Catalysts for the dehydration of hydroxypropionic acid and its derivatives

Patent metadata

Field	Value
Publication number	US-10717070-B2
Application number	US-201916297899-A
Country	US
Kind code	B2
Filing date	Mar 11, 2019
Priority date	Aug 28, 2015
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

Hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof are dehydrated using a catalyst and a method to produce bio-acrylic acid, acrylic acid derivatives, or mixtures thereof. A method to produce the dehydration catalyst is also provided.

First claim

What is claimed is:

1. A dehydration catalyst consisting essentially of one or more amorphous phosphate salts; wherein said one or more amorphous phosphate salts consist essentially of one or more monovalent cations, and one or more phosphate anions selected from the group represented by empirical formula (I):
[H 2(1−x) PO (4−x) ] −   (I);

wherein x is any real number greater than 0 and less than 1; and
wherein said one or more amorphous phosphate salts of said dehydration catalyst are neutrally charged.

2. The dehydration catalyst of claim 1 , wherein said one or more monovalent cations are selected from the group consisting of Na + , K + , Rb + , Cs + , and mixtures thereof.

3. The dehydration catalyst of claim 2 , wherein said one or more amorphous phosphate salts is KH 2(1−x) PO (4−x) ; and wherein x is any real number greater than 0 and less than 1.

4. The dehydration catalyst of claim 1 , wherein said one or more amorphous phosphate salts are selected from the group represented by empirical formula (Ib):
M w I N (1−w) I H 2(1−x) PO (4−x)   (Ib);

wherein M I and N I are two different monovalent cations; wherein x is any real number equal to or greater than 0 and equal to or less than 1; and wherein w is any real number greater than 0 and less than 1.

5. The dehydration catalyst of claim 1 , further comprising amorphous silicon oxide (SiO 2 ); wherein said amorphous silicon oxide is substantially chemically inert to said one or more amorphous phosphate salts.

6. The dehydration catalyst of claim 5 , wherein said one or more monovalent cations are selected from the group consisting of Na + , K + , Rb + , Cs + , and mixtures thereof.

7. The dehydration catalyst of claim 5 , wherein said one or more amorphous phosphate salts are selected from the group represented by empirical formula (Ib):
M w I N (1−w) I H 2(1−x) PO (4−x)   (Ib);

wherein M I and N I are two different monovalent cations; wherein x is any real number equal to or greater than 0 and equal to or less than 1; and wherein w is any real number greater than 0 and less than 1.

8. The dehydration catalyst of claim 5 , wherein the weight ratio between the total amount of said one or more amorphous phosphate salts and the total amount of said amorphous silicon oxide is between about 1:10 and about 4:1.

9. The dehydration catalyst of claim 1 , further comprising one or more oxysalts; wherein said oxysalts comprise one or more polyvalent cations, and one or more oxyanions; wherein said oxyanions are selected from the group represented by molecular formulae (II) and (III):
[H (a−2b) S c O (4c−b) ] (2c−a)−   (II)

[Ta 2d O (5d+e) ] 2e−   (III);

wherein a and b are positive integers or zero; wherein c, d, and e are positive integers;
wherein (a−2b) is equal to or greater than zero; wherein (2c−a) is greater than zero;
wherein said one or more oxysalts are neutrally charged; and wherein said one or more oxysalts are substantially chemically inert to said one or more amorphous phosphate salts.

10. The dehydration catalyst of claim 9 , further comprising amorphous silicon oxide (SiO 2 ); wherein said amorphous silicon oxide is substantially chemically inert to said one or more amorphous phosphate salts.

11. The dehydration catalyst of claim 9 , wherein said one or more polyvalent cations are selected from the group consisting of the cations of the metals Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and mixtures thereof.

12. The dehydration catalyst of claim 11 , wherein said one or more polyvalent cations are selected from the group consisting of the cations of the metals Mg, Ca, Sr, Ba, Y, Mn, Al, Er, and mixtures thereof.

13. The dehydration catalyst of claim 9 , wherein said one or more oxyanions are selected from the group represented by molecular formulae (IIa) to (IId), (IIIa) to (IIIg), and mixtures thereof:
[SO 4 ] 2−   (IIa)

[S 2 O 7 ] 2−   (IIb)

[HSO 4 ] 1−   (IIc)

[SO 4 ] 2− .[HSO 4 ] −   (IId)

[Ta 2 O 6 ] 2−   (IIIa)

[Ta 2 O 7 ] 4−   (IIIb)

[Ta 2 O 9 ] 8−   (IIIc)

[Ta 2 O 10 ] 10−   (IIId)

[Ta 2 O 11 ] 12−   (IIIe)

[Ta 4 O 11 ] 2−   (IIIf)

[Ta 4 O 15 ] 10−   (IIIg).

14. The dehydration catalyst of claim 13 , wherein said one or more oxyanions are selected from the group represented by molecular formulae (IIa), (IIIa), and mixtures thereof:
[SO 4 ] 2−   (IIa)

[Ta 2 O 6 ] 2−   (IIIa).

15. The dehydration catalyst of claim 9 , wherein said one or more oxysalts are selected from the group consisting of CaSO 4 , SrSO 4 , BaSO 4 , SrK 2 (SO 4 ) 2 , SrRb 2 (SO 4 ) 2 , Ca 2 K 2 (SO 4 ) 3 , Ca 2 Rb 2 (SO 4 ) 3 , Ca 2 Cs 2 (SO 4 ) 3 , CaTa 4 O 11 , SrTa 4 O 11 , BaTa 4 O 11 , MgTa 2 O 6 , CaTa 2 O 6 , SrTa 2 O 6 , BaTa 2 O 6 , Mg 2 Ta 2 O 7 , Ca 2 Ta 2 O 7 , Sr 2 Ta 2 O 7 , SrK 2 Ta 2 O 7 , Ba 2 Ta 2 O 7 , Ba 3 Ta 2 O 8 , Mg 4 Ta 2 O 9 , Ca 4 Ta 2 O 9 , Sr 4 Ta 2 O 9 , Ba 4 Ta 2 O 9 , Ca 5 Ta 2 O 10 , Ca 2 KTa 3 O 10 , Ca 2 RbTa 3 O 10 , Ca 2 CsTa 3 O 10 , Sr 2 KTa 3 O 10 , Sr 2 RbTa 3 O 10 , Sr 2 CsTa 3 O 10 , Mg 5 Ta 4 O 15 , Sr 5 Ta 4 O 15 , Ba 5 Ta 4 O 15 , Sr 2 KTa 5 O 15 , Ba 2 KTa 5 O 15 , Sr 6 Ta 2 O 11 , Ba 6 Ta 2 O 11 , any of their hydrated forms, and mixtures thereof.

16. The dehydration catalyst of claim 15 , wherein said one or more oxysalts are selected from the group consisting of CaSO 4 , CaTa 2 O 6 , SrSO 4 , SrTa 2 O 6 , BaSO 4 , BaTa 2 O 6 , any of their hydrated forms, and mixtures thereof.

17. The dehydration catalyst of claim 9 , wherein said one or more amorphous phosphate salts are selected from the group consisting of KH 2(1−x) PO (4−x) , NaH 2(1−x) RbH 2(1−x) PO (4−x) , CsH 2(1−x) PO (4-x) , any of their hydrated forms, and mixtures thereof; wherein x is any real number equal to or greater than 0 and equal to or less than 1; and wherein said one or more oxysalts are selected from the group consisting of CaSO 4 , CaTa 2 O 6 , SrSO 4 , SrTa 2 O 6 , BaSO 4 , BaTa 2 O 6 , any of their hydrated forms, and mixtures thereof.

18. The dehydration catalyst of claim 17 , wherein said one or more amorphous phosphate salts is KH 2(1−x) PO (4−x) , wherein x is any real number equal to or greater than 0 and equal to or less than 1; and wherein said one or more oxysalts is BaSO 4 .

Assignees

• Procter & Gamble

Inventors

• Velasquez Juan Esteban
• Collias Dimitris Ioannis
• Godlewski Jane Ellen
• Wireko Fred Christian

Classifications

• B01J27/1806 Primary

  with alkaline or alkaline earth metals · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• C07C51/377

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• B01J27/18

  with metals {other than Al or Zr} · CPC title

• B01J27/188

  with chromium, molybdenum, tungsten or polonium · CPC title