Desulfurization and novel sorbents for same

• US 20010029311A1
• Filed: 05/24/2001
• Published: 10/11/2001
• Est. Priority Date: 11/01/1999
• Status: Active Grant

• Current Assignee: China Petroleum & Chemical Corporation (Central People's Government of The People's Republic of China)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Khare, Gyanesh P.
• Granted Patent: US 6,428,685 B2
• Time in Patent Office: Days
• US Class Current: 585/826
• CPC Class Codes: B01J 20/02 comprising inorganic material
• CPC Class Codes: B01J 20/045 containing sulfur, e.g. sulfates, thiosulfates, gypsum
• CPC Class Codes: B01J 20/048 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
• 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 20/10 comprising silica or silicate
• 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 20/28016 Particle form
• CPC Class Codes: B01J 20/28019 Spherical, ellipsoidal or cylindrical
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• 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 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3458 in the gas phase
• CPC Class Codes: B01J 20/3483 by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: B01J 20/3491 by pressure treatment
• 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: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03

Abstract

Particulate sorbent compositions which are suitable for the removal of sulfur from streams of cracked-gasoline or diesel fuel are provided which have increased porosity, improved resistance to deactivation through the addition of a calcium compound selected from the group consisting of calcium sulfate, calcium silicate, calcium phosphate or calcium aluminate to the support system comprised of zinc oxide, silica and alumina having thereon a promotor wherein the promotor is metal, metal oxide or metal oxide precursor with the metal being selected from the group consisting of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium or mixtures thereof and wherein the valence of such promotor has been substantially reduced to 2 or less. Process for the preparation such sorbent systems as well s the use of same for the desulfurization of cracked-gasolines and diesel fuels are also provided.

Claims

1. A sorbent composition suitable for removal of sulfur from cracked-gasolines and diesel fuels which is comprised of a promotor metal on a support composition comprised of:

(a) zinc oxide;

(b) silica;

(c) alumina; and

(d) a calcium compound selected from the group consisting of calcium sulfate, calcium aluminate, calcium phosphate and calcium silicate;

wherein said promotor metal is present in a substantially reduced valence and in an amount which effects the removal of sulfur from a stream of cracked-gasoline or diesel fuel when contacted with same under desulfurization conditions and wherein said calcium compound is present in an amount to preclude deactivation of the sorbent composition.

2. A sorbent composition in accordance with

claim 1

wherein said promotor metal is present in an amount in the range of about 5 to about 50 weight percent of total weight of sorbent composition.

3. A sorbent composition in accordance to

claim 1

wherein said zinc oxide is present in an amount in the range of about 10 to about 90 weight percent, said silica is present in an amount in the range of about 5 to about 85 weight percent, said alumina is present in an amount in the range of about 5 to about 30 weight percent and said calcium compound is present in an amount in the range of about 5 to about 90 weight percent of the amount of silica present in the sorbent composition.

4. A sorbent composition in accordance with

claim 3

wherein said calcium compound is calcium sulfate.

5. A sorbent composition in accordance with

claim 4

wherein said calcium compound is present in an amount such that the ratio of calcium compounds to silica is in the range of about 0.1 to about 0.9.

6. A sorbent composition in accordance with

claim 1

wherein said promotor is a metal, metal oxide or metal oxide precursor wherein the metal is selected from the group consisting of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium or mixtures thereof.

7. A sorbent composition in accordance with

claim 6

wherein said promotor metal is nickel.

8. A sorbent composition in accordance with

claim 1

wherein said zinc oxide is present in an amount of about 39 weight percent, said silica is present in an amount of about 23 weight percent, said alumina is present in an amount of about 8 weight percent and said calcium compound is calcium sulfate and is present in am amount of about 8 weight percent and said promotor metal is nickel and is present in an amount of about 23 weight percent prior to reduction substantially to zero valence.

9. A sorbent composition in accordance to

claim 1

wherein said composition is a particulate in the form of one of granule, extrudate, tablet, sphere, pellet or microsphere.

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

(a) admixing of zinc oxide, silica and alumina and a calcium compound selected from the group consisting of calcium sulfate, calcium aluminate, calcium phosphate and calcium silicate;

(b) particulating the resulting mix so as to form particles thereof;

(c) drying the particulate of step (b);

(d) calcining the dried particulate of step (c);

(e) impregnating the resulting calcined particulate of step (d) with a metal, metal oxide or metal oxide precursor promotor wherein the metal is selected from the group consisting of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium or mixtures thereof compound;

(f) drying the impregnated particulate of step (e);

(g) calcining the dried particulate of step (f); and

thereafter

(h) reducing the resulting calcined particulate of step (g) with a suitable reducing agent under suitable conditions to produce a particulate composition having a substantial reduced valence metal content therein such that the reduced valence metal containing composition will affect the removal of sulfur from a stream of cracked-gasoline or diesel fuel when said stream is contacted with same under desulfurization conditions.

11. A process in accordance with

claim 10

wherein said mix is in the form of one of a wet mix, dough, paste or slurry.

12. A process in accordance with

claim 10

wherein said particles are in the form of one of granules, extrudates, tablets, spheres, pellets or microspheres.

13. A process in accordance with

claim 10

wherein said zinc oxide is present in an amount in the range of from about 10 to about 90 weight percent, said silica is present in an amount in the range of about 5 to about 85 weight percent, said alumina is present in an amount in the range of about 5 to about 30 weight percent and said calcium compound is present in an amount in the range of about 5 to about 90 weight percent of the amount of silica present in the sorbent composition.

14. A process in accordance with

claim 13

wherein said calcium compound is present in an amount such that the radio of said calcium compound to said silica is in the range of about 0.1 to about 0.9.

15. A process in accordance with

claim 10

wherein said particulate is dried in steps (c) and (f) at a temperature in the range of about 150°

F. to about 350°

F.

16. A process in accordance with

claim 10

wherein said dried particulate is calcined in steps (d) and (g) at a temperature in the range of about 400°

F. to about 1500°

F.

17. A process in accordance with

claim 10

wherein said zinc oxide is present in an amount of about 39 weight percent, said silica is present in an amount of about 23 weight percent, said alumina is present in an amount of about 8 weight percent, said calcium compound is present in an amount of about 8 weight percent and the said promotor metal is present in an amount of about 23 weight percent prior to reduction substantially to zero valence.

18. A process in accordance with

claim 17

wherein said calcium compound is calcium sulfate and said promotor metal is nickel.

19. A process in accordance with

claim 10

wherein said reducing agent is hydrogen.

20. A process in accordance with

claim 19

wherein the reduction of said calcined particulate is carried out at a temperature in the range of 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 desired reduced valence promotor metal.

21. The sorbent product of the process of

claim 10

.

22. The sorbent product of the process of

claim 14

.

23. The sorbent product of the process of

claim 17

.

24. A process for the removal of sulfur from a stream of a cracked-gasoline or a diesel fuel which comprises:

(a) contacting said stream with a sorbent composition which is comprised of zinc oxide, silica, alumina and a calcium compound selected from the group consisting of calcium sulfate, calcium aluminate, calcium phosphate and calcium silicate wherein said promotor metal is present in a substantially reduced valence state and in amount which effects the removal of sulfur from said stream of cracked-gasoline or diesel fuel under conditions in a desulfurization zone such that there is formed a desulfurized fluid stream of cracked-gasoline or diesel fuel and a sulfurized sorbent;

(b) separating the resulting desulfurized fluid stream from said sulfurized sorbent;

(c) regenerating at least a portion of the separated sulfurized sorbent in a regeneration zone so as to remove at least a portion of the sulfur absorbed thereon;

(d) reducing the resulting desulfurized sorbent in an activation zone so as to provide a reduced valence promotor metal content therein which will affect the removal of sulfur from a stream of a cracked-gasoline or diesel fuel when contacted with same; and

thereafter

(e) returning at least a portion of the resulting desulfurized, reduced sorbent to said desulfurization zone.

25. A process in accordance with

claim 24

wherein said desulfurization is carried out at a temperature in the range of about 100°

F. to about 1000°

F. and a pressure in the range of about 15 to about 1500 psia for a time sufficient to affect the removal of sulfur from said stream.

26. A process in accordance to

claim 24

wherein said regeneration is carried out at a temperature in the range of about 100°

F. to about 1500°

F. and a pressure in the range of about 10 to about 1500 psia for a time sufficient to affect the removal of at least a portion of sulfur from the sulfurized sorbent.

27. A process in accordance with

claim 26

wherein there is employed air as a regeneration agent in said regeneration zone.

28. A process in accordance with

claim 24

wherein said regenerated sorbent is subjected to reduction with hydrogen in a hydrogenation zone which is maintained at a temperature in the range of about 100°

F. to about 1500°

F. and at a pressure in the range of about 15 to about 1500 psia and for a period of time to affect a substantial reduction of the valence of the nickel content of said sorbent.

29. A process in accordance with

claim 28

wherein said promotor metal is nickel.

30. A process in accordance with

claim 24

wherein said calcium compound is present in an amount such that the ratio of calcium compound to silica is in the range of about 0.1 to about 0.9.

31. A process in accordance with

claim 24

wherein the separated sorbent is stripped prior to introduction into said regeneration zone.

32. A process in accordance with

claim 24

wherein said regenerated sorbent is stripped prior to introduction into said activation zone.

33. The cracked-gasoline product of the process of

claim 24

.

34. The diesel fuel product of the process of

claim 24

.