Desulfurizing adsorbent, preparing process and use thereof

• US 8,975,208 B2
• Filed: 12/30/2009
• Issued: 03/10/2015
• Est. Priority Date: 12/31/2008
• Status: Active Grant

• Current Assignee: China Petroleum & Chemical Corporation (Central People's Government of The People's Republic of China), Research Institute of Petroleum Processing Sinopec
• Original Assignee: China Petroleum & Chemical Corporation (Central People's Government of The People's Republic of China), Research Institute of Petroleum Processing Sinopec
• Inventors: Long, Jun, Tian, Huiping, Lin, Wei
• Primary Examiner(s): Robinson, Renee E
• Application Number:
  US13/142,946
• Publication Number:
  US 20110272328A1
• Time in Patent Office: 1,896 Days
• Field of Search: 502/241, 502/247, 502251-253, 502258-260, 502/406, 502/407, 502/415
• US Class Current: 502/407
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/3007 Moulding, shaping or extruding
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 2220/42 Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: B01J 2220/56 Use in the form of a bed
• CPC Class Codes: C10G 2300/104 Light gasoline having a boiling range of about 20 - 100 °C
• CPC Class Codes: C10G 2300/1044 Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• CPC Class Codes: C10G 2300/1055 Diesel having a boiling range of about 230 - 330 °C
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 25/003 : Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 25/09 : according to the "fluidised bed" technique

Abstract

The present invention provides an adsorbent for removing sulfur from cracking gasoline or diesel fuel. The adsorbent has excellent abrasion-resistance and desulfurization activity. The adsorbent comprises from about 5 to about 35 wt % of alumina, from about 3 to about 30 wt % of silica, from about 10 to about 80 wt % of at least one oxide of metal selected from Groups IIB and VB, from about 3 to about 30 wt % of at least one metal accelerant selected from Groups VIIB and VIII, and from about 0.5 to about 10 wt % of at least one oxide of metal selected from Groups IA and IIA, based on the total weight of the adsorbent.

Claims

1. A desulfurization adsorbent comprising,:

1) from about 5 to about 35 wt % of alumina,

2) from about 3 to about 30 wt % of silica,

3) from about 10 to about 80 wt % of at least one oxide of metal selected from Groups IIB and VB,

4) from about 3 to about 30 wt % of at least one metal accelerant selected from Groups VIIB and VIII, and

5) from about 0.5 to about 10 wt % of at least one oxide of metal selected from Groups IA and IIA,

based on the total weight of the adsorbent;

wherein oxide of metal selected from Groups IA and IIA has a uniform distribution of metal in the entire adsorbent, and wherein the silica of component

     2) is not the source of the at least one oxide of metal selected from Groups IA and IIA of component

     5).

2. The adsorbent according to claim 1 wherein the amount of alumina is in the range of from about 10 to about 25 wt %, the amount of silica is in the range of from about 10 to about 20 wt %, the amount of oxide of metal selected from Groups IIB and VB is in the range of from about 35 to about 65 wt %, the amount of metal accelerant is in the range of about 8 to about 20 wt %, and the amount of oxide of metal selected from Groups IA and IIA is in the range of about 1 to about 5 wt %.

3. The adsorbent according to claim 1 wherein said at least one oxide of metal selected from Groups IIB and VB is oxide of vanadium or zinc.

4. The adsorbent according to claim 1 wherein said at least one metal accelerant is metal selected from the group consisting of cobalt, nickel, iron and manganese.

5. The adsorbent according to claim 1 wherein the Group IIA metal oxides comprise oxides of magnesium and/or calcium, and the Group IA metal oxides comprise oxides of sodium and/or potassium.

6. A process for preparing an adsorbent of claim 1, comprising the steps of:

(1) mixing water, acid and binder or further mixing with at least one material selected from clay, silica source and Group IA metal compound/Group IIA metal compound to form a slurry, and aging the slurry to form an acidified slurry;

(2) mixing the acidified slurry with an oxide of metal selected from Groups IIB and VB and un-added material selected from clay, silica source and Group IA metal compound/Group IIA metal compound in step (1) to form a carrier mixture;

(3) molding, drying and calcinating the carrier mixture to form a carrier;

(4) introducing a compound comprising metal accelerant selected from Group VIIB and Group VIII onto the carrier, and drying and calcinating the carrier to form an adsorbent precursor; and

(5) reducing the adsorbent precursor under hydrogen containing atmosphere so that the accelerant metal is substantially present in a reduced state.

7. The process according to claim 6, wherein the silica source can be selected from the group consisting of one or more of diatomite, silica sol, silica gel, macroporous silica and expanded perlite.

8. The process according to claim 6 wherein the clay is selected from the group consisting of one or more of kaolin, rectorite, Yunmeng clay, bentonite and montmorillonite.

9. The process according to claim 6, wherein the binder is selected from the group consisting of one or more of hydrated alumina, aluminum sol, boehmite, pseudo-boehmite, alumina trihydrate, and amorphous aluminium hydroxide.

10. The process according to claim 6 or claim 9 wherein the weight ratio of clay to binder is from about 0.2 to about 1.2:

1, and the weight ratio of silica source and binder is from about 0.5 to about 1.5;

1.

11. The process according to claim 6 wherein the Group IIA metal compound is selected from the group consisting of one or more of nitrate, chloride, formate and acetate of the Group II metal, and the Group IA metal compound is selected from the group consisting of one or more of carbonate, bicarbonate, nitrate, chloride, formate, acetate of Group IA metal.

12. The process according to claim 6 wherein the compound comprising metal accelerant is at least one selected from the group consisting of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal accelerant.

13. The process according to claim 6 wherein water, acid, binder and clay, silica source are mixed to form a slurry, and the slurry is aged to form an acidified slurry in step (1), and the acidified slurry is added with oxide of metal selected from Group IIB and VB, Group IA or IIA metal compound to form a carrier mixture in step (2).

14. The process according to claim 6 wherein water, acid, binder and clay are mixed, and then aged to form an acidified slurry in step (1);

and the acidified slurry is added with oxide of metal selected from Group IIB and VB and pre-treated silica source to form a carrier mixture, wherein pre-treated silica source is obtained by mixing silica source and Group IA or IIA metal compound, and drying and calcinating said carrier mixture at about 400°

C. to about 600°

C. in step (2).

15. The process according to claim 6, 13 or 14 wherein, in step (1), the acid is selected from one or more water soluble inorganic acid and/or organic acid, and the amount of acid used is such that the pH of the slurry is from about 1 to about 5, the amount of water used is such that the concentration of the slurry is from about 10 to about 20 wt %.

16. The process according to claim 6, 13 or 14 wherein the aging temperature is from about 60 to about 80°

C., and the aging time is from about 1 to about 3 hours in step (1).

17. The process according to claim 6 wherein the carrier mixture is in the form of slurry having a solids of from about 10 to about 50 wt %, and the carrier mixture is molded by spray drying into microspheres having a particle size of from about 20 to about 200 micron, dried at from room temperature to about 400 C and calcinated at from about 500 to about 800°

C. in step (3).

18. The process according to claim 6 wherein the metal accelerant is introduced into the carrier by impregnation or precipitation, and the carrier is dried at from about 50 to about 300°

C., and calcinated at from about 300 to about 800°

C. in step (4).

19. A method for desulfurizing cracking gasoline or diesel fuel, comprising fully contacting the sulfur containing feed with the adsorbent according to any one of the claims 1 to 5 at about 350 to about 500°

C., and collecting the product having lowered sulfur content.

20. The method of claim 19 wherein the contacting is conducted in a fluidized bed.