Catalysts for the dehydration of hydroxypropionic acid and its derivatives

Patent metadata

Field	Value
Publication number	US-10272416-B2
Application number	US-201815861728-A
Country	US
Kind code	B2
Filing date	Jan 4, 2018
Priority date	Aug 28, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

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 method of making acrylic acid, acrylic acid derivatives, or mixtures thereof comprising contacting the following compositions:
a) hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof;
b) water vapor; and
c) a dehydration catalyst consisting essentially of one or more amorphous phosphate salts, one or more crystalline phosphate salts, and one or more non-phosphate salts; wherein said one or more crystalline phosphate salts and said one or more non-phosphate salts are substantially chemically inert to said one or more amorphous phosphate salts;
(a) wherein said one or more amorphous phosphate salts consist essentially of:

i) one or more monovalent cations, and
ii) 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; wherein said one or more amorphous phosphate salts are neutrally charged;
or any hydrated form of said one or more amorphous phosphate salts, and mixtures thereof;
(b) wherein said one or more crystalline phosphate salts consist essentially of:

i) one or more polyvalent cations, and
ii) one or more phosphate anions selected from the group represented by molecular formula (II):
( c ) [H (f−2g−h) P f O (4f−g) ] (2f+h)−   (II);

wherein f is a positive integer; wherein g is a positive integer or zero; wherein h is an integer; wherein (f−2g−h) is equal to or greater than zero; wherein (4f−g) is greater than zero; wherein (2f+h) is greater than zero; wherein (4h/f) is equal to or greater than −2 and equal to or less than 1; wherein said one or more crystalline phosphate salts are neutrally charged;
(d) or any hydrated form of said one or more crystalline phosphate salts, and mixtures thereof;
(e) wherein said one or more non-phosphate salts consist essentially of:

i) one or more polyvalent cations, and
ii) one or more non-phosphate anions selected from the group represented by molecular formulae (III) and (IV):
( f ) [H (a−2b) S c O (4c−b) ] (2c−a)−   (III)

( g ) [Ta 2d O (5d+e) ] 2e−   (IV);

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 non-phosphate salts are neutrally charged;
(h) or any hydrated form of said one or more non-phosphate salts, and mixtures thereof;

whereby said acrylic acid, acrylic acid derivatives, or mixtures thereof is produced as a result of said water vapor and said hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof being contacted with said dehydration catalyst.

2. The method of claim 1 , wherein said hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof are in the gas phase during said contacting step with said dehydration catalyst.

3. A method of making acrylic acid, acrylic acid derivatives, or mixtures thereof comprising contacting the following compositions under conditions:
a gas mixture comprising:
a) hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof; and
b) water vapor; with
a dehydration catalyst consisting essentially of one or more amorphous phosphate salts, one or more crystalline phosphate salts, and one or more non-phosphate salts; wherein said one or more crystalline phosphate salts and said one or more non-phosphate salts are substantially chemically inert to said one or more amorphous phosphate salts;
(i) wherein said one or more amorphous phosphate salts consist essentially of:

i) one or more monovalent cations, and
ii) 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;

wherein said one or more amorphous phosphate salts are neutrally charged;
or any hydrated form of said one or more amorphous phosphate salts, and mixtures thereof;
(j) wherein said one or more crystalline phosphate salts consist essentially of:

i) one or more polyvalent cations, and
ii) one or more phosphate anions selected from the group represented by molecular formula (II):
( k ) [H (f−2g−h) PO (4f−g) ] (2f+h)−   (II);

wherein f is a positive integer; wherein g is a positive integer or zero; wherein h is an integer; wherein (f−2g−h) is equal to or greater than zero; wherein (4f−g) is greater than zero; wherein (2f+h) is greater than zero; wherein (4h/f) is equal to or greater than −2 and equal to or less than 1; wherein said one or more crystalline phosphate salts are neutrally charged;
(l) or any hydrated form of said one or more crystalline phosphate salts, and mixtures thereof;
(m) wherein said one or more non-phosphate salts consist essentially of:

i) one or more polyvalent cations, and
ii) one or more non-phosphate anions selected from the group represented by molecular formulae (III) and (IV):
( n ) [H (a−2b) S c O (4c−b) ] (2c−a)−   (III)

( o ) [Ta 2d O (5d+e) ] 2e−   (IV);

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 non-phosphate salts are neutrally charged;
(p) or any hydrated form of said one or more non-phosphate salts, and mixtures thereof;

whereby said acrylic acid, acrylic acid derivatives, or mixtures thereof is produced as a result of said water vapor and said hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof being contacted with said dehydration catalyst.

4. The method of claim 3 , wherein said one or more monovalent cations are selected from the group consisting of K + , Rb + , Cs + , and mixtures thereof.

5. The method of claim 3 , wherein at least one of said one or more amorphous phosphate salts consists of two or more different monovalent cations selected from the group consisting of K + , Rb + , and Cs + .

6. A method of making acrylic acid, acrylic acid derivatives, or mixtures thereof comprising contacting the following compositions under conditions including a water partial pressure and a temperature:
a gas mixture comprising:
a) hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof; and
b) water vapor; with
a dehydration catalyst consisting essentially of one or more amorphous phosphate salts, one or more crystalline phosphate salts, and one or more non-phosphate salts; wherein said one or more crystalline phosphate salts and said one or more non-phosphate salts are substantially chemically inert to said one or more amorphous phosphate salts;
(q) wherein said one or more amorphous phosphate salts consist essentially of:

i) one or more monovalent cations selected from the group consisting of K + , Rb + , Cs + , and mixtures thereof; and
ii) 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;

wherein said one or more amorphous phosphate salts are neutrally charged;
or any hydrated form of said one or more amorphous phosphate salts, and mixtures thereof;
(r) wherein said one or more crystalline phosphate salts consist essentially of:

i) one or more polyvalent cations, and
ii) one or more phosphate anions selected from the group represented by molecular formula (II):
( s ) [H (f−2g−h) P f O (4f−g) ] (2f+h)−   (II);

wherein f is a positive integer; wherein g is a positive integer or zero; wherein h is an integer; wherein (f−2g−h) is equal to or greater than zero; wherein (4f−g) is greater th

Assignees

• Procter & Gamble

Inventors

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

Classifications

• B01J37/0036

  Grinding · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J23/20

  Vanadium, niobium or tantalum · CPC title

• B01J27/055

  with alkali metals, copper, gold or silver · CPC title

• B01J27/1806 Primary

  with alkaline or alkaline earth metals · CPC title