Catalysts conversion of hydroxypropionic acid or its derivatives to acrylic acid or its derivatives

Patent metadata

Field	Value
Publication number	US-9714208-B2
Application number	US-201313760472-A
Country	US
Kind code	B2
Filing date	Feb 6, 2013
Priority date	Apr 11, 2012
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

Methods for catalytically dehydrating hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof to acrylic acid, acrylic acid derivatives, or mixtures thereof with high yield and selectivity and without significant conversion to undesired side products, such as, acetaldehyde, propionic acid, and acetic acid, are provided. The catalysts are mixed condensed phosphates.

First claim

What is claimed is:

1. A method of making acrylic acid, acrylic acid derivatives, or mixtures thereof comprising contacting a stream comprising hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof with a catalyst comprising:
(a) at least two different condensed phosphate anions selected from the group consisting of formulae (I) and (Ib),
[P n O 3n+1 ] (n+2)−   (I)

[PO 3 ] −   (Ib)

wherein in formula I n is at least 2; and
(b) at least two different cations,
wherein the catalyst is essentially neutrally charged; and further, wherein the molar ratio of phosphorus to said at least two different cations is between about 0.7 and about 1.7, whereby acrylic acid, acrylic acid derivatives, or mixtures thereof are produced as a result of said stream being contacted with said catalyst,
further, wherein said cations comprise:
at least one monovalent cation; and
at least one polyvalent cation.

2. The method of claim 1 , wherein said stream further comprises:
(a) diluent; and
(b) inert gas selected from the group consisting of air, nitrogen, helium, argon, carbon dioxide, carbon monoxide, steam, and mixtures thereof.

3. The method of claim 2 , wherein said stream is in the form of a gaseous mixture when contacting the catalyst.

4. The method of claim 3 , wherein said diluent is water.

5. The method of claim 1 , wherein said hydroxypropionic acid is lactic acid.

6. The method of claim 5 , wherein the acrylic acid selectivity from said lactic acid is at least about 50%.

7. The method of claim 5 , wherein the acrylic acid selectivity from said lactic acid is at least about 80%.

8. The method of claim 5 , wherein the propionic acid selectivity from said lactic acid is less than about 5%.

9. The method of claim 5 , wherein the propionic acid selectivity from said lactic acid is less than about 1%.

10. The method of claim 5 , wherein the conversion of said lactic acid is more than about 50%.

11. The method of claim 5 , wherein the conversion of said lactic acid is more than about 80%.

12. The method of claim 1 , wherein said stream contacts said catalyst at a temperature of about 150° C. to about 500° C.

13. The method of claim 5 , wherein said lactic acid contacts said catalyst at a temperature of about 300° C. to about 450° C.

14. The method of claim 3 , wherein said hydroxypropionic acid, hydroxypropionic acid, or mixtures thereof are present in an amount between about 1 mol % and about 10 mol %, based on the total moles of said stream.

15. The method of claim 3 , wherein said stream contacts said catalyst at a GHSV between about 720 h −1 and about 36,000 h −1 .

16. The method of claim 15 , wherein said stream contacts said catalyst at a GHSV of about 3,600 h −1 .

17. The method of claim 3 , wherein said stream contacts said catalyst at a pressure between about 0 psig and about 550 psig.

18. The method of claim 3 , wherein said stream contacts said catalyst at a pressure of about 360 psig.

19. The method of claim 1 , wherein said stream is contacted with said catalyst in a reactor having an interior surface comprising material selected from the group consisting of quartz, borosilicate glass, silicon, hastelloy, inconel, manufactured sapphire, stainless steel, and mixtures thereof.

20. The method of claim 19 , wherein said material is quartz or borosilicate glass.

21. The method of claim 1 , wherein said monovalent cation is selected from the group consisting of H + , Li + , Na + , K + , Rb + , Cs + , and mixtures thereof.

22. The method of claim 1 , wherein said polyvalent cation is selected from the group consisting of divalent cations, trivalent cations, tetravalent cations, pentavalent cations, and mixtures thereof.

23. The method of claim 22 , wherein said polyvalent cation is selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Sn 2+ , Pb 2+ , Ti 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Al 3+ , Ga 3+ , Y 3+ , In 3+ , Sb 3+ , Bi 3+ , Si 4+ , Ti 4+ , Y 4+ , Ge 4+ , Mo 4+ , Pt 4+ , V 5+ , Nb 5+ , Sb 5+ , and mixtures thereof.

24. The method of claim 1 , wherein said condensed phosphate anions are described by formulae (I) and (II).

25. The method of claim 24 , wherein said catalyst comprises:
(a) Ba 2-x-s K 2x H 2s P 2 O 7 or Ca 2-x-s K 2x H 2s P 2 O 7 or Mn 1-x-s K 1+3x H 3s P 2 O 7 or Mn 1-x-s K 2+2x H 2s P 2 O 7 ; and
(b) (KPO 3 ) n ;
wherein x and s are greater or equal to 0 and less than about 0.5 and n is a positive integer.

26. The method of claim 1 , wherein the molar ratio of phosphorus to the cations in said catalyst is between about 0.8 and about 1.3.

27. The method of claim 1 , wherein the molar ratio of phosphorus to the cations in said catalyst is about 1.

28. The method of claim 27 , wherein said cations comprise:
(a) H + , Li + , Na + , K + , Rb + , Cs + , and mixtures thereof; and
(b) Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Sn 2+ , Pb 2+ , Ti 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Al 3+ , Ga 3+ , Y 3+ , In 3+ , Sb 3+ , Bi 3+ , Si 4+ , Ti 4+ , V 4+ , Ge 4+ , Mo 4+ , Pt 4+ , V 5+ , Nb 5+ , Sb 5+ , and mixtures thereof.

29. The method of claim 1 , wherein said catalyst includes an inert support that is constructed of a material comprising silicates, aluminates, carbons, metal oxides, and mixtures thereof.

Assignees

• Procter & Gamble

Inventors

• Villalobos Janette
• Velasquez Juan Estaban
• Godlewski Jane Ellen
• Collias Dimitris Ioannis

Classifications

• B01J2523/25

  Barium · CPC title

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · CPC title

• B01J27/1817

  with copper, silver or gold · CPC title

• B01J2523/13

  Potassium · CPC title

• B01J27/187

  with manganese, technetium or rhenium · CPC title