# US 9,433,925 B2 · Method of preparing epoxidation catalysts

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- Number: US 9,433,925 B2
- Document ID: US9433925B2
- Status: Granted
- Kind: B2
- Application number: 14/602,410
- Filed: 2015-01-22
- Published: 2015-12-31
- Granted: 2016-09-06
- Earliest claimed: 2014-01-22
- Assignees: Lyondell Chemical Technology, L.P.
- Applicants: Lyondell Chemical Technology, L.P.
- Inventors: Roger Grey; Debra Jackson; Daniel F. White; Sandor Nagy
- Web page: https://patentgrep.com/patent/US9433925B2

## CPC

- B01J 21/08: Silica
- B01J 21/06: Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J 29/0308: {Mesoporous materials not having base exchange properties, e.g. Si-MCM-41}
- B01J 29/89: Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)}
- B01J 35/60: characterised by their surface properties or porosity
- B01J 37/02: Impregnation, coating or precipitation ({B01J37/0009 and B01J37/0018 take precedence } ; protection by coating B01J33/00)
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C07D 301/12: with hydrogen peroxide or inorganic peroxides or peracids
- C07D 301/19: with organic hydroperoxides
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 37/0209: {involving a reaction between the support and a fluid}
- B01J 2229/186: not in framework positions
- B01J 2229/32: Reaction with silicon compounds, e.g. TEOS, siliconfluoride
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

A method of preparing epoxidation catalysts is disclosed. The method comprises: (a) adding an inorganic siliceous solid to a column to produce a solid-filled column; (b) adding to the solid-filled column a solution comprising titanium tetrachloride and a hydrocarbon solvent to produce a titanium tetrachloride-impregnated solid; and (c) calcining the titanium tetrachloride-impregnated solid at a temperature from 500° C. to 1000° C. to produce the catalyst. The inorganic siliceous solid has a pore volume of at least 0.8 cm3/g.

## Claims

### Claim 1

A method of preparing a catalyst, comprising:
(a) adding an inorganic siliceous solid to a column to produce a solid-filled column;
(b) adding to the solid-filled column a solution comprising titanium tetrachloride and a hydrocarbon solvent to produce a titanium tetrachloride-impregnated solid; and
(c) calcining the titanium tetrachloride-impregnated solid at a temperature from 500-1000° C. under a nitrogen stream to produce the catalyst wherein the catalyst is prepared in the absence of steam.

### Claim 2 (depends on 1)

The method of claim 1, wherein the titanium tetrachloride-impregnated solid from step (b) is washed with additional hydrocarbon solvent selected from toluene and hexane prior to calcination in step (c).

### Claim 3 (depends on 1)

The method of claim 1, wherein the catalyst from step (c) is washed with a C1-C4 alcohol to produce an alcohol-washed catalyst.

### Claim 4 (depends on 3)

The method of claim 3, wherein the alcohol-washed catalyst is reacted with a silylating agent to produce a silylated catalyst.

### Claim 5 (depends on 1)

The method of claim 1, wherein the siliceous solid has a surface area from 25-1000 m2/g.

### Claim 6 (depends on 1)

The method of claim 1, wherein adiabatic temperature changes that occur in step (b) are controlled by adjusting the concentration of titanium tetrachloride in the solution, the rate of addition of the solution to the column, or both.

### Claim 7 (depends on 1)

The method of claim 1, wherein the catalyst comprises from 0.5 to 10 wt. %, based on the amount of catalyst, of titanium.

### Claim 8 (depends on 1)

A process for forming an epoxide, comprising contacting a solution of an olefin and a peroxide with a catalyst produced by the method of claim 1 to produce the epoxide.

### Claim 9 (depends on 8)

The process of claim 8, wherein the olefin is propylene.

### Claim 10 (depends on 8)

The process of claim 8, wherein the peroxide is selected from the group consisting of hydrogen peroxide and organic hydroperoxides.

### Claim 11 (depends on 10)

The process of claim 10, wherein the organic hydroperoxide is selected from the group consisting of tert-butylhydroperoxide and ethylbenzene hydroperoxide.

### Claim 12 (depends on 8)

The process of claim 8, wherein the peroxide conversion is at least 50%.

### Claim 13 (depends on 8)

The process of claim 8, wherein peroxide selectivity is greater than 95%.

### Claim 14

A method of preparing a catalyst, comprising:
(a) adding a mesoporous siliceous solid comprising a pore volume of 0.98-3.2 cm3/g dried at a temperature of 200° C. for 2 hours to a column to produce a solid-filled column;
(b) adding to the solid-filled column a solution comprising titanium tetrachloride and a hydrocarbon solvent selected from toluene and hexane to produce a titanium tetrachloride-impregnated solid; and
(c) calcining the titanium tetrachloride-impregnated solid at a temperature from 600-700° C. for 2-4 hours under a 100 ml/min-nitrogen stream to produce the catalyst wherein the catalyst is prepared in the absence of steam.

### Claim 15 (depends on 3)

The method of claim 3, wherein the C1-C4 alcohol is selected from methanol and ethanol.

### Claim 16 (depends on 1)

The method of claim 1, wherein the inorganic siliceous solid has a pore volume of at least 0.8 cm3/g.