Process and catalysts for eliminating sulphur compounds from the gasoline fraction

• US 6,846,406 B2
• Filed: 04/11/2003
• Issued: 01/25/2005
• Est. Priority Date: 10/11/2000
• Status: Expired due to Fees

• Current Assignee: Consejo Superior de Investigaciones Científicas,, Universidad Politecnica De Cataluna
• Original Assignee: Consejo Superior de Investigaciones Científicas,, Universidad Politecnica De Cataluna
• Inventors: Sánchez, Cristina Martinez, Canós, Avelino Corma, Domine, Marcelo Eduardo
• Primary Examiner(s): Griffin, Walter D.
• Assistant Examiner(s): Arnold, Jr., James
• Application Number:
  US10/412,116
• Publication Number:
  US 20030183555A1
• Time in Patent Office: 655 Days
• Field of Search: 208/208.R, 208/240, 208/245, 208/249, 208/196
• US Class Current: 208/208.00R
• CPC Class Codes: B01J 2229/32 Reaction with silicon compounds, e.g. TEOS, siliconfluoride
• CPC Class Codes: B01J 2229/37 Acid treatment
• CPC Class Codes: B01J 29/0308 Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 27/12 with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates plumbites or plumbates C10G19/06

Abstract

The object of the present invention is a process for the elimination of sulphur compounds from the gasoline fraction, characterized in that it comprises carrying out an oxidation reaction of said sulphur compounds using at least one organic-inorganic composite as a catalyst which comprises at least:

• • Si,
  • Ti and
  • silicon linked to carbon and using organic or inorganic hydro-peroxides as oxidating agents.

According to the process for the present invention, said organic or inorganic composite is obtained by means of a process that comprises a sililation stage during synthesis or by means of a process that comprises a post-synthesis sililation stage.

Claims

1. A process for eliminating sulphur compounds from a gasoline fraction characterised in that it comprises:

a step of making an oxidation reaction between said sulphur compounds and organic or inorganic hydro-peroxides as oxidation agents in the presence of at least one organic-inorganic composite as a catalyst, wherein said catalyst comprises at least the following;

Si,

Ti and

silicon linked to carbon

said oxidation reaction made at a temperature between 10 and 120°

C. and during a reaction time between 2 minutes and 24 hours, and

a step of separating the products of the oxidation reaction by distillation, extraction with a solvent or combination of both.

2. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, characterised in that said organic-inorganic composite that comprises at least:

Si,

Ti and

silicon linked to carbon

is obtained by means of a process which is characterised in that species that contain Si—

C bonds are introduced in said organic-inorganic composite in a stage during synthesis, by adding said species to a synthesis gel in a reaction mixture.

3. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, characterised in that said organic-inorganic composite that includes at least:

Si,

Ti and

silicon linked to carbon

is obtained by means of a process that comprises a post-synthesis sililation stage, wherein species that contain Si—

C bonds are introduced by reacting the inorganic component of the organic-inorganic composite with a silicon containing organic compound.

4. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, 2 or 3, characterised in that said organic-inorganic composite is a microporous molecular sieve that comprises at least:

Si,

Ti and

silicon linked to carbon.

5. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 4, characterised in that said microporous molecular sieve is a sieve with pores formed by rings with 12 or more members selected from the group consisting of zeolite, ALPO and SAPO.

6. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 5, characterised in that said microporous molecular sieve is a sieve selected from the group consisting of Ti Beta, Ti-ITQ-7, Ti-UTD-1, Ti-Mordenite, Ti-ALPO-5 and Ti-SAPO-5.

7. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 5, characterised in that said microporous molecular sieve is selected from the group consisting of Beta zeolite, any one of its polymorphs and a mixture thereof.

8. A process for the elimination of sulphur compounds from the gasoline fraction according to one of claims 4 to 7, characterised in that said microporous molecular sieve has the following chemical formula in its calcinated and anhydrous state:

y(A_1/nⁿ⁺XO₂);

tTO₂;

SiO₂;

xTiO₂

wherein;

X represents at least one trivalent element,

y is comprised between 0 and 0.2,

A represents mono-, di- or trivalent cations

n1, 2 or 3,

T represents at least one tetravalent element other than Si and Ti,

t is comprised between 0 and 1, and

x is comprised between 0.005 and 1000,

and in that said microporous molecular sieve is synthesised in the presence of compounds that contain Si—

C groups or are subject to a post-synthesis sililation stage creating Si—

C bonds.

9. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 6, characterised in that said microporous molecular sieve is synthesized in a medium selected between a medium that includes F⁻

and a medium that includes OH⁻

anions.

10. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 8, characterised in that said trivalent X element is selected from the group consisting of Fe, Al, B, Ga, Cr and mixtures thereof.

11. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 8, characterised in that said tetravalent T element is selected between V and Sn.

12. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 8, characterised in that t is comprised between 0 and 0.2.

13. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 8, characterised in that x is comprised between 0.01 and 100.

14. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, 2 or 3, characterised in that said organic-inorganic composite is a mesoporous molecular sieve which comprises at least:

Si,

Ti and

silicon linked to carbon.

15. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 14, characterised in that the the mesoporous molecular sieve used as a catalyst has a precursor of the following chemical formula:

y(Aⁿ⁺_1/nXO₂);

tTO₂;

(1-m)S, O₂;

XTiO₂;

mR_(4-p)SiO_p/2;

sS

A represents one or more mono-, di- or trivalent compensation cations or mixtures thereof,

x varies between 0.005 and 0.1;

X corresponds to a trivalent element

y is comprised between 0 and 0.2,

n=1, 2 or 3,

T corresponds to tetravalent elements other than Si and Ti

t is between 0 and 0.2

S is an organic compound,

s varies between 0 and 0.5,

m is comprised between 10<sup>−

6</sup> and 0.66,

p is comprised between 3 and 1,

R is an alkyl group, an aromatic group, or combination thereof, which comes from the sililating agent that contains the Si—

C bonds.

16. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 15, characterized in that the organic compound corresponding to group S is extracted by chemical means.

17. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 14, characterized in that the mesoporous molecular sieve is subjected to a post-synthesis treatment with a sililating agent that leads to the formation of new Si—

C bonds.

18. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 14, characterised in that said mesoporous molecular sieve is selected from the group consisting of Ti-MCM-41, TI-MCM-48, Ti-HMS, Ti-SBA-15, and Ti-TUD-1.

19. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 14, characterised in that the precursor of the mesoporous molecular sieve used as a catalyst has the following chemical formula:

y(A_1/nⁿ⁺XO₂);

tTO₂;

SiO₂;

xTiO₂;

sS

wherein;

x is comprised between 0.005 and 0.1;

X represents at least one trivalent element,

y is comprised between 0 and 0.2,

A represents one or more mono-, di- or trivalent compensation cations or mixtures thereof,

n1, 2 or 3,

T represents tetravalent elements other than Si and Ti,

t is comprised between 0 and 0.2,

S represents an organic compound and

s varies between 0 and 0.5.

20. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 16, characterized in that said trivalent element is selected from the group consisting of between Fe, Al, B, Ga, Cr and mixtures thereof.

21. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that said tetravalent T element is selected between V and Sn.

22. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that t is comprised between 0 and 0.2.

23. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is selected from the group consisting of a cationic, anionic and neutral surface active agent.

24. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is a cationic surface active agent selected from among:

a compound of the formula R₁R₂R₃Q⁺ wherein Q is nitrogen or phosphorus and where at least one of the R₁, R₂, R₃ or R₄ substituent is an alkyl or aryl group containing more than 6 atoms of carbon and less than 36, and each one of the remaining R₁, R₂, R₃ or R₄ groups is a hydrogen or aryl or alkyl group with less than five carbons,

a geminal surface active agent with the formula R₁R₂R₃QR₄QR₁R₂R₃ or R₁R₂R₃Q(R₄R₅QR₆QR₄R₅)Q_nR₁R₂R₃, where Q is a nitrogen or phosphorus and at least one of the R₁-R₆ substituent is an alkyl or aryl group with more than six atoms of carbon and less than 36, and each one of the remaining R₁-R₆ groups are hydrogens or aryl or alkyl groups with less than five atoms of carbon or mixtures thereof, or two of the R₁, R₂, R₃ or R₄ groups can be interconnected leading to cycled compounds.

25. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is a cationic surface active agent selected from the group consisting of cetyl tri-methyl ammonium, dodecyl tri-methyl ammonium, cetyl piridinium, ant cetyl methylphosphonium.

26. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is a cationic surface active agent and is introduced in the composition of a synthesis gel in the form of an hydroxide, halide, nitrate, sulphate, carbonate or silicate or a mixture thereof.

27. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is a neutral surface active agent selected from the group consisting of:

a compound of the formula R₁R₂R₃Q wherein Q is nitrogen or phosphorus and where at least one of the R₁, R₂, or R₃ substituents is an alkyl or aryl group containing more than 6 atoms of carbon and less than 36, and each one of the remaining R₁, R₂, or R₃ groups is a hydrogen or aryl or alkyl group with less than five carbons,

a compound from formula nR-EO that consists of alkylpolyethylene oxides, oxides of alkyl-aryl-polyethylene and co-polymers of alkylpolyproylene and alkylethylene,

esters derived from fatty acids obtained by a reaction with short chain alcohols, sugars, amino acids and amines, and

polymers or co-polymers derived from polypropylene, polyethylene, polyacrylamide or polyvinyl alcohol.

28. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is a neutral surface active agent selected from the group consisting of lisolecitin, lecitin, dodecyl penta-oxyethelene ether, phosphatidyl di-lauryl di-ethanol amine, di-galactose diglyceride and monogalactose diglyceride.

29. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19 or 27, characterized in that S is a neutral surface active agent selected from the group consisting of dodecylamine, cetylamine and cetylpyridine.

30. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that S is an anionic surface active agent that responds to the formula RQ⁻

wherein R is an alkyl or aryl group containing more than 6 atoms of carbon and less than 36, and Q is a sulphate, carboxylic or phosphate group.

31. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19 or 30, characterized in that S is an anionic surface active agent selected from the group consisting of dodecyl sulphate, stearic acid, OT Aerosol and phospholipids.

32. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19 or 30, characterized in that S is an anionic surface active agent selected between phosphatidyl choline and phosphatyl di-ethanolamine.

33. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that the organic compound corresponding to the S group is extracted by calcination in air, N₂ or another inert gas at temperatures between 300°

and 700°

C., and the mesoporous molecular sieve is then subjected to a sililation treatment by means of which Si—

C bonds are formed.

34. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that the organic compound corresponding to the S group is extracted by chemical means and the mesoporous molecular sieve is then subjected to a sililation treatment by means of which Si—

C bonds are formed.

35. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 34, characterized in that said organic compound is extracted by means of treatment with a mineral acid or organic solution in a solvent selected from the group consisting of water, alcohols, hydrocarbons and a mixture thereof and is then subjected to a sililation treatment by means of which Si—

C bonds are formed.

36. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 19, characterized in that said mesoporous molecular sieve includes Ge, V, Sn or mixtures thereof, as well as Si and Ti.

37. A process the elimination of sulphur compounds from the gasoline fraction according to claim 34, characterized in that said mesoporous molecular sieve also comprises Al, B, Ga, Fe, Cr or mixtures thereof.

38. A process the elimination of sulphur compounds from the gasoline fraction according to claim 1, 2 or 3, characterized in that said organic-inorganic composite is a mesoporous molecular sieve that comprises at least:

Si,

Ti and

silicon linked to carbon

and consists of amorphous inorganic siliceous solids, chemically combined with Ti in a ratio of between 0.2 and 8% by weight of Ti, in the form of an oxide on the total catalyst, and which contain silicon linked to carbon.

39. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 38, characterized in that said amorphous inorganic siliceous solids include at least 90% silica.

40. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 38, characterized in that said amorphous inorganic siliceous solids are pyrogenic silicas selected between cab-o-sil and Aerosil with specific surfaces of between 40 and 450 m^2·

g<sup>−

1</sup> and a particle size of between 0.007 and 0.05 microns.

41. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 39, characterized in that said amorphous inorganic siliceous solids are synthetic inorganic oxides of silicon.

42. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 41, characterized in that said synthetic inorganic oxide of silicon is silica gel.

43. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 38, characterized in that said amorphous inorganic siliceous solid, further to Si and Ti, also comprises elements selected from the group consisting of V, B, Zr, Mo and mixtures thereof in a percentage of the total weight, and in the form of oxides, of less than 8%.

44. A process for the elimination of sulphur compounds from the gasoline fraction according to any of claims 38 to 43, characterized in that said amorphous inorganic siliceous solid includes quantities of between 0.01 and 4% by weight of promoters of the alkaline metal or alkali-earth groups or mixtures thereof, in the form of oxides.

45. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, characterized in that said oxidation reaction is carried out in a discontinuous reactor, a CSTR reactor, in a fixed bed continuous reactor, in a fluidised bed reactor, or a boiling bed reactor.

46. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 45, characterized in that said oxidation is carried out in a discontinuous reactor, with a weight ratio of the gasoline fraction to the catalyst of between 5 and 200 and a weight ratio between the gasoline fraction and the oxidising agent of between 200 to 10.

47. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 46, characterized in that said weight ratio of the gasoline fraction to the catalyst is comprised between 10 and 100.

48. A process the elimination of sulphur compounds from the gasoline fraction according to claim 46, characterized in that said weight ratio of the gasoline fraction and the oxidating agent is between 100 and 30.

49. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, characterized in that said oxidation reaction is carried out at a temperature of between 20 and 80°

C.

50. A process for the elimination of sulphur compounds from the gasoline fraction according to claim 1, characterized in that said oxidation reaction includes separation of the products by means of a stage selected between distillation, extraction and both, with a solvent and total or partial re-cycling of the non-reacted products to the reactor.