Claims
- 1. A method for regenerating, replacing or treating the catalyst in a hydroprocessing reactor, which catalyst comprises a platinum group metal on a support, the method comprising admixing with the feedstock, recycle stream or hydrogen stream of the reactor an additive which comprises a nonionic, organometallic platinum group metal coordination composition wherein said composition
- a) has a breakdown temperature between about 40.degree. C. and about 570.degree. C.; and
- b) is substantially free from a disadvantageous amount of phosphorus, arsenic, sulfur, antimony or halides,
- wherein platinum group metal is caused to be deposited on said catalyst.
- 2. The method of claim 1 wherein said composition is selected from the group consisting of
- a) a composition of the general formula
- L.sup.1 PtR.sup.1 R.sup.2
- wherein L.sup.1 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands; and R.sup.1 and R.sup.2 are each, independently, substituted or unsubstituted methyl, benzyl, aryl, cyclooctadiene or pentamethyl cyclopentadiene;
- b) a composition of the general formula
- L.sup.2 M.sup.1 R.sup.3
- wherein L.sup.2 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands; M.sup.1 is rhodium or iridium; and R.sup.3 is cyclopentadiene or pentamethyl cyclopentadiene;
- c) a composition of the general formula
- L.sup.3 M.sup.2 (C.sub.4 R.sup.4.sub.4)
- wherein L.sup.3 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous monodentate ligands; M.sup.2 is platinum, palladium, rhodium or iridium; and R.sup.4 is COOR.sup.5, wherein R.sup.5 is hydrogen or alkyl having from 1 to 10 carbons;
- d) a composition of the general formula
- L.sup.4 M.sup.3 (COOR.sup.6).sub.2
- or a dimer thereof, wherein L.sup.4 is a non-nitrogenous cyclic polyolefin ligand; M.sup.3 is platinum or iridium; and R.sup.6 is alkyl; and
- e) a composition comprising the reaction product of L.sup.5 RhX and R.sup.7 MgX wherein L.sup.5 is a non-nitrogenous cyclic polyolefin ligand; R.sup.7 is methyl, benzyl, aryl, cyclopentadiene or pentamethyl cyclopentadiene; and X is a halide.
- 3. The method of claim 2 wherein L.sup.1, L.sup.2 and L.sup.3 are selected from the group consisting of cyclopentadiene, cyclooctadiene, pentamethyl cyclopentadiene, cyclooctatetrene, o-phenantholine, o-toluidine, norbornadiene, pyridine and bipyridine.
- 4. The method of claim 2 wherein L.sup.4 and L.sup.5 are selected from the group consisting of cyclooctadiene and pentamethyl cyclopentadiene.
- 5. The method of claim 4 wherein said additive further comprises a feedstock- or recycle stream-soluble solvent for said composition.
- 6. The method of claim 5 wherein said solvent is selected from the group consisting of 1 to 4 carbon alcohols, acetone, tetrahydrofuran, methyl tertiary butyl ether and mixtures thereof.
- 7. The method of claim 1 wherein said additive is introduced into the feedstock, the recycle stream or the hydrogen stream in a continuous manner.
- 8. The method of claim 7 wherein said additive is introduced into the feedstock or the recycle stream in an amount of about 0.01 to about 10.0 parts per million of said platinum group metal.
- 9. The process of claim 7 wherein said additive is introduced into the hydrogen stream at a rate of about 0.000002 to about 0.002 grams of platinum group metal per hour per 100 grams of catalyst desired to be present.
- 10. The method of claim 1 wherein said additive is introduced into the feedstock, the recycle stream or the hydrogen stream in an intermittent manner.
- 11. The method of claim 10 wherein said additive is introduced into the feedstock or recycle stream in an amount of about 10 to about 10,000 parts per million of said platinum group metal.
- 12. The process of claim 10 wherein said additive is introduced into the hydrogen stream at a rate of about 0.002 to about 2.0 grams of platinum group metal per hour per 100 grams of catalyst desired to be present.
- 13. A method for regenerating, replacing or treating the catalyst in a hydroprocessing reactor, which catalyst comprises a platinum group metal on a support, the method comprising intermittently admixing with the feedstock or recycle stream of the reactor an additive which comprises a nonionic, organometallic platinum group metal coordination composition at a temperature of below about 200.degree. C. wherein said composition
- a) has a breakdown temperature between about 40.degree. and about 570.degree. C.; and
- b) is substantially free from a disadvantageous amount of phosphorus, arsenic, antimony or halides, wherein platinum group metal is caused to be deposited on said catalyst.
- 14. The method of claim 13 wherein said composition is selected from the group consisting of
- a) a composition of the general formula
- L.sup.1 PtR.sup.1 R.sup.2
- wherein L.sup.1 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands; and R.sup.1 and R.sup.2 are each, independently, substituted or unsubstituted methyl, benzyl, aryl, cyclooctadiene or pentamethyl cyclopentadiene;
- b) a composition of the general formula
- L.sup.2 M.sup.1 R.sup.3
- wherein L.sup.2 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous or acetylenic monodentate ligands; M.sup.1 is rhodium or iridium; and R.sup.3 is cyclopentadiene or pentamethyl cyclopentadiene;
- c) a composition of the general formula
- L.sup.3 M.sup.2 (C.sub.4 R.sup.4.sub.4)
- wherein L.sup.3 is either a single cyclic polyolefin or nitrogenous bidentate ligand or a pair of nitrogenous monodentate ligands; M.sup.2 is platinum, palladium, rhodium or iridium; and R.sup.4 is COOR.sup.5, wherein R.sup.5 is hydrogen or alkyl having from 1 to 10 carbons;
- d) a composition of the general formula
- L.sup.4 M.sup.3 (COOR.sup.6).sub.2
- or a dimer thereof, wherein L.sup.4 is a non-nitrogenous cyclic polyolefin ligand; M.sup.3 is platinum or iridium; and R.sup.6 is alkyl; and
- e) a composition comprising the reaction product of L.sup.5 RhX and R.sup.7 MgX wherein L.sup.5 is a non-nitrogenous cyclic polyolefin ligand; R.sup.7 is methyl, benzyl, aryl, cyclopentadiene or pentamethyl cyclopentadiene; and X is a halide.
- 15. The method of claim 14 wherein L.sup.1, L.sup.2 and L.sup.3 are selected from the group consisting of cyclopentadiene, cyclooctadiene, pentamethyl cyclopentadiene, cyclooctatetrene, o-phenantholine, o-toluidine, norbornadiene, pyridine and bipyridine.
- 16. The method of claim 14 wherein L.sup.4 and L.sup.5 are selected from the group consisting of cyclooctadiene and pentamethyl cyclopentadiene.
- 17. The method of claim 14 wherein said additive further comprises a feedstock- or recycle stream-soluble solvent for said composition.
- 18. The method of claim 17 wherein said solvent is selected from the group consisting of 1 to 4 carbon alcohols, acetone, tetrahydrofuran, methyl tertiary butyl ether and mixtures thereof.
- 19. The method of claim 13 wherein said additive is introduced into the feedstock or recycle stream in an amount of about 10 to about 10,000 parts per million of platinum group metal.
RELATED APPLICATIONS
This application is a continuation-in-part of copending and commonly assigned U.S. Patent Application entitled "Method for Reducing Emissions From or Increasing the Utilizable Energy of Fuel for Powering Internal Combustion Engines", Ser. No. 291,245, filed on Dec. 28, 1988 now abandoned in the names of Epperly, Sprague, Kelso, and Bowers; which in turn is a continuation-in-part of copending and commonly assigned U.S. Patent Application entitled "Diesel Fuel Additives and Diesel Fuels Containing Soluble Platinum Group Metal Compounds and Use in Diesel Engines", Ser. No. 897,864, filed in the names of Bowers and Sprague on Aug. 19, 1986, now U.S. Pat. No. 4,892,562; and copending and commonly assigned U.S. Patent Application entitled "Gasoline Additives and Gasoline Containing Soluble Platinum Group Metal Compounds and Use in Internal Combustion Engines", Ser. No. 897,869, filed in the names of Bowers and Sprague on Aug. 19, 1986, now U.S. Pat. No. 4,891,051; each of which is a continuation-in-part of prior application Ser. No. 796/428, filed Nov. 8, 1985, now abandoned which in turn is a continuation-in-part of prior applications Ser. No. 677,954, filed Dec. 4, 1984, now abandoned and Ser. No. 790,738, filed Oct. 24, 1985, now abandon all by Bowers and Sprague, the inventors herein. The disclosures of each of these prior applications is hereby incorporated by reference herein.
US Referenced Citations (13)
Non-Patent Literature Citations (9)
Entry |
Belluco, Organometallic and Coordination Chemistry of Platinum, Academic Press, NY, pp. 221, 222, 226, 232, 295-297, 441-442, 449, 454 & 455 (1974). |
Deganello, Transition Metal Complexes of Cyclic Polyoefins, Academic Press, N.Y., pp. 97-100, 102, 277-278, 281-283, 288-291 (1979). |
Dickson, Organometallic Chemistry of Rhodium and Iridium, Academic Press, N.Y., pp. 167-169, 178-180, 198-200, 220-226, 248, 258-260, 264, 271 & 277 (1983). |
Maitlis, The Organic Chemistry of Palladium, Academic Press, N.Y., pp. 68, 70, 76, 77, 83, 93, 102, 103, 136, 158, 165, 202-204, 228, 242, 249, 257-258 (1971). |
Chemical Abstracts 76 112565 p (1792). |
Chemical Abstracts 76 11335 g (1792). |
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Chemical Abstracts 97 110175w (1982). |
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Continuation in Parts (6)
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Number |
Date |
Country |
Parent |
291245 |
Dec 1988 |
|
Parent |
897864 |
Aug 1986 |
|
Parent |
897869 |
Aug 1986 |
|
Parent |
796428 |
Nov 1985 |
|
Parent |
677954 |
Dec 1984 |
|
Parent |
790738 |
Oct 1985 |
|