Catalyst for catalytic reduction of industrial flue gas SO2 with CO to prepare sulfur, method for preparing same and use thereof

Patent metadata

Field	Value
Publication number	US-12090467-B2
Application number	US-202217859111-A
Country	US
Kind code	B2
Filing date	Jul 7, 2022
Priority date	Jul 30, 2021
Publication date	Sep 17, 2024
Grant date	Sep 17, 2024

Abstract

The present invention provides a catalyst for catalytic reduction of an industrial flue gas SO 2 with CO to prepare sulfur, a method for preparing the same and use thereof. A CeO 2 nanocarrier is prepared by using a hydrothermal method, La and Y are loaded as active components, pre-sulfurization is conducted with 6% of SO 2 and 3% of CO, and finally, the catalyst is prepared. The catalyst has high reactivity and sulfur selectivity and strong stability. The by-product sulfur generated by the reaction is recovered with a solvent CS 2 , and the solvent CS 2 is recovered by using a distillation process. The preparation method is low in cost, causes no secondary pollution and is high in sulfur recovery rate. The problem of low sulfur production in China at present is solved.

First claim

What is claimed is:

1. A method for preparing a catalyst for catalytic reduction of an industrial flue gas SO 2 with CO, comprising the following steps:
a) respectively dissolving Ce(NO 3 ) 3 ·6H 2 O and NaOH in water to obtain a Ce(NO 3 ) 3 ·6H 2 O aqueous solution and a NaOH aqueous solution, and slowly adding the NaOH aqueous solution dropwise into the Ce(NO 3 ) 3 ·6H 2 O aqueous solution for uniform mixing to obtain a mixed solution 1 ;
b) dissolving cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfonate (SDS) in water to obtain a solution, slowly adding the solution into the mixed solution 1 for stirring for 12-15 h, and conducting a hydrothermal reaction at a temperature of 100-110° C. for 24-26 h;
c) cooling a reactant obtained after the hydrothermal reaction in step b) to room temperature, filtering the cooled reactant to collect a white precipitate, and sequentially washing, drying and calcining the white precipitate to obtain a CeO 2 nanorod;
d) dissolving La(NO 3 ) 3 ·6H 2 O and Y(NO 3 ) 3 ·6H 2 O in water to obtain a mixed solution 2 , and adjusting a pH of the mixed solution 2 to 12 ; adding the CeO 2 nanorod obtained in step c) into the mixed solution 2 , placing the mixed solution 2 on a magnetic stirrer for stirring at a constant speed at 30-40° C. for about 4-6 h, heating the mixed solution to 80-90° C., and continuously stirring the mixed solution until the solution is neutral to obtain a catalyst; and drying the catalyst, and calcining the dried catalyst in an air atmosphere in a muffle furnace at 500-600° C. for 4-6 h to obtain a La-Y/CeO 2 catalyst; and
e) pulverizing and sieving the La-Y/CeO 2 catalyst, placing particles with a particle size of 60-80 mesh in a quartz tube, and placing the quartz tube in an electric tube furnace; and then conducting sulfurization at 550-600° C. at a heating rate of 5-15° C./min in a mixed gas comprising 1-10% of CO, 1-10% of SO 2 and the balance of N 2 by volume at an air speed of 5,000-8,000 h −1 for 1-4 h to obtain a target product sulfurized catalyst.

2. The method according to claim 1 , wherein, in step a), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the NaOH in the mixed solution is (0.1-5):(10-50).

3. The method according to claim 1 , wherein, in step b), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the CTAB to the SDS is (10-30):(0.1-3):(0.1-3).

4. The method according to claim 1 , wherein, a molar ratio of the Ce(NO 3 ) 3 ·6H 2 O to the La(NO 3 ) 3 ·6H 2 O to the Y(NO 3 ) 3 ·6H 2 O is (6-12):(0.5-1.5):(1-3).

5. A catalyst for catalytic reduction of an industrial flue gas SO 2 with CO, prepared by using the following method:
a) respectively dissolving Ce(NO 3 ) 3 ·6H 2 O and NaOH in water to obtain a Ce(NO 3 ) 3 ·6H 2 O aqueous solution and a NaOH aqueous solution, and slowly adding the NaOH aqueous solution dropwise into the Ce(NO 3 ) 3 ·6H 2 O aqueous solution for uniform mixing to obtain a mixed solution 1 ;
b) dissolving cetyl trimethyl ammonium bromide (CTAB) and sodium dodecyl sulfonate (SDS) in water to obtain a solution, slowly adding the solution into the mixed solution 1 for stirring for 12-15 h, and conducting a hydrothermal reaction at a temperature of 100-110° C. for 24-26 h;
c) cooling a reactant obtained after the hydrothermal reaction in step b) to room temperature, filtering the cooled reactant to collect a white precipitate, and sequentially washing, drying and calcining the white precipitate to obtain a CeO 2 nanorod;
d) dissolving La(NO 3 ) 3 ·6H 2 O and Y(NO 3 ) 3 ·6H 2 O in water to obtain a mixed solution 2 , and adjusting a pH of the mixed solution 2 to 12 ; adding the CeO 2 nanorod obtained in step c) into the mixed solution 2 , placing the mixed solution 2 on a magnetic stirrer for stirring at a constant speed at 30-40° C. for about 4-6 h, heating the mixed solution to 80-90° C., and continuously stirring the mixed solution until the solution is neutral to obtain a catalyst; and drying the catalyst, and calcining the dried catalyst in an air atmosphere in a muffle furnace at 500-600° C. for 4-6 h to obtain a La-Y/CeO 2 catalyst; and
e) pulverizing and sieving the La-Y/CeO 2 catalyst, placing particles with a particle size of 60-80 mesh in a quartz tube, and placing the quartz tube in an electric tube furnace; and then conducting sulfurization at 550-600° C. at a heating rate of 5-15° C./min in a mixed gas comprising 1-10% of CO, 1-10% of SO 2 and the balance of N 2 by volume at an air speed of 5,000-8,000 h −1 for 1-4 h to obtain a target product sulfurized catalyst.

6. The catalyst according to claim 5 , wherein, in step a), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the NaOH in the mixed solution is (0.1-5):(10-50).

7. The catalyst according to claim 5 , wherein, in step b), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the CTAB to the SDS is (10-30):(0.1-3):(0.1-3).

8. The catalyst according to claim 5 , wherein, a molar ratio of the CeO 2 to the La(NO 3 ) 3 ·6H 2 O to the Y(NO 3 )3·6H 2 O is (6-12):(0.5-1.5):(1-3).

9. A method of using the catalyst prepared by using the method according to claim 1 in catalytic reduction of an industrial flue gas SO 2 with CO to prepare sulfur, comprising: placing 1 mL of a sulfurized catalyst in a 10 mm quartz tube, and placing the quartz tube in an electric tube furnace for a reaction at a temperature of 300-500° C. at a heating rate of 5-15° C./min in a flue gas comprising 0.5-4% of SO 2 , 1-8% of CO and 88-98.5% of N 2 at a volumetric air speed of 12,000-15,000 h −1 ; and discharging sulfur vapor from a gas outlet of the tube furnace, preserving heat of the sulfur vapor with a heating belt, and condensing the sulfur vapor into sulfur in a cold trap.

10. The method according to claim 9 , wherein, after the reaction is completed, 100-120 mL of CS 2 is added into the cold trap and shaken up and down for completely dissolving the sulfur in a CS 2 solution, an obtained mixed solution is placed in a distillation flask, and the distillation flask is heated at 50-60° C. in a water bath kettle; the CS 2 is vaporized after being heated to obtain vapor, and the vapor enters a condenser through a branch tube and is condensed in a conical flask; and sulfur obtained in the distillation flask is collected.

11. The method according to claim 2 , wherein, in step a), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the NaOH in the mixed solution is (1.5-5):(10-40).

12. The method according to claim 3 , wherein, in step b), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the CTAB to the SDS is (10-25):(0.5-1.5):(0.5-1.5).

13. The catalyst according to claim 6 , wherein, in step a), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the NaOH in the mixed solution is (1.5-5):(10-40).

14. The catalyst according to claim 7 , wherein, in step b), a mass ratio of the Ce(NO 3 ) 3 ·6H 2 O to the CTAB to the SDS is (10-25):(0.5-1.5):(0.5-1.5).

Assignees

• Nanjing University Of Technology
• Nanjing Gekof Institute Of Environmental Protection Tech & Equipment Co Ltd

Inventors

• Xu Haitao
• Ji Wenyu
• Xu Mutao
• Jin Qijie
• Li Mingbo
• Song Jing
• Xu Meng

Classifications

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C01B17/0486 Primary

  with carbon monoxide or carbon monoxide containing mixtures · CPC title

• B01J37/20

  Sulfiding · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title