Catalyst composition, its preparation and use

• US 9,029,283 B2
• Filed: 07/28/2008
• Issued: 05/12/2015
• Est. Priority Date: 07/31/2007
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Berg-Slot, Johanna Jacoba, Domokos, Lszl, Van Vegchel, Ingrid Maria
• Primary Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US12/671,086
• Publication Number:
  US 20100249479A1
• Time in Patent Office: 2,479 Days
• Field of Search: 502/60, 502/63, 502/64.66, 502/71, 502/73, 502/74, 502/77
• US Class Current: 502/66
• CPC Class Codes: B01J 2229/16 to increase the Si/Al ratio; Dealumination
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 23/626 with tin
• CPC Class Codes: B01J 29/405 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• CPC Class Codes: B01J 29/44 Noble metals
• 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: C07C 15/04 Benzene
• CPC Class Codes: C07C 2529/44 Noble metals
• CPC Class Codes: C07C 4/18 Catalytic processes
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A catalyst composition which comprises: a) a carrier which comprises at least 30 wt % of a binder selected from silica, zirconia and titania; at least 20 wt % of a pentasil zeolite, having a bulk silica to alumina ratio in the range of from 20 to 150 and being in its H⁺ form; and less than 10 wt % of other components, all percentages being on the basis of total carrier; b) platinum in an amount in the range of from 0.001 to 0.1 wt %, on the basis of total catalyst; and c) tin in an amount in the range of from 0.01 to 0.5 wt %, on the basis of total catalyst; its preparation and use; are provided.

Claims

1. A catalyst composition which comprises:

a surface-modified carrier, wherein the surface-modified carrier comprises a carrier that has been subjected to a dealumination treatment by contacting the carrier with either an aqueous solution of fluorosilicate salt of the formula (A)_2,b SiF₆, wherein A is a metallic or non-metallic cation other than H⁺ having valence b and b is the valence of A, or an aqueous solution of hexafluorosilicate salt or dicarboxylic acid, wherein the carrier comprises from 30 wt % to 80 wt % of a silica binder comprising a powder form silica and a silica sol in a weight ratio of powder form to sol in the range of from 1;

1 to 10;

1; and

20 wt % to 70 wt % of a pentasil zeolite, having an average crystallite size in the range of from 1 to 10 μ

m and a bulk silica to alumina ratio in the range of from 20 to 150 and being in its H⁺ form, with all percentages being on the basis of total carrier and, wherein the dealumination treatment provides a dealumination ratio in the range of from 1.1 to 3.0; and

platinum in an amount in the range of from 0.001 to 0.1 wt %, on the basis of total catalyst; and

tin in an amount in the range of from 0.01 to 0.5 wt %, on the basis of total catalyst.

2. The catalyst composition as claimed in claim 1, wherein the carrier is composed of in the range of from 30 to 80 wt % silica, and in the range of from 20 to 70 wt % zeolite.

3. The catalyst composition as claimed in claim 2, wherein the dealumination treatment of the carrier includes subjecting the carrier to a dealumination treatment with ammonium hexafluorosilicate.

4. The catalyst composition as claimed in claim 3, wherein the pentasil zeolite is one having an MFI configuration.

5. The catalyst composition as claimed in claim 4, wherein the zeolite having the MFI configuration is ZSM-5.

6. The catalyst composition as claimed in claim 5, wherein the ZSM-5 has a SAR in the range of from 20 to 50 and is present in the carrier in an amount in the range of from 20 to 50 wt %.

7. The catalyst composition as claimed in claim 6, wherein the silica has a mean particle size in the range of from 2 to 60 μ

m.

8. A catalyst composition, comprising:

a carrier comprising from 30 to 80 wt % of a dealuminated pentasil zeolite, wherein the dealuminated pentasil zeolite is prepared with a starting pentasil zeolite having an average crystallite size in the range of from 1 to 10 μ

m and a SAR in the range of from 20 to 150 that has been dealuminated to a dealumination ratio in the range of from 1.1 to 3.0, and from 20 to 70 wt % silica binder, comprising a mixture of a powder form silica and a silica sol in a weight ration of powder form to sol in the range of from 1;

1 to 10;

1 with the weight percentages being based on the total carrier;

a platinum component in an amount in the range of from 0.001 to 0.1 wt %, based on the total catalyst; and

a tin component in an amount in the range of from 0.01 to 0.5 wt %, based on the total catalyst.

9. A catalyst composition as recited in claim 8, wherein said carrier comprises from 30 to 50 wt % of said dealuminated pentasil zeolite and from 50 to 70 wt % of said silica binder.

10. A catalyst composition as recited in claim 8, wherein the pentasil zeolite of said dealuminated pentasil zeolite is of the type having an MFI configuration.

11. A catalyst composition as recited in claim 8, wherein the dealuminated pentasil zeolite is surface dealuminated by subjecting the pentasil zeolite of said dealuminated pentasil zeolite to a dealumination treatment with ammonium hexafluorosilicate.

12. A catalyst composition as recited in claim 8, wherein said pentasil zeolite is ZSM-5.

13. A catalyst composition as recited in claim 8, wherein said dealumination ratio is in the range of from 1.3 to 2.5.

14. A catalyst composition, comprising:

a surface-modified carrier, wherein said surface-modified carrier comprises a carrier that has been subjected to a dealumination treatment by contacting said carrier with either an aqueous solution of fluorosilicate salt of the formula (A)_2/bSiF₆, wherein A is a metallic or non-metallic cation other than H⁺ having valence b and b is the valence of A, or an aqueous solution of hexafluorosilicate salt or dicarboxylic acid, wherein said carrier comprises from 20 to 70 wt % of a pentasil zeolite, having an average crystallite size in the range of from 1 to 10 μ

m, that has not been subjected to said dealumination treatment of said carrier and from 30 to 80 wt % silica binder, comprising a mixture of a powder form silica and a silica sol in a weight ratio of powder form to sol in the range of from 1;

1 to 10;

1, with the weight percentages being based on the total carrier, and wherein said dealumination treatment provides for a dealumination ratio in the range of from 1.1 to 3.0.

a platinum component in an amount in the range of from 0.001 to 0.1 wt %, based on the total catalyst; and

a tin component in an amount in the range of from 0.01 to 0.5 wt %, based on the total catalyst.

15. A catalyst composition as recited in claim 14, wherein said carrier comprises from 30 to 50 wt % of said non-surface modified pentasil zeolite and from 50 to 70 wt % silica.

16. A catalyst composition as recited in claim 14, wherein the pentasil zeolite of said dealuminated pentasil zeolite is of the type having an MFI configuration.

17. A catalyst composition as recited in claim 14, wherein said surface-modified carrier is dealuminated by subjecting the pentasil zeolite of said carrier to a dealumination treatment with ammonium hexafluorosilicate.

18. A catalyst composition as recited in claim 14, wherein said non-surface modified pentasil zeolite is ZSM-5.