Catalysts for the dehydration of hydroxypropionic acid and its derivatives

• US 10,286,387 B2
• Filed: 11/20/2017
• Issued: 05/14/2019
• Est. Priority Date: 08/28/2015
• Status: Active Grant

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Velasquez, Juan Esteban, Collias, Dimitris Ioannis, Godlewski, Jane Ellen, Wireko, Fred Christian
• Primary Examiner(s): Hailey, Patricia L.
• Application Number:
  US15/817,316
• Publication Number:
  US 20180071722A1
• Time in Patent Office: 540 Days
• Field of Search: 502208-214
• CPC Class Codes: B01J 23/20 Vanadium, niobium or tantalum
• CPC Class Codes: B01J 27/16 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 Class Codes: B01J 27/18 with metals other than Al or Zr
• CPC Class Codes: B01J 27/1806 with alkaline or alkaline earth metals
• CPC Class Codes: B01J 27/1811 with gallium, indium or thallium
• CPC Class Codes: B01J 27/1813 with germanium, tin or lead
• CPC Class Codes: B01J 27/186 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 27/187 with manganese, technetium or rhenium
• CPC Class Codes: B01J 27/188 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 27/195 with vanadium, niobium or tantalum
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 37/0036 Grinding
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C07C 51/00 Preparation of carboxylic acids or their salts, halides or anhydrides of acids by hydrolysis of oils, fats or waxes C11C

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.

Claims

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 amorphous phosphate salts are selected from the group represented by empirical formula (Ib);

M¹_wN¹_(1-w)H_2(1-x)PO_(4-x)

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; 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. A dehydration catalyst consisting essentially of one or more amorphous phosphate salts and amorphous silicon oxide (SiO₂);

wherein said one or more amorphous phosphate salts are selected from the group represented by empirical formula (Ib);

M_w^IN_(1-w)^IH_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; and

further, wherein said amorphous silicon oxide is substantially chemically inert to said one or more amorphous phosphate salts;

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.

4. A dehydration catalyst consisting essentially of one or more amorphous phosphate salts and one or more oxysalts;

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 equal to or greater than 0 and equal to or less than 1; and

wherein said one or more amorphous phosphate salts of said dehydration catalyst are neutrally charged; and

further 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_cO_(4c-b)]^(2c-a)−

 

 

(II)

[Ta_2dO_(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.

5. The dehydration catalyst of claim 4, 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.

6. The dehydration catalyst of claim 5, 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.

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

[SO₄]²⁻

 

 

(IIa)

[S₂O₇]²⁻

 

 

(IIb)

[HSO₄]¹⁻

 

 

(IIc)

[SO₄]²⁻

.[HSO₄]⁻

 

 

(IId)

[Ta₂O₆]²⁻

 

 

(IIIa)

[Ta₂O₇]⁴⁻

 

 

(IIIb)

[Ta₂O₉]⁸⁻

 

 

(IIIc)

[Ta₂O₁₀]¹⁰⁻

 

 

(IIId)

[Ta₂O₁₁]¹²⁻

 

 

(IIIe)

[Ta₄O₁₁]²⁻

 

 

(IIIf)

[Ta₄O₁₅]¹⁰⁻

 

 

(IIIg).

8. The dehydration catalyst of claim 7, wherein said one or more oxyanions are selected from the group represented by molecular formulae (IIa), (IIIa), and mixtures thereof:

[SO₄]²⁻

 

 

(IIa)

[Ta₂O₆]²⁻

 

 

(IIIa).

9. The dehydration catalyst of claim 4, wherein said one or more oxysalts are selected from the group consisting of CaSO₄, SrSO₄, BaSO₄, SrK₂(SO₄)₂, SrRb₂(SO₄)₂, Ca₂K₂(SO₄)₃, Ca₂Rb₂(SO₄)₃, Ca₂Cs₂(SO₄)₃, CaTa₄O₁₁, SrTa₄O₁₁, BaTa₄O₁₁, MgTa₂O₆, CaTa₂O₆, SrTa₂O₆, BaTa₂O₆, Mg₂Ta₂O₇, Ca₂Ta₂O₇, Sr₂Ta₂O₇, SrK₂Ta₂O₇, Ba₂Ta₂O₇, Ba₃Ta₂O₈, Mg₄Ta₂O₉, Ca₄Ta₂O₉, Sr₄Ta₂O₉, Ba₄Ta₂O₉, Ca₅Ta₂O₁₀, Ca₂KTa₃O₁₀, Ca₂RbTa₃O₁₀, Ca₂CsTa₃O₁₀, Sr₂KTa₃O₁₀, Sr₂RbTa₃O₁₀, Sr₂CsTa₃O₁₀, Mg₅Ta₄O₁₅, Sr₅Ta₄O₁₅, Ba₅Ta₄O₁₅, Sr₂KTa₅O₁₅, Ba₂KTa₅O₁₅, Sr₆Ta₂O₁₁, Ba₆Ta₂O₁₁, any of their hydrated forms, and mixtures thereof.

10. The dehydration catalyst of claim 9, wherein said one or more oxysalts are selected from the group consisting of CaSO₄, CaTa₂O₆, SrSO₄, SrTa₂O₆, BaSO₄, BaTa₂O₆, any of their hydrated forms, and mixtures thereof.

11. The dehydration catalyst of claim 4, 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)PO_(4-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 CaSO₄, CaTa₂O₆, SrSO₄, SrTa₂O₆, BaSO₄, BaTa₂O₆, any of their hydrated forms, and mixtures thereof.

12. The dehydration catalyst of claim 11, 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 BaSO₄.

13. A dehydration catalyst consisting essentially of one or more amorphous phosphate salts, one or more oxysalts, and amorphous silicon oxide (SiO₂);

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 equal to or greater than 0 and equal to or less than 1; and

wherein said one or more amorphous phosphate salts of said dehydration catalyst are neutrally charged; and

further 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_cO_(4c-b)]^(2c-a)−

 

 

(II)

[Ta_2dO_(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; and

further wherein said amorphous silicon oxide is substantially chemically inert to said one or more amorphous phosphate salts.