Methods of catalytic hydrogenation for ethylene glycol formation

Patent metadata

Field	Value
Publication number	US-10086364-B2
Application number	US-201514749441-A
Country	US
Kind code	B2
Filing date	Jun 24, 2015
Priority date	Jun 26, 2014
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

Embodiments described herein generally relate to hydrogenation catalysts, syntheses of hydrogenation catalysts, and apparatus and methods for hydrogenation. Methods for forming a hydrogenation catalyst may include mixing a silica generating precursor with a copper precursor and adding an ammonium salt to an end pH of between about 5 to about 9. Methods for hydrogenating an oxalate may include forming a reaction mixture by flowing a hydrogenation catalyst to a reactor, flowing a hydrogen source to the reactor, and flowing an oxalate to the reactor, wherein the hydrogenation catalyst has a particle size between about 10 nm to about 40 nm. Methods may further include reacting the oxalate to form ethylene glycol.

First claim

The invention claimed is:

1. A method of hydrogenating an oxalate, comprising:
preparing a hydrogenation catalyst having a particle size between about 10 nm and about 40 nm by a deposition-precipitation of a mixture consisting of water, Cu(NO 3 ) 2 , an ammonium salt, and a zeolite comprising a mol ratio of SiO 2 :Al 2 O 3 of between 0.1:100 and 100:0.1;
flowing the hydrogenation catalyst to a reactor;
flowing a hydrogen source to the reactor;
flowing an oxalate material to the reactor, wherein the hydrogenation catalyst, the hydrogen source, and the oxalate material comprise a reaction mixture; and
reacting the oxalate material to form ethylene glycol.

2. The method of claim 1 , further comprising pressurizing the reactor to between about 100 PSI to about 500 PSI.

3. The method of claim 1 , further comprising maintaining a temperature inside the reactor between about 150° C. to about 240° C.

4. The method of claim 1 , wherein the reaction mixture comprises the hydrogen source between about 50 volume % to about 99.9 volume %.

5. The method of claim 1 , further comprising flowing a carrier gas to the reactor, wherein the reaction mixture comprises between about 1 volume % to about 15 volume % of the carrier gas.

6. The method of claim 1 , wherein a mol ratio of hydrogen source to oxalate in the reaction mixture is between about 90:1 to about 50:1.

7. The method of claim 1 , wherein a weight hourly space velocity (WHSV) is between about 0.3 and about 10.

8. The method of claim 1 , wherein the hydrogen source reduces the hydrogenation catalyst before flowing the oxalate to the reactor.

9. The method of claim 8 , wherein a temperature inside the reactor during the reduction is between about 300° C. to about 400° C. for about 2 hours to about 6 hours.

10. The method of claim 9 , wherein the temperature inside the reactor is reduced before the flowing the oxalate to the reactor.

11. The method of claim 1 , wherein the mixture consisting of water, Cu(NO 3 ) 2 , an ammonium salt, and a zeolite comprising a mol ratio of SiO 2 :Al 2 O 3 of between 0.1:100 and 100:0.1 forms a catalyst precipitate.

12. The method of claim 11 , further comprising:
calcining the precipitate between about 300° C. to about 500° C. for between about 2 hours to about 24 hours.

13. The method of claim 1 , wherein the ammonium salt is ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium acetate ((NH 4 )OCOCH 3 ), ammonium chloride (NH 4 Cl), ammonium bicarbonate ((NH 4 )OCOOH), or mixtures thereof.

14. The method of claim 1 , wherein the ammonium salt is ammonium carbonate ((NH 4 ) 2 CO 3 ).

15. The method of claim 1 , wherein the ammonium salt is ammonium acetate ((NH 4 )OCOCH 3 ).

16. The method of claim 1 , wherein the ammonium salt is ammonium chloride (NH 4 Cl).

17. The method of claim 1 , wherein the ammonium salt is ammonium bicarbonate ((NH 4 )OCOOH).

18. The method of claim 1 , wherein the zeolite comprises a mol ratio of SiO 2 :Al 2 O 3 of between about 50:1 and about 100:0.1.

19. The method of claim 1 , wherein the zeolite comprises a mol ratio of SiO 2 :Al 2 O 3 of about 80:1.

Assignees

• Univ Wyoming

Inventors

• Fan Maohong
• Popa Tiberiu

Classifications

• B01J2523/17

  Copper · CPC title

• B01J37/036

  to form a gel or a cogel · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J2219/00909

  using filters · CPC title

• B01J35/023

  Operations & Transport · mapped topic