Claims
- 1. A composition of matter consisting essentially of palladium and further characterized whereby the palladium component is manufactured by reducing a compound selected from the group consisting of palladium salts and oxidized palladium metals in an aqueous organic solvent with a reducing agent at sufficient temperature and pressure to produce a substantially amorphous palladium.
- 2. The composition as set forth in claim 1 wherein the palladium x-ray diffraction pattern has a d value of about 2.30 A and broadened peak profiles.
- 3. The composition as set forth in claim 1 wherein the palladium salt is palladium acetate.
- 4. The composition as set forth in claim 1 wherein the aqueous organic solvent comprises a member selected from the group consisting of a C2-C6 carboxylic acid, tertiaty-butanol, C3-C6 ketone and mixtures thereof.
- 5. The composition as set forth in claim 1 wherein the reduction is conducted at about 0° C. to about 150° C.
- 6. The composition as set forth in claim 1 wherein the reduction is conducted at from about 0° C. to about 90° C.
- 7. The composition as set forth in claim 1 wherein the reduction is conducted at from 1 to about 50 bar pressure.
- 8. The composition of claim 1 wherein the reducing agent is propylene and the aqueous organic solvent comprises valeric acid.
- 9. A composition of matter consisting essentially of palladium and further characterized by the palladium component is manufactured by reducing palladium acetate in an aqueous organic solvent with propylene at a temperature of about 0° C. to about 150° C. and a pressure of about 1 to about 50 bars to produce a substantially amorphorus palladium which has an x-ray diffraction pattern wherein the d value is about 2.30 A and there are broadened peak profiles.
- 10. The composition as set forth in claim 9 wherein the aqueous organic solvent contains as a co-solvent selected from the group consisting of a C2-C6 carboxylic acid, tertiary-butanol, C3-C6, ketone and mixtures thereof.
- 11. The composition as set forth in claim 10 wherein the co-solvent is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid and mixtures thereof.
- 12. The composition as set forth in claim 10 wherein the co-solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobuty! ketone and mixtures thereof.
- 13. A palladium containing catalyst whereby the palladium component (1) is manufactured by reducing palladium salts in an aqueous organic solvent with propylene and (2) the X-ray diffraction pattern has a d value of about 2.30 A and broadened peak profiles.
- 14. The catalyst of claim 13 wherein the palladium salt is palladium acetate.
- 15. Catalyst of claim 13 wherein the catalyst is supported.
- 16. The catalyst of claim 13 wherein the catalyst is unsupported.
- 17. The catalyst of claim 1 wherein the palladium component is prepared from a oxidized palladium metal.
- 18. The catalyst of claim 1 wherein the palladium component is prepared from a palladium metal ligand complex.
- 19. A continuous method for the manufacture of acrylic acid or methacrylic acid which comprises: a) continuously reacting the precursor with oxygen in a continuous reactor in the presence of a palladium catalyst suspended in an aqueous solvent containing as a co-solvent a maximum concentration of a C2-C6 carboxylic acid, tert.-butanol, or C3-C6 ketone, b) recovering the acrylic acid or methacrylic acid formed, and d) recycling the solvent to the reactor.
- 20. The method of claim 19 wherein the precursor is propylene.
- 21. The method of claim 19 wherein the precursor is isobutylene.
- 22. The method of claim 19 wherein the precursor is acrolein.
- 23. The method of claim 19 wherein the precursor is methacrolein.
- 24. The method of claim 19 wherein the precursor to oxygen ratio is from about 1:1 to about 1:5.
- 25. The method of claim 19 wherein the reaction is carried out at from about 50° C. to about 150° C.
- 26. The method of claim 25 wherein the reaction is carried out at from about 60° C. to about 90° C.
- 27. The method of claim 19 wherein the reaction is carried out at from about 1 to about 50 bar.
- 28. The method of claim 19 wherein the co-solvent is propionic acid.
- 29. The method of claim 19 wherein the co-solvent is valeric acid.
- 30. The method of claim 19 wherein the co-solvent is butyric acid.
- 31. The method of claim 19 wherein the co-solvent is acetone.
- 32. The method of claim 19 wherein the co-solvent is methyl isobutyl ketone.
- 33. The composition as set forth in claim 19 wherein the palladium x-ray diffraction pattern has a d value of about 2.30 A and broadened peak profiles.
- 34. The composition as set forth in claim 19 wherein the palladium salt is palladium acetate.
- 35. The method of claim 19 wherein the propylene to oxygen ratio is from about 1:1 to about 1:5.
- 36. The method of claim 35 wherein steps a) and b) of the reaction are carried out at from about 50° C. to about 150° C.
- 37. The method of claim 19 wherein steps a) and b) of the reaction are carried out at from about 60° C. to about 90° C.
- 38. The method of claim 19 wherein steps a) and b) of the reaction is carried out at from about 1 to about 50 bar.
- 39. The method of claim 48 wherein the precursor is propylene.
- 40. The method of claim 48 wherein the precursor is isobutylene.
- 41. The method of claim 48 wherein the precursor is acrolein.
- 42. The method of claim 48 wherein the precursor is methacrolein.
- 43. The method of claim 48 wherein the precursor is oxygen ratio is from about 1:1 to about 1:5.
- 44. The method of claim 48 wherein the reaction is carried out at from about 50° C. to about 150° C.
- 45. The method of claim 44 wherein the reaction is carried out at from about 60° C. to about 90° C.
- 46. The method of claim 48 wherein the reaction is carried out at from about 1 to about 50 bar.
- 47. The composition of claim 1 wherein the reducing agent is propylene and the aqueous organic solvent comprises valeric acid.
- 48. The method of claim 27 wherein the aqueous organic solvent comprises valeric acid.
- 49. A method for the manufacture of C1-C6 esters from an acid selected from the group consisting of acrylic acid and methacrylic acid by the oxidation of a precursor comprising the steps of: a) in a continuous reactor reacting an oxygen-containing gas, a C1-C6 primary alcohol, and a precursor selected from the group consisting of propylene, acrolein, isobutylene, methacrolein, and mixtures thereof in the presence of palladium catalyst prepared by the reduction of a compound selected from the group consisting of palladium salts and oxidized palladium metals with propylene in an oxygen-free organic solvent system comprising as a co-solvent a C2-C6 carboxylic acid, b) recovering the acrylic ester or methacrylic ester formed, and c) recycling the solvent system to the reactor.
Priority Claims (1)
Number |
Date |
Country |
Kind |
09833945 |
Apr 2001 |
US |
|
RELATIONSHIP TO PRIOR APPLICATIONS
[0001] This application is a continuation-in-part of U.S. patent application Ser. No. 09/833945, filed Apr. 12, 2001.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
PCT/US02/11386 |
4/11/2002 |
WO |
|