Anatase polymorph titania-bound ZSM-12 zeolite composition and method of making and using such composition

Patent metadata

Field	Value
Publication number	US-10076747-B2
Application number	US-201213715192-A
Country	US
Kind code	B2
Filing date	Dec 14, 2012
Priority date	Dec 16, 2011
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

Presented is a composition useful in the catalytic dewaxing of a waxy hydrocarbon feedstock. The composition includes a mixture of ZSM-12 zeolite and titania and may further include a noble metal. The ZSM-12 zeolite preferably has a high silica-to-alumina ratio within its framework. The mixture may be dealuminated either by acid leaching using a fluorosilicate salt or by steam treating.

First claim

What is claimed is:

1. A dewaxing catalyst composition, comprising: a calcined particle, consisting essentially of ZSM-12 zeolite having a silica-to-alumina ratio of at least 50:1 and titania powder in an amount exceeding 50% anatase titania with the balance being in either in a rutile form or a brookite form or a combination of both forms and having a surface area in the range of from 10 m 2 /gm to 700 m 2 /gm, that is either acid treated or steam treated; and a noble metal component selected from the group of noble metals consisting of platinum and palladium that is incorporated into said particle after said acid treatment or said steam treatment at a noble metal concentration in the range upwardly to about 3 wt. % based on the noble metal as an element and the total dry weight of said dewaxing catalyst composition.

2. A dewaxing catalyst composition as recited in claim 1 , wherein said ZSM-12 zeolite is present in said dewaxing catalyst composition in an amount of at least 10% wt. and at most 70% wt. and said titania is present in said dewaxing catalyst composition in an amount of at least 30% wt. and no more than 90% wt., with such % wt. being based on the dry weight of said composition.

3. A dewaxing catalyst composition as recited in claim 2 , wherein said calcined particle is treated with an acid solution to thereby provide dealuminated ZSM-12 zeolite.

4. A dewaxing catalyst composition as recited in claim 3 , wherein said ZSM-12 zeolite has a silica-to-alumina ratio greater than 70:1.

5. A dewaxing catalyst composition as recited in claim 1 , wherein said ZSM-12 zeolite has a silica-to-alumina molar ratio greater than 70:1.

6. A dewaxing catalyst composition as recited in claim 1 , wherein said calcined particle is substantially free of silica other than the silica contained in the ZSM-12 zeolite framework.

7. A dewaxing catalyst composition as recited in claim 1 , wherein said mixture calcined particle is substantially free of alumina other than the alumina contained in the ZSM-12 zeolite framework.

8. A dewaxing catalyst composition as recited in claim 1 , wherein said titania has a substantial absence of silica.

9. A dewaxing catalyst composition as recited in claim 1 , wherein said titania has a substantial absence of alumina.

10. A dewaxing composition as recited in claim 3 , wherein the acid treatment of said calcined particle with said acid solution comprises contacting said calcined particle with an aqueous solution of a fluorosilicate salt of the formula (A) 2/b SiF 6 , wherein A is a metallic or non-metallic cation other than H + having a valence of b.

11. A dewaxing composition as recited in claim 10 , wherein said aqueous solution has a pH in the range of from 2 to 8.

12. A dewaxing composition as recited in claim 11 , wherein the acid treatment includes contacting said calcined particle with said aqueous solution for a contacting time period in the range of from 0.5 hours to 20 hours and at a contacting temperature in the range of from 20° C. to 100° C.

13. A process for the catalytic dewaxing of a hydrocarbon oil feed, wherein said process comprises: contacting under catalytic dewaxing conditions said hydrocarbon oil feed with the composition of claim 1 .

14. A method for preparing a dewaxing catalyst composition, wherein said method comprises: preparing a formed particle that is dried and calcined to provide a calcined particle consisting essentially of ZSM-12 zeolite having a silica-to-alumina ratio of at least 50:1 and titania powder in an amount exceeding 50% anatase titania with the balance being in either in a rutile form or a brookite form or a combination of both forms and having a surface area in the range of from 10 m 2 /gm to 700 m 2 /gm; and treating said calcined particle with either steam or an acid solution to thereby provide a treated particle comprising dealuminated zeolite; and incorporating into said treated particle a noble metal selected from the group consisting of platinum and palladium at a noble metal concentration in the range upwardly to about 3 wt. % based on the metal as an element and the total dry weight of said dewaxing catalyst composition.

15. A method as recited in claim 14 , wherein the treating of said calcined particle is with an acid solution to thereby provide an acid treated particle comprising dealuminated zeolite.

16. A composition prepared by the method of claim 14 .

Assignees

• Shell Oil Co

Inventors

• Geerinck Peter
• Jongkind Hermanus
• Rigutto Marcello Stefano

Classifications

• B01J29/06 Primary

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• B01J29/7469

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• B01J29/7034 Primary

  MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3 · CPC title

• C10G47/20

  the catalyst containing other metals or compounds thereof · CPC title