Process for preparing microporous crystalline titanium silicate

• US 20040024075A1
• Filed: 05/30/2003
• Published: 02/05/2004
• Est. Priority Date: 07/31/2002
• Status: Active Grant

• Current Assignee: Council of Scientific & Industrial Research
• Original Assignee: Council of Scientific & Industrial Research
• Inventors: Malshe, Kusum Madhukar, Dongare, Mohan Keraba, Patil, Pratap Tukaram
• Granted Patent: US 6,991,678 B2
• Time in Patent Office: Days
• US Class Current: 521/153
• CPC Class Codes: C01B 37/005 Silicates, i.e. so-called metallosilicalites or metallozeosilites

Abstract

A process for the preparation of crystalline microporous titanium silicates using ethylsilicate-40 and titanium peroxide as silicon and titanium sources respectively is described. The process permits a significant decrease in the production cost of titanium silicate containing higher amount of titanium (Si/Ti=20) because of cheaper raw materials as well as reduction in the quantity of tetarpropylammonium hydroxide (TPAOH) template (SiO₂:TPAOH=1:0.06-0.1) required for preparation. The material obtained by the present invention is useful as an active catalyst in the reactions such as oxidation of hydrocarbons, alcohols, sulphides, and thioethers.

Claims

1. A process for preparation of microporous, crystalline titanium silicate having a silicalite-1 structure and a chemical composition of formula xTiO₂:

(1−

x) SiO₂ wherein x is in the range of 0.001 to 0.05, which comprises;

a) adding a titanium source to ethyl silicate with or without an organic solvent to obtain a homogenous gel,

b) hydrolyzing the homogeneous gel obtained in step (a) by adding an organic base to the above said resultant gel with silica to organic base ratio in the range of 1;

0.06 to 0.15 followed by adding deionised water when yellow white gel turns into greenish white gel,

c) stirring the above greenish white gel for about 1 hr,

d) heating the stirred greenish white gel at autogenous pressure, at a temperature in the range of 100 to 110°

C. for a period of 1-4 days to obtain a solid composite material, separating the resultant solid composite material, drying and calcining the resultant solid composite material at a temperature in the range of 350-550°

C. in the presence of air to obtain the desired product.

2. A process as claimed in claim 1 wherein the titanium source comprises a solution of titanium peroxide.

3. A process as claimed in claim 1 wherein the organic base comprises aqueous tetrapropyl ammonium hydroxide (TPAOH).

4. A process as claimed in claim 1 wherein the ethyl silicate is used as a source of silicon oxide.

5. A process as claimed in claim 1 wherein the ethyl silicate used is ethyl silicate 40.

6. A process as claimed in claim 5 wherein the ethyl silicate 40 used is a condensed product of orthosilicate selected from the group consisting of tetramer, pentamer and hexamer.

7. A process as claimed in claim 1 wherein the organic solvent used is an alcohol with 2 to 5 carbon atoms.

8. A process as claimed in claim 7 wherein the alcohol is selected from the group consisting of ethyl, propyl and butyl.

9. A process as claimed in claim 1 wherein the silica to TPAOH ratio used is 1:

0.1.

10. A process as claimed in claim 1 wherein the starting mixture has a chemical molar composition of 0.0.6-R₄N⁺OH:

0.001-0.05TiO₂;

SiO₂;

25-55 H₂O where R is a propyl group.