Decarboxylation processes using mixed metal oxide catalysts

• US 5,164,497 A
• Filed: 09/20/1990
• Issued: 11/17/1992
• Est. Priority Date: 09/20/1990
• Status: Expired due to Fees

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Inventors: King, Stephen W., Olson, Kurt D., Ream, Bernard C.
• Primary Examiner(s): Tsang, Cecilia
• Assistant Examiner(s): Datlow, Philip I.
• Application Number:
  US07/585,556
• Time in Patent Office: 789 Days
• Field of Search: 544/87, 544/177, 544/398, 544/404, 544/351-352, 549/510, 564/468, 568/579, 568/613, 568/618, 568/619, 568/671, 568/625, 568/699
• US Class Current: 544/87
• CPC Class Codes: B01J 21/02 Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/10 Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/00 Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 B01J21/16 takes precedence
• CPC Class Codes: C07B 37/06 Decomposition, e.g. elimination of carbon dioxide
• CPC Class Codes: C07C 213/08 by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
• CPC Class Codes: C07C 41/01 Preparation of ethers
• CPC Class Codes: C07C 41/16 by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• CPC Class Codes: C07C 43/04 Saturated ethers
• CPC Class Codes: C07C 43/11 Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
• CPC Class Codes: C07C 43/18 having an ether-oxygen atom bound to a carbon atom of a ring other than a six-membered aromatic ring
• CPC Class Codes: C07D 295/023 Preparation; Separation; Stabilisation; Use of additives
• CPC Class Codes: C07D 295/088 to an acyclic saturated chain
• CPC Class Codes: C07D 305/06 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

A decarboxylation process which comprises contacting a carboxylated compound with a metal oxide catalyst under conditions effective to decarboxylate the carboxylated compound.

Claims

1. A decarboxylation process which comprises contacting a carboxylated compound with a mixed metal oxide catalyst, where the mixed metal oxide catalyst comprises:

(a) a material having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ O.sub.y.sup.3+ (OH).sub.2x+3y-nz A.sub.z.sup.n-, a H.sub.2 O (I)

wherein M is at least one divalent metal cation;

Q is at least one trivalent metal cation; and

A is at least one anion providing a valence (N^-), wherein n is 1 to 4 and wherein a is a positive number, M, Q and A are provided in a proportion such that x/y is a number equal to or greater than 1, z has a value greater than zero and 2x+3y-nz is a positive number, or

(b) a material prepared by calcining the material of formula (I) having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ Q.sub.y.sup.3+ (O).sub.(2x+36-nz)/2 D.sub.z.sup.n-(II)

wherein M, Q, x, y, z and n have the same meanings defined above in connection with formula (I), and D is at least one nonvolatile anion;

under conditions effective to decarboxylate the carboxylated compound.

2. The process of claim 1 wherein the carboxylated compound comprises a substituted or unsubstituted carboxylated alcohol or phenol;

carboxylated amine;

carboxylated amide;

carboxylated ether or epoxide;

carboxylated ester;

carboxylated carboxylic acid or anhydride;

carboxylated ketone;

carboxylated olefin;

carboxylated acetylene;

carboxylated halide or sulfonate;

carboxylated aldehyde;

carboxylated nitrile;

or carboxylated hydrocarbon.

3. The process of claim 1 wherein x/y is a number between 1 and 12 and z has a value which satisfies the relationship:

x/z is between n and 12n.

4. The process of claim 1 wherein A is selected from the group consisting of carbonate, halide, phosphite, phosphate, chromate, sulfate, hydroxide, oxalate, acetate, nitrate, hexanoate, sebacate, vanadate, molybdate, tungstate and ferrocyanate.

5. The process of claim 1 wherein D is selected from the group consisting of halides phosphite, sulfite, sulfate, chromate, arsenate, borate and chlorate.

6. The process of claim 1 wherein x/y is a number between 1 and 6 and z has a value which satisfies the relationship:

x/z is between n and 6n.

7. The process of claim 1 wherein said material prepared by calcining the material of formula (I) has been heat treated at a temperature in the range of 200°

C. to 800°

C. for 12 to 24 hours.

8. The process of claim 1 wherein M is magnesium and Q is aluminum.

9. The process of claim 1 wherein the temperature is from about 150°

C. to about 500°

C.

10. The process of claim 1 wherein the temperature is from about 175°

C. to about 375°

C.

11. The process of claim 1 wherein the reaction time is from about 0.5 hours or less to about 100 hours.

12. The process of claim 1 in which the product comprises a substituted or unsubstituted alcohol or phenol;

amine;

amide;

ether or epoxide;

ester;

carboxylic acid or anhydride;

ketone;

olefin;

acetylene;

halide or sulfonate;

aldehyde;

nitrile;

or hydrocarbon.

13. The process of claim 1 wherein M is at least one divalent metal cation selected from the group consisting of Transition elements and Group IIA, Group IIIB and Group IVA elements.

14. The process of claim 1 wherein M is at least one divalent metal cation selected from magnesium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium, mercury, tin, lead and strontium.

15. The process of claim 1 wherein Q is at least one trivalent metal cation selected from the group consisting of Transition elements and Group IIIB, Group IIIA and Group VA elements.

16. The process of claim 1 wherein Q is at least one trivalent metal cation selected from aluminum, antimony, titanium, scandium, bismuth, vanadium, yttrium, chromium, iron, manganese, cobalt, ruthenium, nickel, gold, gallium, thallium, cerium, boron and lanthanum.

17. A decarboxylation process which comprises (i) contacting an active hydrogen-containing compound with a CO₂ synthon under conditions effective to produce a carboxylated compound, and (ii) contacting the carboxylated compound with a mixed metal oxide catalyst;

where the mixed metal oxide catalyst comprises;

(a) a material having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ Q.sub.y.sup.3+ (OH).sub.2x+3y-nz A.sub.z.sup.n-·

a H.sub.2 O (I)

wherein M is at least one divalent metal cation;

Q is at least one trivalent metal cation; and

A is at least one anion providing a valence (n^-), wherein n is 1 to 4 and wherein a is a positive number, M, Q and A are provided in a proportion such that x/y is a number equal to or greater than 1, z has a value greater than zero and 2x+3y-nz is a positive number, or

(b) a material prepared by calcining the material of formula (I) having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ Q.sub.y.sup.3+ (O).sub.(2x+3y-nz)/2 D.sub.z.sup.n-(II)

wherein M, Q, x, y, z and n have the same meanings defined above in connection with formula (I), and D is at least one nonvolatile anion;

under conditions effective to decarboxylate the carboxylated compound.

18. The process of claim 17 wherein the active hydrogen-containing compound comprises a substituted or unsubstituted alcohol, phenol, carboxylic acid, amine, thiophenol, mercaptan or amide.

19. The process of claim 17 wherein the CO₂ synthon comprises a substituted or unsubstituted carbonate, chlorocarbonate, carbonic acid, carbamate, carbamic acid, oxalate, 2-oxazolidinone, urea, ester, phosgene, chloroformate, carbon dioxide, orthocarboxylate, sulfurous acid or sulfurous acid ester.

20. The process of claim 17 wherein the carboxylated compound comprises a substituted or unsubstituted carboxylated amide;

carboxylated ether or epoxide;

carboxylated ester;

carboxylated carboxylic acid or anhydride;

carboxylated ketone;

carboxylated olefin;

carboxylated acetylene;

carboxylated halide or sulfonate;

carboxylated aldehyde;

carboxylated nitrile;

or carboxylated hydrocarbon.

21. The process of claim 17 wherein the temperature is from about 150°

C. to about 500°

C.

22. The process of claim 17 wherein the temperature is from about 175°

C. to about 375°

C.

23. The process of claim 17 wherein the reaction time is from about 0.5 hours to about 100 hours.

24. The process of claim 17 in which the product comprises a substituted or unsubstituted alcohol or phenol;

amine;

ether or epoxide;

ester;

carboxylic acid or anhydride;

ketone;

olefin;

acetylene, halide or sulfonate;

aldehyde;

nitrile;

or hydrocarbon.

25. The process of claim 17 wherein M is at least one divalent metal cations selected from the group consisting of Transition elements and Group IIA, Group IIIB and Group IVA elements.

26. The process of claim 17 wherein M is at least one divalent metal cation selected from magnesium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium, mercury, tin, lead and strontium.

27. The process of claim 17 wherein Q is at least one trivalent metal cation selected from the group consisting of Transition elements and Group IIIB, Group IIIA and Group VA elements.

28. The process of claim 17 wherein Q is at least one trivalent metal cation selected from aluminum, antimony, titanium, scandium, bismuth, vanadium, yttrium, chromium, iron, manganese, cobalt, ruthenium, nickel, gold, gallium, thallium, cerium, boron and lanthanum.

29. The process of claim 17 wherein x/y is a number between 1 and 12 and z has a value which satisfies the relationship:

x/z is between n and 12n.

30. The process of claim 17 wherein A is selected from the group consisting of carbonate, halide, phosphite, phosphate, chromate, sulfate, hydroxide, oxalate, acetate, nitrate, hexanoate, sebacate, vanadate, molybdate, tungstate and ferrocyanate.

31. The process of claim 17 wherein D is selected from the group consisting of halides, phosphite, phosphate, vanadate, molybdate, tungstate, sulfite, sulfate, chromate, arsenate, borate and chlorate.

32. The process of claim 17 wherein x/y is a number between 1 and 6 and z has a value which satisfies the relationship:

x/z is between n and 6n.

33. The process of claim 17 wherein said material prepared by calcining the material of formula (I) has been heat treated at a temperature in the range of 200°

C. to 800°

C. for 12 to 24 hours.

34. A decarboxylation process which comprises contacting an active hydrogen-containing compound with a CO₂ synthon in the presence of a mixed metal oxide catalyst;

where the mixed metal oxide catalyst comprises;

(a) a material having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ Q.sub.y.sup.3+ (OH).sub.(2x+3y-nz A.sub.z.sup.n- ·

a H.sub.2 O (I)

wherein M is at least one divalent metal cation;

Q is at least one trivalent metal cation; and

A is at least one anion providing a valence (N^-), wherein n is 1 to 4 and wherein a is a positive number, M, Q and A are provided in a proportion such that x/y is a number equal to or greater than 1, z has a value greater than zero and 2x+3y-nz is a positive number, or

(b) a material prepared by calcining the material of formula (I) having the formula

space="preserve" listing-type="equation">M.sub.x.sup.2+ Q.sub.y.sup.3+ (O).sub.(2x+3y-nz)/2 D.sub.z.sup.n-(II)

wherein M, Q, x, y, z and n have the same meanings defined above in connection with formula (I), and D is at least one nonvolatile anion;

under conditions effective for decarboxylation.

35. The process of claim 34 wherein the active hydrogen-containing compound comprises a substituted or unsubstituted alcohol, phenol, carboxylic acid, amine, thiophenol, mercaptan or amide.

36. The process of claim 34 wherein the CO₂ synthon comprises a substituted or unsubstituted carbonate, chlorocarbonate, carbonic acid, carbamate, carbamic acid, oxalate, 2-oxazolidinone, urea, ester, phosgene, chloroformate, carbon dioxide, orthocarboxylate, sulfurous acid or sulfuros acid ester.

37. The process of claim 34 wherein the temperature is from about 150°

C. to about 500°

C.

38. The process of claim 34 wherein the temperature is from about 175°

C. to about 375°

C.

39. The process of claim 34 wherein the reaction time is from about 0.5 hours or less to about 100 hours.

40. The process of claim 34 in which the product comprises a substituted or unsubstituted alcohol or phenol;

amine;

amide;

ether or epoxide;

ester;

carboxylic acid or anhydride;

ketone;

olefin;

acetylene;

halide or sulfonate;

aldehyde;

nitrile;

or hydrocarbon.

41. The process of claim 34 wherein M is at least one divalent metal cation selected from the group consisting of Transition elements and Group IIA, Group IIIB and Group IVA elements.

42. The process of claim 34 wherein M is at least one divalent metal cation selected from magnesium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper, zinc, cadmium, mercury, tin, lead and strontium.

43. The process of claim 34 wherein Q is at least one trivalent metal cation selected from the group consisting of Transition elements and Group IIIB, Group IIIA and Group VA elements.

44. The process of claim 34 wherein Q is at least one trivalent metal cation selected from aluminum, antimony, titanium, scandium, bismuth, vanadium, yttrium, chromium, iron, manganese, cobalt, ruthenium, nickel, gold, gallium, thallium, cerium, boron and lanthanum.

45. The process of claim 34 wherein x/y is a number between 1 and 12 and z has a value which satisfies the relationship:

x/z is between n and 12n.

46. The process of claim 34 wherein A is selected from the group consisting of carbonate, halide, phosphite, phosphate, chromate, sulfate, hydroxide, oxalate, acetate, nitrate, hexanoate, sebacate, vanadate, molybdate, tungstate and ferrocyanate.

47. The process of claim 34 wherein D is selected from the group consisting of halides, phosphite, phosphate, vanadate, molybdate, tungstate, sulfit, sulfate, chromate, arsenate, borate and chlorate.

48. The process of claim 34 wherein x/y is a number between 1 and 6 and z has a value which satisfies the relationship:

x/z is between n and 6n.

49. The process of claim 34 wherein said material prepared by calcining the material of formula (I) has been heat treated at a temperature in the range of 200°

C. to 800°

C. for 12 to 24 hours.