherein the copper source comprises at least one of copper chloride dihydrate or copper nitrate trihydrate.
4. 4. The method of claim 3, wherein the molar ratio of Fe in the iron source to Cu in the copper source is 10 (1-5).
5. 5. The process according to claim 1, wherein the molar ratio of trimesic acid to benzoic acid is 1 (0.2-1).
6. 6. The method of claim 1, wherein the solvent comprises at least one of N, N-dimethylformamide, ethanol, or deionized water.
7. 7. The method according to claim 1, wherein the ratio of the amount of cetyltrimethylammonium bromide added to the total molar amount of trimesic acid and benzoic acid is 1 (10-20).
8. 8. The preparation method of claim 1, wherein the solvothermal reaction is carried out at a temperature of 120-140 ℃ for 20-28 h.
9. 9. An Fe/Cu-BTC-BA catalyst prepared by the preparation method of any one of claims 1 to 8.
10. 10. Use of the Fe/Cu-BTC-BA catalyst of claim 9 for catalytic desulfurization of sulfur-containing gases.

Description

Fe/Cu-BTC-BA catalyst, preparation method and desulfurization application Technical Field The invention relates to the technical field of metal organic framework materials, in particular to a Fe/Cu-BTC-BA catalyst, a preparation method and desulfurization application. Background The metal organic framework compounds (MOFs) are formed by connecting metal or metal cluster center ions with organic ligands through self-assembly, are inorganic-organic hybrid coordination polymer materials with periodic network structures, have the characteristics of large porosity, large specific surface area and the like of traditional porous materials, have the special advantages of the MOFs, such as adjustable pore channel shape, easy surface modification, open metal active sites and the like, and are widely studied in the adsorption desulfurization field. However, MOFs desulfurization generally suffers from low sulfur capacity. Increasing sulfur capacity by modifying MOFs is one method commonly employed by researchers. Research shows that the metal sites are important active sites for MOFs to adsorb sulfide and have key effects on improving sulfur capacity. The current research shows that the Fe-MOF has larger specific surface area and more Lewis acid sites, can effectively improve the H 2 S removal efficiency, but the single Fe-MOF has slower H 2 S removal rate and lower sulfur capacity. The invention aims to design an iron-copper bimetallic material, and part of Cu 2+ is changed into Cu + by adjusting the types of ligands, so that the number of Lewis acid sites is increased, and the sulfur capacity is improved while hydrogen sulfide is efficiently removed. Disclosure of Invention In order to solve the defects and shortcomings in the prior art, the application aims to provide an Fe/Cu-BTC-BA catalyst, a preparation method and application. The Fe-Cu bimetal synergistic active site is constructed by a one-step solvothermal method, cu 2+ is induced to be directionally converted into Cu + by matching with trimesic acid (BTC) and Benzoic Acid (BA) double ligands, hexadecyl trimethyl ammonium bromide (CTAB) is introduced as a structure guiding agent to regulate and control a pore channel structure, and under the optimized reaction conditions of 120-140 ℃ and 20-28 hours, the Lewis acidity, the hydrogen sulfide adsorption activation capacity and the framework stability of the catalyst are synchronously enhanced, so that the desulfurization catalyst with high specific surface area, excellent sulfur capacity, high desulfurization rate and stable structure is finally obtained, and the technical bottlenecks of low desulfurization sulfur capacity and poor removal efficiency of the traditional MOF material are effectively broken through. The invention aims at providing a preparation method of a Fe/Cu-BTC-BA catalyst, which comprises the following steps: Mixing an iron source, a copper source, trimesic acid, benzoic acid and hexadecyl trimethyl ammonium bromide with a solvent, and performing solvothermal reaction to obtain the Fe/Cu-BTC-BA catalyst. Preferably, the iron source comprises at least one of ferric chloride hexahydrate or ferric nitrate nonahydrate. Preferably, the copper source comprises at least one of copper chloride dihydrate or copper nitrate trihydrate; preferably, the molar ratio of Fe in the iron source to Cu in the copper source is 10 (1-5). Preferably, the molar ratio of Fe in the iron source to Cu in the copper source is 10:2. Preferably, the molar ratio of trimesic acid to benzoic acid is 1 (0.2-1). Preferably, the solvent is selected from at least one of N, N-dimethylformamide, ethanol or deionized water. Preferably, the ratio of the addition amount of cetyl trimethyl ammonium bromide to the total molar amount of trimesic acid and benzoic acid is 1 (10-20). Preferably, the solvothermal reaction condition is that the reaction temperature is 120-140 ℃ and the reaction time is 20-28 h. The second object of the invention is to provide a Fe/Cu-BTC-BA catalyst prepared by the preparation method. The invention further aims to provide an application of the Fe/Cu-BTC-BA catalyst in catalytic desulfurization of sulfur-containing gas. The invention has the beneficial effects that: The Fe/Cu-BTC-BA catalyst with high specific surface area, high sulfur capacity and stable structure is prepared by mixing an iron source, a copper source, trimesic acid, benzoic acid and hexadecyl trimethyl ammonium bromide with a solvent and performing solvothermal reaction. Fe-Cu double active sites are constructed through a one-step hydrothermal method to form a synergistic reaction system, fe 3+ is combined with S atom lone pair electrons in H 2 S through strong Lewis acidity to weaken H-S bonds and promote dissociation of the H-S bonds, and Cu sites activate O 2 to generate super-oxygen/peroxy active species to quickly react and dissociate sulfur species, so that the removal rate of H 2 S is greatly improved. With the dual ligand design by me