Metal oxide catalyst systems for conversion of ethanol to butadiene

Patent metadata

Field	Value
Publication number	US-10179323-B2
Application number	US-201615175727-A
Country	US
Kind code	B2
Filing date	Jun 7, 2016
Priority date	Jun 7, 2016
Publication date	Jan 15, 2019
Grant date	Jan 15, 2019

Abstract

A process includes reacting a feed stream containing ethanol and optionally acetaldehyde in a dehydration reactor in the presence of a dehydration catalyst system having a Group 4 or Group 5 metal oxide and a support. The process includes obtaining a product stream containing butadiene from the dehydration reactor. Another process includes reacting a feed stream containing ethanol and optionally acetaldehyde in a dehydration reactor in the presence of a dehydration catalyst system containing a tungsten oxide supported on a zeolite or a tantalum oxide supported on a zeolite. The process includes obtaining a product stream containing butadiene from the dehydration reactor.

First claim

What is claimed is:

1. A process comprising:
reacting a feed stream comprising ethanol and aldehyde in a dehydration reactor in the presence of a dehydration catalyst system comprising a Group 4 metal oxide and a silica support wherein the dehydration catalyst system contains only a single metal oxide, wherein the single metal oxide is a Group 4 metal oxide;
obtaining a product stream comprising butadiene from the dehydration reactor, wherein the process has a selectivity of butadiene of between 15 and 20 mole percent, a process yield of butadiene of 1 to 4 mole percent, an acetaldehyde efficiency of 10 to 50 mole percent, or an acetaldehyde conversion of from 35 to 75 percent; and
regenerating the dehydration catalyst system in-situ in the presence of hydrogen at between 300 and 600° C.

2. The process of claim 1 , wherein the Group 4 metal oxide is a zirconium metal oxide.

3. The process of claim 1 , wherein the support comprises MgO/SiO 2 .

4. The process of claim 1 , further comprising, prior to reacting the feed stream comprising ethanol in the dehydration reactor, dehydrogenating a stream comprising ethanol in a dehydrogenation reactor using a catalyst comprising silver located upstream of the dehydration reactor to form the feed stream, wherein the feed stream comprises ethanol and acetaldehyde.

5. The process of claim 1 , further comprising:
obtaining a recycle stream containing unreacted ethanol from the dehydration reactor; and
feeding the recycle stream into the dehydration reactor with the feed stream.

6. The process of claim 5 , wherein the a reflux ratio ranges from 0.5 to 1.0, wherein the reflux ratio is a ratio of the amount of the recycle stream to the amount of the feed stream fed to the dehydration reactor, as determined by volume.

7. The process of claim 1 , wherein the ethanol comprises bioethanol.

8. The process of claim 1 , wherein a temperature in the dehydration reactor during reaction of the feed stream ranges from 148 to 500° C.

9. The process of claim 1 , wherein a pressure in the dehydration reactor during reaction of the feed stream is from 0.01 to 0.6 MPa.

10. The process of claim 1 , wherein a liquid hourly space velocity in the dehydration reactor during reaction of the feed stream is from 0.1 to 5 hr −1 .

11. The process of claim 1 , wherein the feed stream comprises ethanol and acetaldehyde, and wherein a volumetric ratio of ethanol to acetaldehyde in the feed stream ranges from 9:1 to 1:1.

12. A process comprising:
reacting a feed stream comprising ethanol in a dehydration reactor in the presence of a dehydration catalyst system wherein the dehydration catalyst system comprises a bimetallic catalyst system containing only two metal oxides, and wherein at least one of the two metal oxides is a Group 4 metal oxide;
obtaining a product stream comprising butadiene from the dehydration reactor;
obtaining a recycle stream containing unreacted ethanol, acetaldehyde, butadiene, diethyl ether, or combinations thereof from the dehydration reactor;
feeding the recycle stream into the dehydration reactor with the feed stream; and
regenerating the dehydration catalyst system in-situ in the presence of hydrogen at between 300 and 600° C.

13. The process of claim 12 , wherein the dehydration catalyst system comprises a cobalt-zirconium oxide, or a cerium-zirconium oxide.

14. The process of claim 12 , wherein the dehydration catalyst system comprises Zr/Zn oxides supported on silica or Zr/Zn oxides supported on magnesia silica.

15. A process comprising:
reacting a feed stream comprising ethanol in a dehydration reactor in the presence of a dehydration catalyst system wherein the dehydration catalyst system comprises a trimetallic catalyst system containing only three metal oxides, and wherein at least one of the three metal oxides is a Group 4 metal oxide;
obtaining a product stream comprising butadiene from the dehydration reactor;
obtaining a recycle stream containing unreacted ethanol from the dehydration reactor;
feeding the recycle stream into the dehydration reactor with the feed stream; and
regenerating the dehydration catalyst system in-situ in the presence of hydrogen at between 300 and 600° C.

16. The process of claim 7 , wherein the dehydration catalyst system comprises Zr/Zn/Cu oxides supported on silica, or Zr/Zn/Cu oxides supported on magnesia-silica.

Assignees

• Fina Technology

Inventors

• Chinta Sivadinarayana
• Gandhi Kaushik

Classifications

• B01J23/20

  Vanadium, niobium or tantalum · CPC title

• C07C2523/06

  of zinc, cadmium or mercury · CPC title

• B01J23/36

  Rhenium · CPC title

• C07C2521/08

  Silica · CPC title

• B01J23/06 Primary

  of zinc, cadmium or mercury · CPC title