# US 9,434,683 B2 · Titanium-silicalite molecular sieve, method for preparing the same and method for preparing cyclohexanone oxime using the molecular sieve

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- Number: US 9,434,683 B2
- Document ID: US9434683B2
- Status: Granted
- Kind: B2
- Application number: 13/350,045
- Filed: 2012-01-13
- Published: 2013-02-14
- Granted: 2016-09-06
- Earliest claimed: 2011-08-11
- Assignees: China Petrochemical Development Corporation
- Applicants: Ya-Ping Chen; Cheng-Fa Hsieh; Pin-To Yao; Chien-Chang Chiang
- Inventors: Ya-Ping Chen; Cheng-Fa Hsieh; Pin-To Yao; Chien-Chang Chiang
- Web page: https://patentgrep.com/patent/US9434683B2

## CPC

- C07C 249/04: of oximes
- B01J 29/89: Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)}
- C01B 37/005: {Silicates, i.e. so-called metallosilicalites or metallozeosilites}
- C07C 251/44: with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
- B01J 29/87: Gallosilicates; Aluminogallosilicates; Galloborosilicates {(B01J29/005 takes precedence)}
- B01J 2229/183: in framework positions
- C01B 39/06: Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements {, i.e. by direct or secondary synthesis}
- C01B 39/082: {Gallosilicates}
- C01B 39/085: {Group IVB- metallosilicates}
- C07C 2601/14: The ring being saturated
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

The present invention provides a titanium-silicalite molecular sieve and a method for preparing the same. The method includes the steps of preparing a mixture of a titanium source, a silicon source, a metal source selected from IIA to IVA elements and a template agent; heating the mixture to form a gel mixture; heating the gel mixture in a water bath; and calcining the gel mixture after the gel mixture in the water bath to form the titanium-silicalite molecular sieve. The present invention further provides a method for preparing cyclohexanone oxime by using the titanium-silicalite molecular sieve as the catalyst which results in high conversion rate, high selectivity and high usage efficiency of hydrogen peroxide.

## Claims

### Claim 1

A method for preparing a titanium-silicalite molecular sieve, comprising the steps of:
preparing a mixture of a titanium source, a silicon source, a metal source and a template agent, wherein the metal source is at least one selected from IIA to IVA elements, and the template agent is dissolved in an alcohol solvent;
heating the mixture to form a gel mixture;
heating the gel mixture in a water bath; and
calcining the gel mixture after heating the gel mixture in the water bath to form the titanium-silicalite molecular sieve.

### Claim 2 (depends on 1)

The method of claim 1, wherein the titanium source is tetraalkyl titanate.

### Claim 3 (depends on 1)

The method of claim 1, wherein the silicon source is tetraalkyl silicate or polyethoxysiloxane.

### Claim 4 (depends on 1)

The method of claim 1, wherein the template agent is tetrapropylammonium hydroxide.

### Claim 5 (depends on 1)

The method of claim 1, wherein the titanium source, the silicon source and the template agent are mixed prior to being further mixed with the metal source.

### Claim 6 (depends on 1)

The method of claim 1, wherein the template agent is dissolved in the alcohol solvent in a concentration of 5 wt % to 50 wt %, and the gel mixture is heated to remove the alcohol solvent.

### Claim 7 (depends on 6)

The method of claim 6, wherein after the gel mixture is heated to remove the alcohol solvent, the gel mixture is mixed with water.

### Claim 8 (depends on 6)

The method of claim 6, wherein the alcohol solvent is one or more selected from the group consisting of methanol, ethanol, isopropanol, n-butanol and tert-butanol.

### Claim 9 (depends on 1)

The method of claim 1, wherein a molar ratio of the template agent to the silicon source is less than or equal to 0.5.

### Claim 10 (depends on 1)

The method of claim 1, wherein the metal source is selected from the group consisting of an acidic metal salt, a metal alkoxide and a metal complex.

### Claim 11 (depends on 10)

The method of claim 10, wherein the metal source is dissolved in water to be in an aqueous form prior to being mixed with the titanium source, the silicon source and the template agent to form the mixture.

### Claim 12 (depends on 1)

The method of claim 1, wherein a molar ratio of titanium to silicon in the titanium-silicalite molecular sieve is in a range of from 0.005 to 0.1, and a molar ratio of a metal in a metal oxide to the silicon in the titanium-silicalite molecular sieve is in a range of from 0.00001 to 0.05.

### Claim 13 (depends on 1)

The method of claim 1, further comprising the steps of:
after forming the gel mixture, mixing the gel mixture with water or colloidal silica; and
heating the gel mixture mixed with the water or the colloidal silica in the water bath.

### Claim 14 (depends on 13)

The method of claim 13, wherein the colloidal silica is silicon dioxide gel solution, and an amount of the silicon dioxide is 0.1 to 50 wt % of the colloidal silica.

### Claim 15 (depends on 13)

The method of claim 13, wherein a weight ratio of the colloidal silica to the gel mixture is in a range of from 0.001:1 to 0.5:1.