Patent US4152246A successfully refreshed from Google Patents.
US4152246A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Catalyzed processes for the hydrotreatment of hydrocarbons
Assignee: Compagnie Francaise de Raffinage SA
•
Filing: 1977-07-18
•
Granted: 1979-05-01
•
Expires: 1997-07-18
Abstract
Abstract The processes of the present invention employ catalysts in the hydrotreatment of hydrocarbons and comprise, on a refractory inorganic oxide support, the following metals: (a) from 0.02 to 2% of at least one platinum metal; (b) from 0.02 to 2% of at least one metal belonging to the group consisting of zirconium, titanium, and tungsten; (c) from 0.02 to 2% tin. This catalyst is preferably halogenated, typically with chlorine, from 0.4 to 2%. The preferred process according to this invention is the isomerization of a charge of alkylaromatic hydrocarbons, and particularly those having eight carbon atoms. The preferred isomerization catalyst is a platinum, tin and zirconium trimetallic catalyst halogenated with chlorine approximately from 1 to 2% based on the total catalyst weight. The preferred isomerization process is practiced in at least two successive stages with the contacting of the catalyst taking place in at least one of said stages; and especially under the following conditions: (a) Pressure: Comprised between 3 and 40 bars. (b) Temperature: Comprised between 250° and 550° C. (c) Molar ratio of hydrogen to hydrocarbons: Comprised between 3 and 15. (d) Overall space velocity (v/v/h), measured in the liquid state: Comprised between 0.5 and 4, and preferably between 1 and 2.5. Said catalysts are also useful for hydroreforming and aromatizing being surprisingly superior for all these types of reactions.
Inventors
- 👤 Joseph E. Weisang
- 👤 Philippe Engelhard
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 06:25
CPC Classifications
C; C10; C10G; C10G35/00; C10G35/04; C10G35/06; C10G35/085; C10G35/09; B; B01; B01J; B01J23/00; B01J23/38; B01J23/54; B01J23/56; B01J23/62; B01J23/622; B01J23/626; B01J23/64; B01J23/652; B01J23/6527; B01J35/00; B01J35/60; B01J35/61; B01J35/615; B01J35/63; B01J35/633; C07; C07C; C07C5/00; C07C5/22; C07C5/27; C07C5/2702; C07C5/2724
Claims Analysis
Total Claims: 66
Claim 1
Independent Claim
114 words
A process of reforming a hydrocarbon charge comprising placing said hydrocarbon charge, hydrogen, and a catalyst under reforming conditions, said catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support; (a) about 0.02 to 2% of at least one platinummetal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentages being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 2
Dependent Claim
114 words
A process of reforming a hydrocarbon charge comprising placing said hydrocarbon charge, hydrogen, and a catalyst under reforming conditions, said catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support; (a) about 0.02 to 2% of at least one platinummetal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentages being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 3
Dependent Claim
52 words
A process according to claim 1, wherein said ingredients are only of tin, of platinum and of zirconium, the support is an alumina whose specific surface is between 100 and 350 m 2 /g and whose specific pore volume is of more than 0.1 cm 3 /g, and said halogen is chlorine.
Claim 4
Dependent Claim
13 words
A process according to claim 1, comprising first reducing said catalyst by hydrogen.
Claim 5
Dependent Claim
20 words
A process according to claim 2, comprising first subjecting said catalyst to reduction by hydrogen and presulfurizing by hydrogen sulfide.
Claim 6
Dependent Claim
114 words
A process of aromatizing a hydrocarbon charge comprising placing said hydrocarbon charge, hydrogen, and a catalyst under aromatizing conditions, said catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said seight percentages being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 7
Dependent Claim
114 words
A process of aromatizing a hydrocarbon charge comprising placing said hydrocarbon charge, hydrogen, and a catalyst under aromatizing conditions, said catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said seight percentages being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 8
Dependent Claim
52 words
A process according to claim 5, wherein said ingredients are only of tin, of platinum and of zirconium, the support is an alumina whose specific surface is between 100 and 350 m 2 /g and whose specific pore volume is of more than 0.1 cm 3 /g, and said halogen is chlorine.
Claim 9
Dependent Claim
13 words
A process according to claim 5, comprising first reducing said catalyst by hydrogen.
Claim 10
Dependent Claim
20 words
A process according to claim 6, comprising first subjecting said catalyst to reduction by hydrogen and presulfurizing by hydrogen sulfide.
Claim 11
Dependent Claim
116 words
A process for isomerization of charge of alkyl-aromatic hydrocarbons which comprises contacting, under conditions of isomerization, said hydrocarbon charge, hydrogen and a catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient; (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentges being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 12
Dependent Claim
116 words
A process for isomerization of charge of alkyl-aromatic hydrocarbons which comprises contacting, under conditions of isomerization, said hydrocarbon charge, hydrogen and a catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient; (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentges being calculated with respect to the respective elemental forms of said components and based on the total weight of the catalyst.
Claim 13
Dependent Claim
52 words
A process according to claim 9, wherein said ingredients are only of tin, of platinum and of zirconium, the support is an alumina whose specific surface is between 100 and 350 m 2 /g and whose specific pore volume is of more than 0.1 cm 3 /g, and said halogen is chlorine.
Claim 14
Dependent Claim
27 words
A process according to claim 9, which comprises (a) reducing said catalyst with hydrogen before contacting said hydrocarbon charge with the catalyst so prepared, under isomerization conditions
Claim 15
Dependent Claim
26 words
A process according to claim 10, which comprises reducing said catalyst with hydrogen befre contacting said hydrocarbon charge with the catalyst so prepared, under isomerization conditions.
Claim 16
Dependent Claim
16 words
A process according to claim 12, further comprising a presulfurization of the catalyst with sulfurized hydrogen.
Claim 17
Dependent Claim
21 words
An isomerization process according to claim 9, further comprising said catalyst consisting of from 1 to 2% by weight of halogen.
Claim 18
Dependent Claim
21 words
An isomerization process according to claim 12, further comprising said catalyst consisting of from 1 to 2% by weight of chlorine.
Claim 19
Dependent Claim
11 words
A process according to claim 14, wherein said halogen is chlorine.
Claim 20
Dependent Claim
17 words
A process according to claim 9, wherein said hydrocarbons are alkylaromatic hydrocarbons and have eight carbon atoms.
Claim 21
Dependent Claim
17 words
A process according to claim 15, wherein said hydrocarbons are alkylaromatic hydrocarbons and have eight carbon atoms.
Claim 22
Dependent Claim
143 words
In a process for the isomerization of alkyl-aromatic hydrocarbons comprising the contacting of the hydrocarbon charge, hydrogen, and a catalyst the improvement to said process, comprising practicing said isomerization in at least two successive stages, said contacting taking place in at least one of said stages with a specific catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentages being calculated with respect to the respective elementl forms of said components and based on the total weight of the catalyst.
Claim 23
Dependent Claim
143 words
In a process for the isomerization of alkyl-aromatic hydrocarbons comprising the contacting of the hydrocarbon charge, hydrogen, and a catalyst the improvement to said process, comprising practicing said isomerization in at least two successive stages, said contacting taking place in at least one of said stages with a specific catalyst comprising a refractory inorganic oxide support having acid sites, having between about 0.4 and 2% of halogen present in combined form with other catalyst components, and consisting essentially of the following on said support: (a) about 0.02 to 2% of at least one platinum-metal ingredient, (b) about 0.02 to 2% of at least one additional zirconium or titanium ingredient, and (c) about 0.02 to 2% of a tin ingredient; said weight percentages being calculated with respect to the respective elementl forms of said components and based on the total weight of the catalyst.
Claim 24
Dependent Claim
59 words
Process in accordance with claim 19, wherein the operating conditions of the stages are as follows: (a) Pressure: Comprised between 3 and 40 bars, (b) Temperature: Comprised between 250° and 550° C., (c) Overall space velocity (v/v/h), measured in the liquid state: Comprised between 0.5 and 4, (d) Molar ratio of hydrogen to hydrocarbons: Comprised between 3 and 15.
Claim 25
Dependent Claim
12 words
Process according to claim 20, wherein v/v/h is between 1 and 2.5.
Claim 26
Dependent Claim
52 words
Process in accordance with claim 19, wherein the number of stages is two and the operating conditions of the first stage are as follows: (a) Pressure: 10 to 40 bars, (b) Temperature: 100° to 450° C., (c) Space velocity: 1 to 4, (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 27
Dependent Claim
52 words
Process in accordance with claim 19, wherein the number of stages is two and the operating conditions of the first stage are as follows: (a) Pressure: 20 to 35 bars, (b) Temperature: 250° to 450° C., (c) Space velocity: 1 to 4. (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 28
Dependent Claim
52 words
Process in accordance with claim 19, wherein the number of stages is two and the operating conditions of the second stage are as follows: (a) Pressure: 3 to 30 bars, (b) Temperature: 30° to 550° C. (c) Space velocity: 1 to 6, (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 29
Dependent Claim
52 words
Process in accordance with claim 22, wherein the number of stages is two and the operating conditions of the second stage are as follows: (a) Pressure: 3 to 30 bars, (b) Temperature: 30° to 550° C., (c) Space velocity: 1 to 6 (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 30
Dependent Claim
52 words
Process in accordance with claim 19, wherein the number of stages is two and the operating conditions of the second stage are as follows: (a) Pressure 10 to 25 bars, (b) Temperature: 350° to 500° C., (c) Space velocity: 1 to 6, (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 31
Dependent Claim
52 words
Process in accordance with claim 23, wherein the number of stages is two and the operating conditions of the second stage are as follows: (a) Pressure: 10 to 25 bars, (b) Temperature: 250° to 500° C., (c) Space velocity: 1 to 6, (d) Molar ratio of hydrogen to hydrocarbons: 3 to 15.
Claim 32
Dependent Claim
16 words
Process in accordance with claim 19, wherein the operating conditions of the two stages are identical.
Claim 33
Dependent Claim
16 words
Process in accordance with claim 20, wherein the operating conditions of the two stages are identical.
Claim 34
Dependent Claim
66 words
Process in accordance with claim 19, wherein the operating conditions of the two stages differ as follows: ______________________________________
First Stage
Second Stage
______________________________________
Partial space
velocity (v/v/h):
Between 1 and 4
Between 1 and 6
Molar ratio of
hydrogen to hydrocarbons:
3 to 15 3 to 15
Temperature: 100° to 450° C.
300° to 550° C.
Pressure: 10 to 40 bars
3 to 30 bars.
______________________________________
Claim 35
Dependent Claim
66 words
Process in accordance with claim 25, wherein the operating conditions of the two stages differ as follows: ______________________________________
First Stage
Second Stage
______________________________________
Partial space
velocity (v/v/h):
Between 1 and 4
Between 1 and 6
Molar ratio of
hydrogen to hydrocarbons:
3 to 15 3 to 15
Temperature: 100° to 450° C.
300° to 550° C.
Pressure: 10 to 40 bars
3 to 30 bars.
______________________________________
Claim 36
Dependent Claim
59 words
Process in accordance woth claim 27, wherein the operating conditions of the two stages differ as follows: ______________________________________
First Stage
Second Stage
______________________________________
Partial space
velocity (v/v/h):
Between 1 and 4
Between 1 and 6
Molar ratio of
hydrogen to hydrocarbons:
100° to 450° C.
300° to 550° C.
Pressure: 10 to 40 bars
3 to 30 bars.
______________________________________
Claim 37
Dependent Claim
16 words
Process in accordance with claim 28, wherein the catalysts used in said successive stages are identical.
Claim 38
Dependent Claim
16 words
Process in accordance with claim 29, wherein the catalysts used in said successive stages are identical.
Claim 39
Dependent Claim
16 words
Process in accordance with claim 30, wherein the catalysts used in said successive stages are identical.
Claim 40
Dependent Claim
16 words
Process in accordance with claim 31, wherein the catalysts used in said successive stages are identical.
Claim 41
Dependent Claim
21 words
Process in accordance with claim 28, wherein the catalysts used in the successive stages are different in their metal ingredient composition.
Claim 42
Dependent Claim
21 words
Process in accordance with claim 29, wherein the catalysts used in the successive stages are different in their metal ingredient composition.
Claim 43
Dependent Claim
21 words
Process in accordance with claim 30, wherein the catalysts used in the successive stages are different in their metal ingredient composition.
Claim 44
Dependent Claim
21 words
Process in accordance with claim 31 wherein the catalysts used in the successive stages are different in their metal ingredient composition.
Claim 45
Dependent Claim
44 words
Process in accordance with claim 19, wherein the halogen content of the catalysts varies from one stage to the next, the first stage using a catalyst containing approximately from 0.05% more halogen, based on the total weight of the catalysts, than the second stage.
Claim 46
Dependent Claim
46 words
Process in accordance with claim 20, wherein the halogen content of the catalysts varies from one stage to the next, the first stage using a catalyst containing approximately from 0.05 to 0.50% more halogen, based on the total weight of the catalysts, than the second stage.
Claim 47
Dependent Claim
46 words
Process in accordance with claim 25, wherein the halogen content of the catalysts varies from one stage to the next, the first stage using a catalyst containing approximately from 0.05 to 0.50% more halogen, based on the total weight of the catalysts, than the second stage.
Claim 48
Dependent Claim
46 words
Process in accordance with claim 31, wherein the halogen content of the catalyst varies from one stage to the next, the first stage using a catalyst containing approximately from 0.05 to 0.50% more halogen, based on the total weight of the catalysts, than the second stage.
Claim 49
Dependent Claim
16 words
Process in accordance with claim 19, wherein said specific catalyst is used in the last stage.
Claim 50
Dependent Claim
16 words
Process in accordance with claim 20, wherein said specific catalyst is used in the last stage.
Claim 51
Dependent Claim
16 words
Process in accordance with claim 25, wherein said specific cataysts is used in the last stage.
Claim 52
Dependent Claim
16 words
Process in accordance with claim 43, wherein said specific catalyst is used in the last stage.
Claim 53
Dependent Claim
20 words
Process in accordance with claim 20, wherein the first stage uses a catalyst containing only platinum as the active metal.
Claim 54
Dependent Claim
22 words
Process in accordance with claim 20, wherein the first stage uses a catalyst containing platinum and also silicon as the active metal.
Claim 55
Dependent Claim
20 words
Process in accordance with claim 1, wherein the first stage uses a catalyst containing platinum and tin as active metals.
Claim 56
Dependent Claim
20 words
Process in accordance with claim 41, wherein the first stage uses a catalyst containing platinum and tin as active metals.
Claim 57
Dependent Claim
23 words
Process in accordance with claim 31, wherein the first stage uses a catalyst containing platinum and tin as active metals and also silicon.
Claim 58
Dependent Claim
17 words
Process in accordance with claim 20, said specific catalyst further contains from 0.1 to 2% of silicon.
Claim 59
Dependent Claim
17 words
Process in accordance with claim 40, said specific catalyst further contains from 0.1 to 2% of silicon.
Claim 60
Dependent Claim
17 words
Process in accordance with claim 48, said specific catalyst further contains from 0.1 to 2% of silicon.
Claim 61
Dependent Claim
19 words
Application of said process in accordance with claim 20 to the isomerization of alkylaromatic hydrocarbons having eight carbon atoms.
Claim 62
Dependent Claim
19 words
Application of said process in accordance with claim 43 to the isomerization of alkylaromatic hydrocarbons having eight carbon atoms.
Claim 63
Dependent Claim
19 words
Application of said process in accordance with claim 56 to the isomerization of alkylaromatic hydrocarbons having eight carbon atoms.
Claim 64
Dependent Claim
28 words
Application of said process in accordance with claim 20, to the treatment of a charge of alkylaromatic hydrocarbons containing approximately from 5 to 50% by weight of ethylbenzene.
Claim 65
Dependent Claim
28 words
Application of said process in accordance with claim 52 to the treatment of a charge of alkylaromatic hydrocarbons containing approximately from 5 to 50% by weight of ethylebenzene.
Claim 66
Dependent Claim
28 words
Application of said process in accordance with claim 56 to the treatment of a charge of alkylaromatic hydrocarbons containing approximately from 5 to 50% by weight of ethylbenzene.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-04-30 | 1982-10-30 | 1983-05-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-04-30 | 1986-10-30 | 1987-05-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-04-30 | 1990-10-30 | 1991-05-01 | $7700.00 | Window Closed / Lapsed |