IP Library Granted Patent US 12,233,397
Granted Patent B2
US 12,233,397 · App. 17/768,108 · Granted Feb 25, 2025

Composite material and use thereof in desulfurization

Inventors: Cuicui Xu (Shandong, CN); Aihua Liu (Shandong, CN); Feng Han (Shandong, CN); Jianli Liu (Shandong, CN); Zengrang Liu (Shandong, CN); Weidong Tao (Shandong, CN); Wenzhi Chang (Shandong, CN); Caishan Lyu (Shandong, CN)
Assignees: CHINA PETROLEUM & CHEMICAL CORPORATION; SINOPEC QILU COMPANY
B01J20/20B01D53/0423B01D53/508B01D53/75B01D53/82B01D53/96B01J20/041B01J20/103B01J20/28064B01J20/28071B01J20/2808B01J20/28083B01J20/28092C01B17/164C01B17/508B01D2253/102B01D2253/106B01D2253/1124B01D2253/25B01D2253/308B01D2253/31B01D2253/311B01D2257/302B01D2259/4009
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Quick Facts
Patent No.
US 12,233,397
App. No.
17/768,108
Granted
Feb 25, 2025
Kind
B2
Abstract

A composite material is used for desulfurization. The composite material contains activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides. The weight ratio among the activated carbon, iron oxides and rare earth element oxides is 100:(0.5-5):(1-10). The composite material, used as a sulfur adsorbent, has a higher sulfur breakthrough capacity and desulfurization rate.

Claims (59)

1. A composite material, comprising activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides, wherein the weight ratio between the activated carbon, iron oxides and rare earth element oxides is 100:(0.5-5):(1-10), and the composite material satisfies the following formula I:

M

1

30

(

M

3

+

M

4

+

3

×

M

5

)

M

2

1.5

×

M

3

M

4

formula

I

in formula I:

M 1 represents the weight content of activated carbon in the composite material;

M 2 represents the weight content of alkali metal oxides in the composite material;

M 3 represents the weight content of silicon oxides in the composite material;

M 4 represents the weight content of iron oxides in the composite material;

M 5 represents the weight content of oxides of rare earth elements other than cerium in the composite material.

2. The composite material of claim 1 , wherein the pore volume of the pores having a pore size below 3 nm accounts for 80% or more of the total pore volume of the composite material.

3. The composite material of claim 1 , wherein the pore volume of the pores having a pore size below 3 nm accounts for 80-88% of the total pore volume of the composite material.

4. The composite material of claim 1 , wherein the pore volume of the pores having a pore size below 1 nm accounts for 5-10% of the total pore volume of the composite material; the pore volume of the pores having a pore size within a range of 1-2 nm accounts for 40-55% of the total pore volume; the pore volume of the pores having a pore size larger than 2 nm and equal to or less than 3 nm accounts for 25-35% of the total pore volume.

5. The composite material of claim 1 , wherein a weight ratio between the activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides is 100:(0.2-3):(0.8-5):(0.5-5):(1-10).

6. The composite material of claim 1 , wherein the alkali metal oxide is K 2 O and/or Na 2 O, the silicon oxide is SiO 2 , the iron oxide is Fe 2 O 3 , and the rare earth element oxide is CeO 2 and/or La 2 O 3 .

7. The composite material of claim 1 , wherein the rare earth element oxides are CeO 2 and La 2 O 3 , and the weight ratio of CeO 2 and La 2 O 3 is within a range of 1-3.

8. The composite material of claim 1 , wherein the composite material has a specific surface area larger than or equal to 550 m 2 /g, a pore volume larger than or equal to 0.35 ml/g, a saturated sulfur volume larger than or equal to 15%, and a sulfur breakthrough capacity larger than or equal to 12%.

9. The composite material of claim 1 , wherein the composite material has a specific surface area within a range of 560-590 m 2 /g, a pore volume within a range of 0.36-0.4 ml/g, a saturated sulfur volume within a range of 20-25%, and a sulfur breakthrough capacity within a range of 15.5-16%.

10. The composite material of claim 1 , wherein the composite material does not contain a detectable amount of Y, Cu, Al, Ni, Mn, Co, Zn, Mg, V, Zr, Ti, or Mo.

11. A system with a desulfurization function, wherein the system comprises:

an oxidation unit for treating sulfur-containing gas and recovering sulfur;

a hydrogenation purification unit, which is connected with the oxidation unit for subjecting the oxidation tail gas from the oxidation unit to hydrogenation reduction and recovering hydrogen sulfide in the reduced product obtained from the hydrogenation reduction;

an incineration unit for incinerating the purified tail gas discharged from the hydrogenation purification unit;

an adsorption unit for adsorbing SO 2 from the SO 2 -containing flue gas obtained by incineration, wherein the adsorbent used in the adsorption unit is the composite material of claim 1 .

12. The system of claim 11 , wherein the adsorption unit further comprises an inlet and an outlet of substance used for regeneration, for introducing the substance used for regeneration into the adsorption unit for regenerating the adsorbent, and the adsorption unit is further connected with the oxidation unit, such that the SO 2 -containing regeneration gas obtained from regeneration is returned to the oxidation unit and subjected to retreatment.

13. A method for desulfurization, wherein the method comprises the following steps:

(a) oxidizing the sulfur-containing gas to be treated and recovering the sulfur;

(b) subjecting the oxidized tail gas to hydrogenation reduction and recovering hydrogen sulfide from the reduction product obtained from the hydrogenation reduction;

(c) incinerating the tail gas obtained after the hydrogenation reduction;

(d) contacting the incinerated SO 2 -containing flue gas with a sorbent to adsorb SO 2 , the sorbent is the composite material of claim 1 .

14. The method of claim 13 , wherein the conditions of the contacting in step (d) comprise a temperature within a range of 100-150° C. and a gas volume hourly space velocity within a range of 1,500-2,000 h −1 ;

and/or, the method further comprises regenerating the sorbent, and returning the regenerated SO 2 -containing regeneration gas to step (a) for subjecting to retreatment.

15. The composite material of claim 1 , wherein a weight ratio between the activated carbon, alkali metal oxides, silicon oxides, iron oxides, and rare earth element oxides is 100:(0.5-2):(1-2.8):(1-2.2):(2-5).

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 18, 2022
From: XU, CUICUI; LIU, AIHUA; HAN, FENG; LIU, JIANLI; LIU, ZENGRANG; TAO, WEIDONG; CHANG, WENZHI; LYU, CAISHAN
To: CHINA PETROLEUM & CHEMICAL CORPORATION; SINOPEC QILU COMPANY
Reel/Frame 059620/0337 →
Priority Claims (1)
CN 201910962508.2 · Oct 11, 2019 · national
Continuity (1)
Related Publication 20230149892A1 · May 18, 2023
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Cited By (1)
US 12,708,874