Sorbents for desulfurizing gasolines and diesel fuel

• US 6,429,170 B1
• Filed: 05/30/2000
• Issued: 08/06/2002
• Est. Priority Date: 05/30/2000
• Status: Expired due to Term

• Current Assignee: China Petroleum & Chemical Corporation (Central People's Government of The People's Republic of China)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Dodwell, Glenn W.
• Primary Examiner(s): Silverman, Stanley S.
• Assistant Examiner(s): Vanoy, Timothy C
• Application Number:
  US09/580,611
• Time in Patent Office: 798 Days
• Field of Search: 208/208.R, 208/243, 208/244, 208/246, 208/247, 208/249, 208/299, 502/400, 502/406, 502/407, 502/415, 502/439, 502/514, 502/517, 502/504
• US Class Current: 502/400
• CPC Class Codes: B01J 20/02 comprising inorganic material
• 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 20/106 Perlite
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/28042 Shaped bodies; Monolithic structures
• CPC Class Codes: B01J 20/3021 Milling, crushing or grinding
• 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 23/06 of zinc, cadmium or mercury
• CPC Class Codes: B01J 23/16 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 23/22 Vanadium
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/30 Tungsten
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/50 Silver
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/75 : Cobalt
• CPC Class Codes: B01J 23/755 : Nickel
• CPC Class Codes: B01J 23/80 : with zinc, cadmium or mercury
• CPC Class Codes: B01J 27/1853 : with iron, cobalt or nickel
• CPC Class Codes: B01J 35/40 : characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/50 : characterised by their shape or configuration
• CPC Class Codes: B01J 37/0009 : Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0045 : Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/0201 : Impregnation
• CPC Class Codes: B01J 37/18 : with gases containing free hydrogen
• CPC Class Codes: C10G 2300/104 : Light gasoline having a boiling range of about 20 - 100 °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 2300/207 : Acid gases, e.g. H2S, COS, SO2, HCN
• CPC Class Codes: C10G 2300/4093 : Catalyst stripping
• CPC Class Codes: C10G 2300/703 : Activation
• 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: Y10S 502/514 : Process applicable either to preparing or to regenerating or to rehabilitating catalyst or sorbent
• CPC Class Codes: Y10S 502/517 : Sulfur or sulfur compound removal

Abstract

Attrition resistant, sorbent compositions for the removal of elemental sulfur and sulfur compounds, such as hydrogen sulfide and organic sulfides, from cracked-gasoline and diesel fuels are prepared by the impregnation of a sorbent support comprising zinc oxide, expanded perlite, and alumina with a promoter such as nickel, nickel oxide or a precursor of nickel oxide followed by reduction of the valence of the promoter metal in the resulting promoter metal sorbent support composition.

Claims

1. A calcined and reduced sorbent composition suitable for removal of elemental sulfur and sulfur compounds from cracked-gasoline and diesel fuels which prior to calcining and reduction is comprised of:

(a) zinc oxide;

(b) expanded perlite;

(c) alumina; and

(d) a promoter metal

wherein said promoter metal is present in an amount which will effect the removal of sulfur or sulfur compounds from a stream of cracked-gasoline or diesel fuel when contacted with same under desulfurization conditions and at least a portion of said promoter metal is present in a zero valence state.

2. A sorbent composition in accordance with claim 1 wherein said promoter metal is at least one metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium.

3. A sorbent composition in accordance with claim 2 wherein said calcined and reduced promoter metal is present in an amount in the range of about 1.0 to about 60 weight percent.

4. A sorbent composition in accordance with claim 2 wherein prior to calcining and reduction said zinc oxide is present in an amount in the range of about 10 to about 90 weight percent, said expanded perlite is present in an amount in the range of about 10 to about 40 weight percent, and said alumina is present in an amount in the range of about 5 to about 30 weight percent, said weight percent being based on the weight of the sorbent support.

5. A sorbent composition in accordance with claim 4 wherein said zinc oxide is present in an amount of about 48.3 weight percent, said expanded perlite is present in an amount of about 12.08 weight percent, said alumina is present in an amount of about 9.63 weight percent, and said promoter metal is present in an amount of about 30 weight percent based on the total weight of the sorbent composition.

6. A sorbent composition in accordance with claim 2 wherein said promoter metal is nickel.

7. A sorbent composition in accordance with claim 2 wherein said promoter metal is cobalt.

8. A sorbent composition in accordance with claim 2 wherein said promoter metal is a mixture of nickel and cobalt.

9. A sorbent composition in accordance with claim 1 wherein said expanded perlite is milled.

10. A sorbent composition in accordance with claim 1 wherein said composition is a particulate in the form of one of granule, extrudate, tablet, sphere, pellet, or microsphere.

11. A sorbent composition in accordance with claim 10 wherein said particulate is a microsphere.

12. A process for the production of a sorbent composition for the removal of elemental sulfur or sulfur compounds from a cracked-gasoline or diesel fuel stream which comprises:

(a) admixing zinc oxide, expanded perlite and alumina so as to form a mix thereof, wherein said mix is in a form of a wet mix, dough paste or slurry;

(b) particulating the resulting mix to form a particulate thereof;

(c) drying the particulate of step (b) to form a dried particulate;

(d) calcining the dried particulate of step (c) to form a calcined particulate;

(e) impregnating the resulting calcined particulate of step (d) with a promoter metal or promoter metal containing compound to form an impregnated particulate;

(f) optionally, when the impregnating process of step (e) does not produce a dry, impregnated particulate, drying the impregnated particulate of step (e) to form a dried, impregnated particulate;

(g) calcining the dried particulate of step (f) to form a calcined, impregnated particulate; and

thereafter

(h) reducing the resulting calcined, impregnated particulate of step (g) with a reducing agent under conditions to produce a particulate composition having a reduced promoter metal content such that the reduced metal containing composition will effect the removal of sulfur or sulfur compounds from the stream of a cracked-gasoline or diesel fuel when such stream is contacted with same under desulfurization conditions.

13. A process in accordance with claim 12 wherein said particulate composition is in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres.

14. A process in accordance with claim 12 wherein said particulate of step (b) is formed by spray drying of the mix of step (a).

15. A process in accordance with claim 12 wherein prior to calcining and reduction said zinc oxide is present in an amount in the range of about 10 to about 90 weight percent, said expanded perlite is present in an amount in the range of about 10 to about 40 weight percent, and said alumina is present in an amount in the range of about 1 to about 30 weight percent of the sorbent support composition.

16. A process in accordance with claim 12 wherein said calcined particulate is impregnated with a promoter derived from one or more metals, metal oxides or metal oxide precursors wherein the metal is selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, and vanadium.

17. A process in accordance with claim 16 wherein said calcined and reduced promoter metal is present in an amount in the range of about 1.0 to about 60 weight percent based on the total weight of the sorbent composition.

18. The sorbent product of the process of claim 17.

19. A process in accordance with claim 12 wherein said particulate is dried in steps (c) and (f) at a temperature in the range of about 150°

F. to about 3500°

F.

20. A process in accordance with claim 19 wherein said calcined and reduced promoter is nickel and is present in an amount of about 30 weight percent based on the total weight of the sorbent composition.

21. A process in accordance with claim 12 wherein said dried particulate is calcined in steps (d) and (g) at a temperature in the range of about 400 to about 1500°

F.

22. A process in accordance with claim 12 wherein prior to calcining and reduction said zinc oxide is present in an amount in the range of about 40 to about 80 weight percent, said expanded perlite is present in an amount in the range of about 1 to about 30 weight percent, and said alumina is present in an amount in the range of about 1.0 to about 20 weight percent, and said promoter is present in an amount in the range of about 10 to about 30 weight percent.

23. The sorbent product of the process of claim 22.

24. A process in accordance with claim 12 wherein prior to calcining and reduction said zinc oxide is present in an amount of about 69 weight percent, said expanded perlite is present in an amount of about 17.25 weight percent, and said alumina is present in an amount in the range of about 5 to about 30 weight percent, said weight percent being based on the weight of the sorbent support.

25. A process in accordance with claim 24 wherein said calcined and reduced promoter is nickel and is present in an amount of about 12 weight percent based on the total weight of the sorbent composition.

26. A process in accordance with claim 12 wherein the reduction of the promoter metal is carried out at a temperature in the range of from about 100°

F. to about 1500°

F. and at a pressure in the range of about 15 to about 1500 psia for a time sufficient to permit the formation of the reduced promoter metal.

27. The sorbent product of the process of claim 12.