US4145314A
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Preparation of highly dispersed supported group viii metal catalysts and the redispersion of sintered or agglomerated supported group viii metal catalysts by the addition of phosphorus
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1977-06-17
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Granted: 1979-03-20
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Expires: 1997-06-17
Abstract
Abstract The instant invention relates to a method of preparing highly dispersed supported Group VIII metal catalysts. The instant invention further relates to the redispersion of sintered or agglomerated supported Group VIII metal catalysts. The process comprises the formation of supported Group VIII metal-phosphorus intermediate compounds followed by the treatment of these supported Group VIII metal-phosphorus compounds in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C., preferably, about 550° C. to about 700° C., most preferably from 630°-700° C. The composition resultant from the dispersion heating step will form the highly dispersed, supported Group VIII metal catalysts by decomposition when reacting with an oxygen containing atmosphere, e.g. air, or reacting with water.
Inventors
- 👤 Shun C. Fung
- 👤 Yen-Chi Pan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 02:45
CPC Classifications
B; B01; B01J; B01J37/00; B01J37/28; B01J23/00; B01J23/38; B01J23/40
Claims Analysis
Total Claims: 53
Claim 1
Independent Claim
275 words
A process for preparing Group VIII noble metal compositions, wherein the Group VIII noble metal particle size is less than 100A, supported on a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process consists of the steps of: (a) depositing onto said support at least one Group VIII noble metal by impregnating said support with a water soluble Group VIII noble metal salt selected from the group consisting of Group VIII noble metal chloride. Group VIII noble metal nitrate and Group VIII noble metal ammonia complexes and reducing said Group VIII noble metal; salt to the Group VIII noble metal; (b) depositing onto said support elemental phosphorus in an amount sufficient to result in a phosphorus-Group VIII noble metal atomic ratio of about 0.3 to about 3.0, wherein steps (a) and (b) may be performed sequentially in any order; (c) heating said composition resulting from the completion of steps (a) and (b) in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C., and a pressure in the range of about 0.1 atmospheres to about 10 atmospheres, for a time sufficient to form supported Group VIII noble metal-phosphorus compounds; (d) decomposing said composition resulting from the completion of step (c) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C., or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 2
Dependent Claim
275 words
A process for preparing Group VIII noble metal compositions, wherein the Group VIII noble metal particle size is less than 100A, supported on a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process consists of the steps of: (a) depositing onto said support at least one Group VIII noble metal by impregnating said support with a water soluble Group VIII noble metal salt selected from the group consisting of Group VIII noble metal chloride. Group VIII noble metal nitrate and Group VIII noble metal ammonia complexes and reducing said Group VIII noble metal; salt to the Group VIII noble metal; (b) depositing onto said support elemental phosphorus in an amount sufficient to result in a phosphorus-Group VIII noble metal atomic ratio of about 0.3 to about 3.0, wherein steps (a) and (b) may be performed sequentially in any order; (c) heating said composition resulting from the completion of steps (a) and (b) in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C., and a pressure in the range of about 0.1 atmospheres to about 10 atmospheres, for a time sufficient to form supported Group VIII noble metal-phosphorus compounds; (d) decomposing said composition resulting from the completion of step (c) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C., or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 3
Dependent Claim
31 words
The process of claim 1 wherein said water soluble Group VIII noble metal salts are selected from the group consisting of water soluble platinum chloride, platinum nitrate and platinum ammonia complexes.
Claim 4
Dependent Claim
29 words
The process of claim 2 wherein said water soluble Group metal salt is H 2 PtCl 6 and said solution of H 2 PtCl 6 is an aqueous solution.
Claim 5
Dependent Claim
41 words
The process of claim 1 wherein said high surface area support is selected from the group consisting of carbon, alumina, silica-alumina, and mixtures thereof, and the surface area of said support ranges from about 10 to about 2000 m 2 /g.
Claim 6
Dependent Claim
13 words
The process of claim 3 wherein said high surface area support is carbon.
Claim 7
Dependent Claim
31 words
The process of claim 1 wherein said elemental phosphorus is deposited onto said support by impregnating onto said support a water soluble phosphorus salt and subsequently reducing said impregnated phosphorus salt.
Claim 8
Dependent Claim
24 words
The process of claim 6 wherein said water soluble phosphate salt is ammonium phosphate and said solution of ammonium phosphate is an aqueous solution.
Claim 9
Dependent Claim
22 words
The process of claim 1 wherein said elemental phosphorus is deposited onto said support by the vapor deposition method in a vacuum.
Claim 10
Dependent Claim
13 words
The process of claim 8 wherein said support is impregnated with red phosphorus.
Claim 11
Dependent Claim
14 words
The process of claim 1 wherein said inert atmosphere in step (c) is He.
Claim 12
Dependent Claim
18 words
The process of claim 1 wherein said phosphorus to Group VIII metal atomic ratio is above about 2.0.
Claim 13
Dependent Claim
18 words
The process of claim 1 wherein said phosphorus to Group VIII metal atomic ratio is above about 1.0.
Claim 14
Dependent Claim
35 words
The process of claim 1 wherein the temperature of step (c) ranges from about 550° C. to about 700° C., and the pressure of step (c) ranges from about 1.0 atm. to about 2.0 atm.
Claim 15
Dependent Claim
41 words
The process of claim 1 wherein the temperature of the decomposition in an oxygen-containing atmosphere ranges from about 25° C. to about 40° C., and the temperature of the decomposition in water ranges from about 20° C. to about 40° C.
Claim 16
Dependent Claim
28 words
The process of claim 1 wherein said decomposition step (d) is performed by exposing to air at room temperature said composition resulting from the completion of step (c).
Claim 17
Dependent Claim
15 words
The process of claim 1 wherein said heating step (c) is performed for 1-6 hours.
Claim 18
Dependent Claim
193 words
A process for preparing, supported Group VIII metal compositions, wherein the Group VIII metal particle size is less than 100 A, from the corresponding supported Group VIII metal compositions possessing low degrees of dispersion, wherein said support is a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process comprises the steps of: (a) heating said supported Group VIII metal composition of low dispersion in the presence of phosphorus in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres, for a time sufficient to form highly dispersed, supported Group VIII metal-phosphorus compounds; and (b) decomposing said composition resulting from the completion of step (a) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 19
Dependent Claim
193 words
A process for preparing, supported Group VIII metal compositions, wherein the Group VIII metal particle size is less than 100 A, from the corresponding supported Group VIII metal compositions possessing low degrees of dispersion, wherein said support is a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process comprises the steps of: (a) heating said supported Group VIII metal composition of low dispersion in the presence of phosphorus in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres, for a time sufficient to form highly dispersed, supported Group VIII metal-phosphorus compounds; and (b) decomposing said composition resulting from the completion of step (a) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 20
Dependent Claim
29 words
The process of claim 17 wherein phosphorus is deposited onto said support by impregnating onto said support a water soluble phosphorus salt and subsequently reducing said impregnated phosphorus salt.
Claim 21
Dependent Claim
24 words
The process of claim 18 wherein said water soluble phosphate salt is ammonium phosphate and said solution of ammonium phosphate is an aqueous solution.
Claim 22
Dependent Claim
21 words
The process of claim 17 wherein elemental phosphorus is deposited onto said support by the vapor deposition method in a vacuum.
Claim 23
Dependent Claim
13 words
The process of claim 20 wherein said support is impregnated with red phosphorus.
Claim 24
Dependent Claim
41 words
The process of claim 17 wherein said high surface area support is selected from the group consisting of carbon, alumina, silica-alumina, and mixtures thereof, and the surface area of said support ranges from about 10 to about 2000 m 2 /g.
Claim 25
Dependent Claim
13 words
The process of claim 22 wherein said high surface area support is carbon.
Claim 26
Dependent Claim
24 words
The process of claim 17 wherein said Group VIII metal is selected from the group consisting of Group VIII noble metals and mixtures thereof.
Claim 27
Dependent Claim
12 words
The process of claim 17 wherein said Group VIII metal is Pt.
Claim 28
Dependent Claim
12 words
The process of claim 23 wherein said Group VIII metal is Pt.
Claim 29
Dependent Claim
14 words
The process of claim 17 where the inert atmosphere of step (a) is He.
Claim 30
Dependent Claim
29 words
The process of claim 18 wherein said phosphorus is deposited in an amount sufficient to result in a phosphorus/Group VIII metal atomic ratio of about 0.3 to about 3.0.
Claim 31
Dependent Claim
18 words
The process of claim 28 wherein said phosphorus to Group VIII metal atomic ratio is above about 2.0.
Claim 32
Dependent Claim
18 words
The process of claim 29 wherein said phosphorus to Group VIII metal atomic ratio is above about 1.0.
Claim 33
Dependent Claim
29 words
The process of claim 20 wherein said phosphorus is deposited in an amount sufficient to result in a phosphorus/Group VIII metal atomic ratio of about 0.3 to about 3.0.
Claim 34
Dependent Claim
18 words
The process of claim 31 wherein said phosphorus to Group VIII metal atomic ratio is above about 2.0.
Claim 35
Dependent Claim
18 words
The process of claim 32 wherein said phosphorus to Group VIII metal atomic ratio is above about 1.0.
Claim 36
Dependent Claim
35 words
The process of claim 17 wherein the temperature of step (a) ranges from above 550° C. to about 700° C., and the pressure of step (a) ranges from about 1.0 atm. to about 2.0 atm.
Claim 37
Dependent Claim
41 words
The process of claim 17 wherein the temperature of the decomposition in an oxygen-containing atmosphere ranges from about 25° C. to about 40° C., and the temperature of the decomposition in water ranges from about 20° C. to about 40° C.
Claim 38
Dependent Claim
28 words
The process of claim 17 wherein said decomposition step (b) is performed by exposing to air at room temperature said composition resulting from the completion of step (a).
Claim 39
Dependent Claim
15 words
The process of claim 17 wherein said heating step (a) is performed for 1-6 hours.
Claim 40
Dependent Claim
260 words
A process for preparing supported Group VIII noble metal compositions wherein the Group VIII noble metal particle size is less than 100° A, wherein the support is a high surface area solid support selected from the group consisting of carbon, alumina, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein said support contains elemental phosphorus, wherein the process consists of the steps of: (a) depositing onto said support at least one Group VIII noble metal, by impregnating said support with a water soluble Group VIII noble metal salt selected from the group consisting of Group VIII noble metal chloride, Group VIII noble metal nitrate and Group VIII noble metal ammonia complexes and reducing said Group VIII noble metal salt to the Group VIII noble metal, in an amount sufficient to result in a phosphorus/Group VIII noble metal atomic ratio of about 0.3 to about 3.0; (b) heating the composition resulting from step (a) in an inert atmosphere at a temperature in the range of 400° C. to 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres, for a time sufficient to form the supported Group VIII noble metal-phosphorus compounds; and (c) decomposing said combination resulting from the completion of step (b) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 41
Dependent Claim
260 words
A process for preparing supported Group VIII noble metal compositions wherein the Group VIII noble metal particle size is less than 100° A, wherein the support is a high surface area solid support selected from the group consisting of carbon, alumina, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein said support contains elemental phosphorus, wherein the process consists of the steps of: (a) depositing onto said support at least one Group VIII noble metal, by impregnating said support with a water soluble Group VIII noble metal salt selected from the group consisting of Group VIII noble metal chloride, Group VIII noble metal nitrate and Group VIII noble metal ammonia complexes and reducing said Group VIII noble metal salt to the Group VIII noble metal, in an amount sufficient to result in a phosphorus/Group VIII noble metal atomic ratio of about 0.3 to about 3.0; (b) heating the composition resulting from step (a) in an inert atmosphere at a temperature in the range of 400° C. to 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres, for a time sufficient to form the supported Group VIII noble metal-phosphorus compounds; and (c) decomposing said combination resulting from the completion of step (b) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 42
Dependent Claim
30 words
The process of claim 38 wherein said water soluble Group VIII metal salts are selected from the group consisting of water soluble platinum cloride, platinum nitrate and platinum ammonia complexes.
Claim 43
Dependent Claim
30 words
The process of claim 43 wherein said water soluble Group VIII metal salt is H 2 PtCl 6 and said solution of H 2 PtCl 6 is an aqueous solution.
Claim 44
Dependent Claim
14 words
The process of claim 40 wherein said high surface area support is activated carbon.
Claim 45
Dependent Claim
14 words
The process of claim 38 wherein said inert atmosphere in step (b) is He.
Claim 46
Dependent Claim
18 words
The process of claim 38 wherein said phosphorus to Group VIII metal atomic ratio is above about 2.0.
Claim 47
Dependent Claim
17 words
The process of claim 43 wherein said phosphorus to Group VIII metal atomic is above about 1.0.
Claim 48
Dependent Claim
35 words
The process of claim 38 wherein the temperature of step (b) ranges from about 550° C. to about 700° C., and the pressure of step (b) ranges from about 1.0 atm. to about 2.0. atm.
Claim 49
Dependent Claim
41 words
The process of claim 38 wherein the temperature of the decomposition in an oxygen-containing atmosphere ranges from about 25° C. to about 40° C., and the temperature of the decomposition in water ranges from about 20° C. to about 40° C.
Claim 50
Dependent Claim
28 words
The process of claim 38 wherein said decomposition step (c) is performed by exposing to air at room temperature said composition resulting from the completion of step (b).
Claim 51
Dependent Claim
15 words
The process of claim 36 wherein said heating step (b) is performed for 1-6 hours.
Claim 52
Dependent Claim
174 words
A process for preparing supported Group VIII metal compositions, wherein the Group VIII metal particle size is less than 100 A, from the corresponding supported Group VIII metal-phosphorus compounds possessing low degrees of dispersion, wherein said support is a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process comprises the steps of: (a) heating said supported Group VIII metal-phosphorus compounds of low dispersion in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres; (b) decomposing said composition resulting from the completion of step (a) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
Claim 53
Dependent Claim
174 words
A process for preparing supported Group VIII metal compositions, wherein the Group VIII metal particle size is less than 100 A, from the corresponding supported Group VIII metal-phosphorus compounds possessing low degrees of dispersion, wherein said support is a high surface area solid support selected from the group consisting of carbon, alumina, silica, silica-alumina, zeolite, kieselguhr, vermiculite, the refractory oxides of Group IVb and Vb transition metals, and mixtures thereof, wherein the process comprises the steps of: (a) heating said supported Group VIII metal-phosphorus compounds of low dispersion in an inert atmosphere at a temperature in the range of about 400° C. to about 750° C. and a pressure in the range of about 10 atmospheres to about 0.1 atmospheres; (b) decomposing said composition resulting from the completion of step (a) by either reacting said composition with an oxygen-containing atmosphere at a temperature in the range of about 0° C. to about 150° C. or reacting said composition with water at a temperature in the range of about 20° C. to about 100° C.
References Cited (Backward Citations)
US2890167A
Cited
US2983997A
Cited
US3179694A
Cited
US3236693A
Cited
US3411953A
Cited
US3448165A
Cited
US3784483A
Cited
US3792086A
Cited
US3884798A
Cited
US3961987A
Cited
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