Claims
- 1. A method for making an organometallic treated molecular sieve comprising:
a) providing a molecular sieve having at least [A1O4] and [PO4] tetrahedral units and having an average pore dimension less than or equal to about 5Å, the molecular sieve having at least one hydroxyl group; b) contacting said molecular sieve with a solution comprising an organometallic compound and a non-proton donating solvent, wherein said organometallic compound comprises at least one metal bound to at least one alkyl group; and c) separating the organometallic treated molecular sieve from the solution.
- 2. The method of claim 1, wherein said molecular sieve comprises [SiO4], [AlO4] and [PO4] tetrahedral units.
- 3. The method of claim 1, wherein said molecular sieve is an aluminophosphate or a silicoaluminophosphate.
- 4. The method of claim 1, wherein said molecular sieve is a silicoaluminophosphate.
- 5. The method of claim 4, wherein said molecular sieve is selected from SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-47, SAPO-56 and inter-growths and mixtures thereof.
- 6. The method of claim 1, wherein said molecular sieve has an average pore dimension in the range of from 3Å to about 5Å
- 7. The method of claim 1, wherein said organometallic compound has a kinetic diameter less than the average pore dimension of the molecular sieve.
- 8. The method of claim 1, wherein said at least one metal of said organometallic compound is selected from zinc, lithium, magnesium, gallium, germanium, and mixtures thereof.
- 9. The method of claim 1, wherein said at least one alkyl group has from 1 to 20 carbon atoms.
- 10. The method of claim 1, wherein said at least one alkyl group has from 1 to 6 carbon atoms.
- 11. The method of claim 1, wherein said organometallic compound is selected from methyl lithium, butyl lithium, dimethyl zinc, diethyl zinc, ethylmagnesium bromide, methylmagnesium bromide, methylmagnesium chloride, trimethyl gallium, triethyl gallium, tetraethyl gallium, tetramethylgallium, and mixtures thereof.
- 12. The method of claim 1, wherein said organometallic compound is dimethyl zinc.
- 13. The method of claim 1, wherein said organometallic compound is methylmagnesium bromide.
- 14. The method of claim 1, wherein b) is carried out for at a temperature of about −40° C. to about 200° C. for a period of about 1 hour to about 48 hours.
- 15. The method of claim 1, wherein b) is carried out for at a temperature of about −25° C. to about 150° C. for a period of about 2 hour to about 24 hours.
- 16. The method of claim 1, wherein b) is carried out for at a temperature of about 0° C. to about 100° C. for a period of about 3 hour to about 20 hours.
- 17. The method of claim 1, wherein the concentration of said organometallic compound in said solution is about 0.001 M to about 10 M.
- 18. The method of claim 1, wherein the concentration of said organometallic compound in said solution is about 0.005 M to about 5 M.
- 19. The method of claim 1, wherein the concentration of said organometallic compound in said solution is about 0.01 M to about 3 M.
- 20. The method of claim 1, wherein said non-proton donating solvent is selected from heptane, tetrahydrofuran, benzene, toluene, xylenes, diethyl ether and mixtures thereof.
- 21. The method of claim 2, wherein the atomic ratio of said at least one metal to the silicon in said molecular sieve in said contacting b) is from about 0.001 to about 3.0.
- 22. The method of claim 2, wherein the atomic ratio of said at least one metal to the silicon in said molecular sieve in said contacting b) is from about 0.01 to about 2.5.
- 23. The method of claim 2, wherein the atomic ratio of said at least one metal to the silicon in said molecular sieve in said contacting b) is from about 0.02 to about 2.0.
- 24. The method of claim 1, wherein the amount of metal in said organometallic treated molecular sieve is about 0.05% to about 20% by wt.
- 25. The method of claim 1, wherein the amount of metal in said organometallic treated molecular sieve is about 0.5% to about 10% by wt.
- 26. The method of claim 1, wherein the amount of metal in said organometallic treated molecular sieve is about 1% to about 8% by wt.
- 27. The method of claim 1, and further comprising calcining the molecular sieve prior to b).
- 28. The method of claim 27, wherein said calcining is carried out at temperature of about 300° C. to about 800° C. for a period of about 1 hour to about 24 hours.
- 29. The method of claim 27, wherein said calcining is carried out at temperature of about 450° C. to about 750° C. for a period of about 2 hours to about 12 hours.
- 30. The method of claim 27, wherein said calcining is carried out at temperature of about 550° C. to about 700° C. for a period of about 3 hours to about 10 hours.
- 31. The method of claim 27, wherein said calcining is carried out in the presence of oxygen.
- 32. The method of claim 1, further comprising calcining the organometallic treated molecular sieve separated in c).
- 33. The method of claim 32, wherein said calcining is carried out at temperature of about 300° C. to about 800° C. for a period of about 1 hour to about 24 hours.
- 34. The method of claim 32, wherein said calcining is carried out at temperature of about 450° C. to about 750° C. for a period of about 2 hours to about 12 hours.
- 35. The method of claim 32, wherein said calcining is carried out at temperature of about 550° C. to about 700° C. for a period of about 3 hours to about 10 hours.
- 36. The method of claim 32, wherein said calcining is carried out in the presence of oxygen.
- 37. The method of claim 1 and further comprising physically mixing the organometallic treated molecular sieve with an oxide of at least one metal selected from Group 2, Group 3 and Group 4 of the Periodic Table of Elements.
- 38. The method of claim 37, wherein said oxide is selected from oxides of zirconium, hafnium, magnesium, calcium, strontium, barium, yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, thorium and mixtures thereof.
- 39. The method of claim 37, wherein the organometallic treated molecular sieve is physically mixed with oxides of lanthanum and zirconium.
- 40. The method of claim 37, wherein said oxide has an uptake of carbon dioxide at 100° C. of at least 0.03 mg/m2 of the metal oxide.
- 41. An organometallic treated molecular sieve prepared by the method of claim 1.
- 42. A calcined, dimethyl zinc treated SAPO-34 having signature peak at about δ=1.0 ppm, as measured by MAS 1H NMR.
- 43. A catalyst composition comprising a calcined, organometallic treated molecular sieve prepared by the method of claim 32.
- 44. The catalyst composition of claim 43 and further comprising an oxide of at least one metal selected from Group 2, Group 3 and Group 4 of the Periodic Table of Elements.
- 45. The catalyst composition of claim 44, wherein said oxide is selected from oxides of zirconium, hafnium, magnesium, calcium, strontium, barium, yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, thorium and mixtures thereof.
- 46. The catalyst composition of claim 44, wherein said oxide has an uptake of carbon dioxide at 1 00° C. of at least 0.03 mg/m2 of the metal oxide.
- 47. The catalyst composition of claim 43 and further comprising at least one of a binder and a matrix.
- 48. The catalyst composition of claim 47, wherein the binder and/or matrix is selected from alumina, aluminum chlorohydrol, clay, and mixtures thereof.
- 49. A molecular sieve composition comprising a molecular sieve having at least [AlO4] and [PO4] tetrahedral units and having an average pore dimension less than or equal to about 5Å and an organometallic species bound to at least one oxygen atom of the molecular sieve.
- 50. The composition of claim 49 wherein the molecular sieve is a silicoaluminophosphate.
- 51. The composition of claim 49, wherein the molecular sieve is SAPO-18, SAPO-34 or an intergrowth of SAPO-18 and SAPO-34 and the organometallic species is derived from dimethyl zinc or methylmagnesium bromide.
- 52. A process of making an olefin product, comprising contacting a feedstock comprising at least one organic compound that contains at least one oxygen atom with the catalyst composition of claim 43 under conditions suitable to convert said organic compound into olefins.
- 53. The process of claim 52 wherein the molecular sieve is a silicoaluminophosphate.
- 54. The process of claim 52, wherein the molecular sieve is SAPO-18, SAPO-34 or an intergrowth of SAPO-18 and SAPO-34.
- 55. The process of claim 52, wherein said catalyst composition further comprises an oxide of at least one metal selected from Group 2, Group 3 and Group 4 of the Periodic Table of Elements.
- 56. The process of claim 55, wherein said oxide is selected from oxides of zirconium, hafnium, magnesium, calcium, strontium, barium, yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, thorium and mixtures thereof
- 57. The process of claim 55, wherein said oxide has an uptake of carbon dioxide at 100° C. of at least 0.03 mg/m2 of the metal oxide.
- 58. The process of claim 52, wherein said catalyst composition further comprises at least one of a binder and a matrix.
- 59. The process of claim 58, wherein the binder and/or matrix is selected from alumina, aluminum chlorohydrol, clay, and mixtures thereof.
- 60. The process of claim 52, wherein said organic compound is selected from methanol, ethanol, dimethyl ether, methylethyl ether, diethyl ether, dimethyl carbonate, methyl formate, and mixtures thereof.
- 61. The process of claim 52, wherein said organic compound is methanol.
- 62. A process of making an olefin product, comprising contacting a feedstock comprising at least one organic compound that contains at least one oxygen atom with a catalyst composition under conditions suitable to convert said organic compound into olefins, said catalyst composition comprising a molecular sieve which has been treated with a solution comprising an organometallic compound and a non-proton donating solvent, wherein said organometallic compound comprises at least one metal bound to at least one alkyl group.
- 63. The process of claim 62, wherein said molecular sieve has an average pore dimension less than or equal to about 5Å.
- 64. The process of claim 62, wherein the molecular sieve is a silicoaluminophosphate.
- 65. The process of claim 62, wherein said catalyst composition further comprises an oxide of at least one metal selected from Group 2, Group 3 and Group 4 of the Periodic Table of Elements.
- 66. The catalyst composition of claim 65, wherein said catalyst composition further comprises at least one of a binder and a matrix different from said metal oxide.
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuing application from U.S. patent application Ser. No. 10/112,250 filed Mar. 29, 2002, the entire contents of which application are incorporated herein by reference.
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
10112250 |
Mar 2002 |
US |
Child |
10377192 |
Feb 2003 |
US |