US4313820A
Expired / Lapsed
US
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Hydrodesulfurization of organic sulfur compounds and hydrogen sulfide removal with incompletely sulfided zinc titanate materials
Assignee: Phillips Petroleum Co
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Filing: 1980-09-23
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Granted: 1982-02-02
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Expires: 2000-09-23
Abstract
Abstract Hydrogen sulfide is removed from a fluid stream by contacting the fluid stream which contains hydrogen sulfide with an absorbing composition comprising zinc, titanium and at least one promoter selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, molybdenum, rhenium, and compounds thereof. If organic sulfur compounds are present in the fluid stream, the absorbing composition acts as a hydrodesulfurization catalyst to convert the sulfur in the organic sulfur compounds to hydrogen sulfide which is subsequently removed from the fluid stream by the absorbing composition. If olefin contaminants are present in the fluid stream, the absorbing composition acts as hydrogenation catalyst to hydrogenate the olefin contaminants to paraffins.
Inventors
- 👤 Floyd E. Farha, Jr.
- 👤 Lloyd E. Gardner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 01:51
CPC Classifications
C; C10; C10G; C10G45/00; C10G45/02; C10G45/04; C10G45/10; B; B01; B01J; B01J23/00; B01J23/16; B01J23/70; B01J23/76; B01J23/80; B01J23/84; B01J23/85; B01J23/88; B01J23/887; B01J23/8873
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
108 words
A process for hydrodesulfurizing an organic sulfur compound contained in a fluid stream to convert the sulfur in the organic sulfur compound to hydrogen sulfide and for removing hydrogen sulfide from the fluid stream comprising the step of contacting said fluid stream under suitable hydrodesulfurization conditions with an incompletely sulfided catalyst/absorbing composition comprising zinc titanate, and at least one promoter selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, molybdenum, rhenium, and compounds thereof, wherein the concentration by weight of said at least one promoter in said catalyst/absorbing composition is less than the total concentration by weight of said zinc titanate in said catalyst/absorbing composition.
Claim 2
Dependent Claim
108 words
A process for hydrodesulfurizing an organic sulfur compound contained in a fluid stream to convert the sulfur in the organic sulfur compound to hydrogen sulfide and for removing hydrogen sulfide from the fluid stream comprising the step of contacting said fluid stream under suitable hydrodesulfurization conditions with an incompletely sulfided catalyst/absorbing composition comprising zinc titanate, and at least one promoter selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, molybdenum, rhenium, and compounds thereof, wherein the concentration by weight of said at least one promoter in said catalyst/absorbing composition is less than the total concentration by weight of said zinc titanate in said catalyst/absorbing composition.
Claim 3
Dependent Claim
35 words
A process in accordance with claim 1 wherein said organic sulfur compound is selected from the group consisting of sulfides, disulfides, mercaptans, carbonyl sulfide, thiophenes, benzothiophenes, dibenzothiophenes and mixtures of any two or more thereof.
Claim 4
Dependent Claim
28 words
A process in accordance with claim 1 wherein said fluid stream contains an olefin contaminant which is hydrogenated when said fluid stream is contacted with said catalyst/absorbing composition.
Claim 5
Dependent Claim
51 words
A process in accordance with claim 3 wherein said fluid stream is an aerosol propellant selected from the group consisting of isobutane, n-butane, propane and mixtures of any two or more thereof and said olefin contaminant is selected from the group consisting of ethylene, propylene, n-butenes, isobutene, n-pentenes and branched pentenes.
Claim 6
Dependent Claim
93 words
A process in accordance with claim 3 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 205° C. to about 538° C., a total system pressure in the range of about 100 psig to about 1000 psig, a hydrogen flow rate in the range of about 100 to about 10,000 SCF/bbl and a residence time for said liquid stream in the presence of said catalyst/absorbing composition in the range of about 0.1 to about 50 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 7
Dependent Claim
94 words
A process in accordance with claim 3 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 260° C. to about 427° C., a total system pressure in the range of about 100 psig to about 500 psig, a hydrogen flow rate in the range of about 250 SCF/bbl to about 3,000 SCF/bbl and a residence time for said fluid stream in the presence of said catalyst/absorbing composition in the range of about 1 to about 20 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 8
Dependent Claim
43 words
A process in accordance with claim 1 wherein said zinc titanate is prepared by calcining a mixture of zinc oxide and titanium dioxide in the presence of molecular oxygen at a temperature in the range of about 650° C. to about 1050° C.
Claim 9
Dependent Claim
29 words
A process in accordance with claim 7 wherein the atomic ratio of zinc to titanium in said catalyst/absorbing composition is in the range of about 1:1 to about 3:1.
Claim 10
Dependent Claim
29 words
A process in accordance with claim 7 wherein the atomic ratio of zinc to titanium in said catalyst/absorbing composition is in the range of about 1.8:1 to about 2.2:1.
Claim 11
Dependent Claim
46 words
A process in accordance with claim 7 wherein said catalyst/absorbing composition has been calcined in the presence of molecular oxygen at a temperature in the range of about 500° to about 650° C. after said at least one promotor has been added to said zinc titanate.
Claim 12
Dependent Claim
83 words
A process in accordance with claim 10 wherein the concentration of vanadium, chromium, manganese, iron, cobalt, nickel, or molybdenum as individual promoters, if present, expressed as an element, is in the range of about 0.4 to about 16 weight percent based on the weight of said catalyst/absorbing composition and the concentration of rhenium as an individual promoter, if present, expressed as an element, is in the range of about 0.05 to about 2.5 weight percent based on the weight of said catalyst/absorbing composition.
Claim 13
Dependent Claim
50 words
A process in accordance with claim 11 wherein the total concentration of any combination of the group from which said at least one promoter is selected, expressed as an element, is in the range of about 1 to about 28 weight percent based on the weight of said catalyst/absorbing composition.
Claim 14
Dependent Claim
20 words
A process in accordance with claim 1 wherein said at least one promoter is the combination of cobalt and molybdenum.
Claim 15
Dependent Claim
26 words
A process in accordance with claim 11 wherein the cobalt:molybdenum atomic ratio in said catalyst/absorbing composition is in the range of about 0.3:1 to about 0.8:1.
Claim 16
Dependent Claim
34 words
A process in accordance with claim 1 wherein said catalyst/absorbing composition additionally comprises at least one oxidation promoter selected from the group consisting of ruthenium, rhodium, palladium, silver, tungsten, iridium, platinum, and compounds thereof.
Claim 17
Dependent Claim
83 words
A process in accordance with claim 15 wherein the concentration of ruthenium, rodium, palladium, silver, iridium or platinum as individual oxidation promoters, expressed as an element, if present, is in the range of about 0.05 to about 2.5 weight percent based on the weight of said catalyst/absorbing composition and the concentration of tungsten as an individual promoter, expressed as an element, if present, is in the range of about 0.4 to about 16 weight percent based on the weight of said catalyst/absorbing composition.
Claim 18
Dependent Claim
51 words
A process in accordance with claim 16 wherein the total concentration of any combination of said at least one promoter and said at least one oxidation promoter, expressed as an element, is in the range of about 1 to about 28 weight percent based on the weight of said catalyst/absorbing composition.
Claim 19
Dependent Claim
92 words
A process in accordance with claim 1 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 205° C. to about 538° C., a total system pressure in the range of about atmospheric to about 1000 psig, a hydrogen flow rate in the range of about 100 to about 10,000 SCF/bbl and a residence time for said fluid stream in the presence of said catalyst/absorbing composition in the range of about 0.1 to about 50 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 20
Dependent Claim
94 words
A process in accordance with claim 1 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 260° C. to about 427° C., a total system pressure in the range of about 15 psig to about 200 psig, a hydrogen flow rate in the range of about 250 SCF/bbl to about 3,000 SCF/bbl and a residence time for said fluid stream in the presence of said catalyst/absorbing composition in the range of about 1 to about 20 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 21
Dependent Claim
17 words
A process in accordance with claim 1 wherein said catalyst/absorbing composition is sulfided during said hydrodesulfurization process.
Claim 22
Dependent Claim
51 words
A process in accordance with claim 20 additionally comprising steps of: discontinuing the flow of said fluid stream over said catalyst/absorbing composition; and contacting said catalyst/absorbing composition, after the flow of said fluid stream is discontinued, with a molecular oxygen-containing fluid under suitable regeneration conditions to thereby regenerate said catalyst/absorbing composition.
Claim 23
Dependent Claim
62 words
A process in accordance with claim 21 wherein said suitable regeneration conditions comprise a feed rate of said molecular oxygen-containing fluid suitable to supply sufficient oxygen to remove substantially all of the sulfur from said catalyst/absorbing composition, a temperature in the range of about 370° to about 815° C., and a pressure in the range of about atmospheric to about 1000 psig.
Claim 24
Dependent Claim
18 words
A process in accordance with claim 22 wherein sulfur is removed as an oxide during said regeneration period.
Claim 25
Dependent Claim
40 words
A process in accordance with claim 21 additionally comprising the step of purging said catalyst/absorbing composition with an inert fluid after the step of terminating the flow of said fluid stream and before the step of regenerating said catalyst/absorbing composition.
Claim 26
Dependent Claim
93 words
A process in accordance with claim 21 additionally comprising the steps of: terminating the flow of said molecular oxygen-containing fluid over said catalyst/absorbing composition after said catalyst/absorbing composition is regenerated; purging said catalyst/aborbing composition with an inert fluid after the flow of said molecular oxygen-containing fluid is terminated; terminating the flow of said inert fluid over said catalyst/absorbing composition after said molecular oxygen-containing fluid is substantially purged from said catalyst/absorbing composition; and recontacting said catalyst/absorbing composition with said fluid stream after the flow of said inert fluid over said catalyst/absorbing composition is terminated.
Claim 27
Dependent Claim
68 words
A process for hydrodesulfurizing an organic sulfur compound contained in a fluid stream, which does not contain hydrocarbons which are subject to dehydrogenation, reforming or hydrocracking, to convert the sulfur in the organic sulfur compound to hydrogen sulfide and for removing hydrogen sulfide from the fluid stream comprising the step of contacting said fluid stream under suitable hydrodesulfurization conditions with an incompletely sulfided catalyst/absorbing composition comprising zinc titanate.
Claim 28
Dependent Claim
68 words
A process for hydrodesulfurizing an organic sulfur compound contained in a fluid stream, which does not contain hydrocarbons which are subject to dehydrogenation, reforming or hydrocracking, to convert the sulfur in the organic sulfur compound to hydrogen sulfide and for removing hydrogen sulfide from the fluid stream comprising the step of contacting said fluid stream under suitable hydrodesulfurization conditions with an incompletely sulfided catalyst/absorbing composition comprising zinc titanate.
Claim 29
Dependent Claim
35 words
A process in accordance with claim 26 wherein said organic sulfur compound is selected from the group consisting of sulfides, disulfides, mercaptans, carbonyl sulfides, thiophenes, benzothiophenes, dibenzothiophenes and mixtures of any two or more thereof.
Claim 30
Dependent Claim
43 words
A process in accordance with claim 26 wherein said zinc titanate is prepared by calcining a mixture of zinc oxide and titanium dioxide in the presence of molecular oxygen at a temperature in the range of about 650° C. to about 1050° C.
Claim 31
Dependent Claim
29 words
A process in accordance with claim 28 wherein the atomic ratio of zinc to titanium in said catalyst/absorbing composition is in the range of about 1:1 to about 3:1.
Claim 32
Dependent Claim
29 words
A process in accordance with claim 28 wherein the atomic ratio of zinc to titanium in said catalyst/absorbing composition is in the range of about 1.8:1 to about 2.2:1.
Claim 33
Dependent Claim
92 words
A process in accordance with claim 26 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 205° C. to about 538° C., a total system pressure in the range of about atmospheric to about 1000 psig, a hydrogen flow rate in the range of about 100 to about 10,000 SCF/bbl and a residence time for said fluid stream in the presence of said catalyst/absorbing composition in the range of about 0.1 to about 50 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 34
Dependent Claim
94 words
A process in accordance with claim 26 wherein said suitable hydrodesulfurization conditions comprise a temperature in the range of about 260° C. to about 427° C., a total system pressure in the range of about 15 psig to about 200 psig, a hydrogen flow rate in the range of about 250 SCF/bbl to about 3,000 SCF/bbl and a residence time for said fluid stream in the presence of said catalyst/absorbing composition in the range of about 1 to about 20 liquid volumes of said fluid stream per volume of said catalyst/absorbing composition per hour.
Claim 35
Dependent Claim
17 words
A process in accordance with claim 26 wherein said catalyst/absorbing composition is sulfided during said hydrodesulfurization process.
Claim 36
Dependent Claim
52 words
A process in accordance with claim 33 additionally comprising the steps of: discontinuing the flow of said fluid stream over said catalyst/absorbing composition; and contacting said catalyst/absorbing composition, after the flow of said fluid stream is discontinued, with a molecular oxygen-containing fluid under suitable regeneration conditions to thereby regenerate said catalyst/absorbing composition.
Claim 37
Dependent Claim
63 words
A process in accordance with claim 34 wherein said suitable regeneration conditions comprise a feed rate of said molecular oxygen-containing fluid suitable to supply sufficient oxygen to remove substantially all of the sulfur from said catalyst/absorbing composition, a temperature in the range of about 370° C. to about 815° C., and a pressure in the range of about atmospheric to about 1000 psig.
Claim 38
Dependent Claim
18 words
A process in accordance with claim 34 wherein sulfur is removed as an oxide during the regeneration period.
Claim 39
Dependent Claim
40 words
A process in accordance with claim 34 additionally comprising the step of purging said catalyst/absorbing composition with an inert fluid after the step of terminating the flow of said fluid stream and before the step of regenerating said catalyst/absorbing composition.
Claim 40
Dependent Claim
93 words
A process in accordance with claim 34 additionally comprising the steps of: terminating the flow of said molecular oxygen-containing fluid over said catalyst/absorbing composition after said catalyst/absorbing composition is regenerated; purging said catalyst/absorbing composition with an inert fluid after the flow of said molecular oxygen-containing fluid is terminated; terminating the flow of said inert fluid over said catalyst/absorbing composition after said molecular oxygen-containing fluid is substantially purged from said catalyst/absorbing composition; and recontacting said catalyst/absorbing composition with said fluid stream after the flow of said inert fluid over said catalyst/absorbing composition is terminated.
References Cited (Backward Citations)
US2037790A
Cited
US2279198A
Cited
US2298347A
Cited
US2393288A
Cited
US2591525A
Cited
GB828934A
Cited
US3105811A
Cited
US3427253A
Cited
US4029599A
Cited
US4071439A
Cited
US4144277A
Cited
US4052296A
Cited
US4128205A
Cited
US4155835A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-02-01 | 1985-08-03 | 1986-02-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-02-01 | 1989-08-03 | 1990-02-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-02-01 | 1993-08-03 | 1994-02-02 | $7700.00 | Window Closed / Lapsed |