Compositions and methods related to the production of acrylonitrile

Patent metadata

Field	Value
Publication number	US-9708249-B1
Application number	US-201615245835-A
Country	US
Kind code	B1
Filing date	Aug 24, 2016
Priority date	Aug 24, 2016
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

Disclosed herein are a catalyst and method useful in the process of converting sugars to acrylonitrile.

First claim

What is claimed is:

1. A method comprising the step of:
a) separating at least a portion of ethylene glycol and propylene glycol from a first product comprising ethylene glycol, propylene glycol, and glycerol, thereby producing a second product comprising glycerol; and
b) contacting the second product comprising glycerol with a first catalyst composition, thereby producing a third product comprising acrolein and hydroxyacetone,
wherein the first catalyst composition comprises a first catalyst comprising the formula:
M2 x M3 y O z

wherein M2 is a metal with acid sites promoting dehydration,
wherein M3 is an amphoteric catalyst support, with acid and base sites,
wherein x is a molar ratio from about 0.25 to about 4,
wherein y is a molar ratio from about 0.25 to about 4,
wherein z is the total amount of oxygen bound to M2, and M3, and corresponds to the sum of the oxidation states of M2, and M3.

2. The method of claim 1 , wherein the method further comprises the steps of:
c) separating at least a portion of the hydroxyacetone from the third product, thereby forming a fourth product comprising acrolein; and
d) following step c) converting at least a portion of the acrolein in the fourth product to acrylonitrile.

3. The method of claim 1 , wherein the method further comprises prior to step a), in a single step, converting C5 and/or C6 sugars to the first product comprising ethylene glycol, propylene glycol, and glycerol in the presence of a multifunctional catalyst.

4. The method of claim 1 , wherein the method further comprises contacting at least a portion of the separated propylene glycol with a second catalyst composition, thereby producing propanal, wherein the second catalyst composition comprises a second catalyst having the formula:
M4M5 a M6 b O z
wherein M4 is a metal with acid sites promoting dehydration,
wherein M5 is an amphoteric catalyst support, with acid and base sites, promoting selective dehydration in conjunction with M6 when present,
wherein M6 is a metal promoting C—O cleavage,
wherein a is a molar ratio from about 0.25 to about 4,
wherein b is a molar ratio from 0 to about 4,
wherein z is the total amount of oxygen bound to M4, M5, and M6, and corresponds to the sum of the oxidation states of M4, M5, and M6.

5. The method of claim 1 , wherein M2 is selected from the group consisting of W, Fe, P, and, a zeolite.

6. The method of claim 1 , wherein M3 is selected from the group consisting of Zr, Al, Si, Mg, Ti, La, and Ce.

7. The method of claim 1 , wherein M2 is W.

8. The method of claim 1 , wherein M3 is Zr.

9. The method of claim 1 , wherein the first catalyst has the formula WO 3 ZrO 2 or WO 3 SiO 2 .

10. The method of claim 3 , wherein the C5 and/or C6 sugars is C5 and/or C6 hemicellulose and cellulose derived sugars.

11. The method of claim 3 , wherein the multifunctional catalyst comprises one or more metals selected from the group consisting of Cu, Zn, Sn, Ni, Pt, Pd, Ru, and Re, and a support.

12. The method of claim 11 , wherein the support is selected from the group consisting of Al 2 O 3 , SiO 2 , carbon, TiO 2 , and MgO.

13. The method of claim 1 , wherein at least 60 wt % of the propylene glycol is separated from the first product.

14. The method of claim 1 , wherein the third product comprises at least 50 wt % of acrolein.

15. The method of claim 1 , wherein the second product comprises at least 2 times more glycerol than propylene glycol by weight.

16. The method of claim 1 , wherein the first catalyst further comprises M1, wherein M1 is a metal promoting C—O cleavage,
wherein M2 and M3 promotes selective dehydration in conjunction with M1,
wherein z is the total amount of oxygen bound to M1, M2, and M3, and corresponds to the sum of the oxidation states of M1, M2, and M3.

17. The method of claim 16 , wherein M1 is selected from the group consisting of Cu, Zn, and Sn.

18. The method of claim 16 , wherein M1 is Cu.

19. The method of claim 4 , wherein
M4 is selected from the group consisting of W, Fe, P, and a zeolite,
M5 is selected from the group consisting of Zr, Al, Si, Mg, Ti, La, and Ce, and
M6 is selected from the group consisting of Cu, Zn, and Sn.

20. The method of claim 19 , wherein the first catalyst has the formula WO 3 ZrO 2 or WO 3 SiO 2 .

Assignees

• Southern Res Inst

Inventors

• Goyal Amit
• Samad Jadid

Classifications

• C07C45/52

  by dehydration and rearrangement involving two hydroxy groups in the same molecule · CPC title

• C07C29/132

  by reduction of an oxygen containing functional group · CPC title

• C07C253/26 Primary

  containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes · CPC title

• B01J23/8926

  Copper and noble metals · CPC title

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title