IP Library Granted Patent US 8,168,562
Granted Patent B2
US 8,168,562 · App. 11/346,500 · Granted May 1, 2012

Preparation of palladium-gold catalysts

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Quick Facts
Patent No.
US 8,168,562
App. No.
11/346,500
Granted
May 1, 2012
Kind
B2
Abstract

A new method for preparing supported palladium-gold catalysts is disclosed. The method comprises sulfating a titanium dioxide support, calcining the sulfated support, impregnating the calcined support with a palladium salt, a gold salt, and an alkali metal or ammonium compound, calcining the impregnated support, and reducing the calcined support. The resultant supported palladium-gold catalysts have increased activity and stability in the acetoxylation.

Claims (21)

1. A method for preparing a supported palladium-gold catalyst, said method comprising

(a) sulfating a titanium dioxide support with a sulfating agent selected from the group consisting of persulfuric acid, its salts, and mixtures thereof;

(b) calcining the sulfated support;

(c) impregnating the calcined support with a palladium salt, a gold salt, and an alkali metal or ammonium compound;

(d) calcining the impregnated support; and

(e) reducing the calcined support from step (d) to form the supported palladium-gold catalyst.

2. The method of claim 1 , wherein the sulfating agent is ammonium persulfate.

3. The method of claim 1 , wherein the calcining in step (b) is performed at a temperature within the range of 600° C. to 900° C.

4. The method of claim 3 , wherein the temperature is within the range of 650° C. to 750° C.

5. The method of claim 1 , wherein the alkali metal or ammonium compound is selected from the group consisting of hydroxides, carbonates, bicarbonates, metasilicates, and mixtures thereof.

6. The method of claim 1 , wherein the alkali metal or ammonium compound is a carbonate or bicarbonate.

7. The method of claim 1 , wherein the palladium and gold salts are selected from the group consisting of palladium chloride, sodium chloropalladite, palladium nitrate, palladium sulfate, auric chloride, tetrachloroauric acid, sodium tetrachloroaurate, and mixtures thereof.

8. The method of claim 1 , wherein the calcination of step (d) is performed in a non-reducing atmosphere at a temperature within the range of 100° C. to 600° C.

9. The method of claim 8 , the non-reducing atmosphere is selected from the group consisting of helium, nitrogen, argon, neon, nitrogen oxides, oxygen, air, carbon dioxide, and mixtures thereof.

10. The method of claim 8 , wherein the calcination temperature is within the range of 100° C. to 300° C.

11. The method of claim 1 , wherein the reduction is performed in hydrogen or a mixture of hydrogen and an inert gas.

12. The method of claim 11 , wherein the reduction is performed at a temperature within the range of 300° C. to 600° C.

13. The method of claim 11 , wherein the reduction is performed at a temperature within the temperature of 450° C. to 550° C.

14. The method of claim 1 , which further comprises treating the supported palladium-gold catalyst from step (e) with a potassium salt.

15. A supported palladium-gold catalyst prepared by the method of claim 1 .

16. A method for preparing vinyl acetate comprising oxidizing ethylene in the presence of acetic acid and the supported palladium-gold catalyst of claim 15 .

Assignments (16)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 16, 2014
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: LYONDELLBASELL ACETYLS, LLC
Reel/Frame 033182/0019 →
RELEASE OF SECURITY INTEREST Recorded Jan 23, 2014
From: CITIBANK, N.A.
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.
Reel/Frame 032125/0296 →
RELEASE OF SECURITY INTEREST Recorded Jan 23, 2014
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.
Reel/Frame 032137/0156 →
APPOINTMENT OF SUCCESSOR ADMINISTRATIVE AGENT Recorded Jan 23, 2014
From: UBS AG, STAMFORD BRANCH
To: BANK OF AMERICA, N.A.
Reel/Frame 032137/0639 →
RELEASE OF SECURITY INTEREST Recorded Jan 23, 2014
From: BANK OF AMERICA, N.A.
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.
Reel/Frame 032138/0134 →
RELEASE OF SECURITY INTEREST Recorded Jan 23, 2014
From: DEUTSCHE BANK TRUST COMPANY AMERICAS
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.
Reel/Frame 032123/0799 →
SECURITY AGREEMENT Recorded May 19, 2010
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 024402/0681 →
SECURITY AGREEMENT Recorded May 18, 2010
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 024397/0818 →
SECURITY AGREEMENT Recorded May 7, 2010
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 024342/0801 →
SECURITY AGREEMENT Recorded May 6, 2010
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERAL AGENT
Reel/Frame 024342/0421 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, LP
Reel/Frame 024337/0285 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, LP
Reel/Frame 024337/0020 →
SECURITY AGREEMENT Recorded Oct 30, 2009
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 023449/0138 →
SECURITY AGREEMENT Recorded Apr 9, 2009
From: LYONDELL CHEMICAL TECHNOLOGY, L.P.
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT
Reel/Frame 022708/0830 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE'S NAME, PREVIOUSLY RECORDED AT REEL 017542 FRAME 0938. Recorded Jul 20, 2006
From: AUGUSTINE, STEVEN M.
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.
Reel/Frame 017968/0385 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 2, 2006
From: AUGUSTINE, STEVEN M.
To: MILLENNIUM SPECIALTY CHEMICALS INC.
Reel/Frame 017542/0938 →