US4416806A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Catalyst for production of aromatic hydrocarbons and process for preparation
Assignee: Elf Antar France
•
Filing: 1983-03-04
•
Granted: 1983-11-22
•
Expires: 2003-03-04
Abstract
Abstract Monofunctional dehydrocyclization catalyst of paraffins, characterized in that it contains: 0.1 to 1.5% platinum, o.1 to 1.5% rhenium incorporated in the form of carbonyl, a small proportion of sulphur introduced by a sulphur compound reducible or decomposable by hydrogen such that the ratio x of the number of sulphur atoms to the number of platinum and rhenium atoms deposited on the catalyst be comprised between 0.05 and 0.6, the carrier being constituted by a zeolitic crystalline aluminosilicate compensated in more than 90% by alkaline cations having a pore diameter of more than 6.5 Angstroms.
Inventors
- 👤 Jean-Rene Bernard
- 👤 Michele Breysse
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 14:41
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/60; B01J29/64; B01J29/076; B01J29/70; B01J29/78; B01J29/7823; C; C07; C07C; C07C5/00; C07C5/32; C07C5/373; C07C5/393; C07C5/41; C07C5/415; C07C5/417; C10; C10G; C10G35/00; C10G35/04; C10G35/06; C10G35/095
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
178 words
A process for preparing a bimetallic catalyst for the dehydrocyclization of paraffins comprising a carrier comprised of a zeolitic crystalline aluminosilicate exchanged with more than 90% of alkali metal cations and having a pore diamter larger than 6.5 Angstroms; 0.1 to 1.5% platinum; 0.1 to 1.5% rhenium obtained from rhenium carbonyl, the ratio of the rhenium/platinum varying with the pressure of use; a small amount of sulphur such that the ratio x of the number of sulphur atoms to platinum and rhenium atoms is from betweeon about 0.05 and 0.6, said process comprising the impregnating steps carried out in any desired order (a) charging the carrier with rhenium by sublimation of rhenium carbonyl; (b) impregnating the carrier with an aqueous solution or water soluble complex of platinum; (c) incorporating sulphur into the carrier by contacting with a sulphur containing compound; (d) the impregnated carrier having received the charges of rhenium carbonyl, platinum complex, and sulphur compound being then dried, optionally calcined, and reduced by hydrogen at a temperature from about 300° C. to 500° C. prior to use.
Claim 2
Dependent Claim
178 words
A process for preparing a bimetallic catalyst for the dehydrocyclization of paraffins comprising a carrier comprised of a zeolitic crystalline aluminosilicate exchanged with more than 90% of alkali metal cations and having a pore diamter larger than 6.5 Angstroms; 0.1 to 1.5% platinum; 0.1 to 1.5% rhenium obtained from rhenium carbonyl, the ratio of the rhenium/platinum varying with the pressure of use; a small amount of sulphur such that the ratio x of the number of sulphur atoms to platinum and rhenium atoms is from betweeon about 0.05 and 0.6, said process comprising the impregnating steps carried out in any desired order (a) charging the carrier with rhenium by sublimation of rhenium carbonyl; (b) impregnating the carrier with an aqueous solution or water soluble complex of platinum; (c) incorporating sulphur into the carrier by contacting with a sulphur containing compound; (d) the impregnated carrier having received the charges of rhenium carbonyl, platinum complex, and sulphur compound being then dried, optionally calcined, and reduced by hydrogen at a temperature from about 300° C. to 500° C. prior to use.
Claim 3
Dependent Claim
30 words
A dehydrocyclization catalyst according to claim 1, wherein for use at a pressure of about 15 bars to 35 bars the proportion of rhenium is less than that of platinum.
Claim 4
Dependent Claim
28 words
A dehydrocyclization catalyst according to claim 1, wherein for use at low pressure, the content of rhenium is more than that of platinum whereby its stability is maintained.
Claim 5
Dependent Claim
28 words
A catalyst according to claim 1, wherein the carrier is selected from the group consisting of faujasite X, faujasite Y, zeolite L, zeolite omega and zeolite ZSM 4.
Claim 6
Dependent Claim
33 words
A catalyst according to claim 4, wherein the carrier is an exchange zeolite L containing at least one of the alkali metals selected from the group consisting of sodium, potassium, rubidium and cesium.
Claim 7
Dependent Claim
19 words
A catalyst according to claim 1 wherein the carrier is in the shape of small balls, tablets or pastilles.
Claim 8
Dependent Claim
20 words
A catalyst of claim 1 wherein the atomic ratio of platinum to rhenium is from about 3:1 to about 0.87:1.
Claim 9
Dependent Claim
31 words
The process of claim 1 wherein the aqueous solution or water soluble complex of platinum is selected from the group consisting of solutions of hexachloroplatinic acid tetramine platinum chloride and dinitrodiaminoplatinum.
Claim 10
Dependent Claim
19 words
The process of claim 1 wherein the carrier is impregnated by exchange of ions with cationic complex of platinum.
Claim 11
Dependent Claim
26 words
The process of claim 9 wherein the cationic complex of platinum is in an aqueous solution of an excess of a salt of the zeolite cation.
Claim 12
Dependent Claim
27 words
The process of claim 1, wherein the carrier is charged with rhenium by sublimation of rhenium carbonyl at a pressure of from about 0.01 to 100 tors.
Claim 13
Dependent Claim
47 words
The process of claim 1 wherein the sulphur is incorporated into the carrier by pretreatment of the carrier charged with rhenium and platinum in the dehydrocyclization reactor by contact with a sulphur containing compound selected from the group consisting of hydrogen sulphide, dimethyl disulphide and carbon disulphide.
Claim 14
Dependent Claim
177 words
A process for making a bimetallic catalyst for the dehydrocyclization of paraffins, comprising a carrier comprised of a zeolitic crystalline aluminosilicate exchanged with more than 90% of alkali metal cations and having a pore diameter larger than 6.5 Angstroms; 0.1 to 1.5% platinum; 0.1 to 1.5% rhenium obtained from rhenium carbonyl, the ratio of the rhenium/platinum varying with the pressure of use; a small amount of sulphur such that the ratio x of the number of sulphur atoms to platinum and rhenium atoms is from between about 0.05 and 0.6, said process comprising the impregnating steps carried out in any order desired: (a) charging the carrier with rhenium by impregnation with a solution of rhenium carbonyl in acetone; (b) impregnating the carrier with an aqueous solution or water soluble complex of platinum; (c) impregnating sulphur by impregnation of the carrier with a solution of a sulphur containing compound; and (d) after the impregnation steps, drying, heat treating and reducing the impregnated carrier with hydrogen at a temperature between about 300° C. and 550° C. prior to use.
Claim 15
Dependent Claim
177 words
A process for making a bimetallic catalyst for the dehydrocyclization of paraffins, comprising a carrier comprised of a zeolitic crystalline aluminosilicate exchanged with more than 90% of alkali metal cations and having a pore diameter larger than 6.5 Angstroms; 0.1 to 1.5% platinum; 0.1 to 1.5% rhenium obtained from rhenium carbonyl, the ratio of the rhenium/platinum varying with the pressure of use; a small amount of sulphur such that the ratio x of the number of sulphur atoms to platinum and rhenium atoms is from between about 0.05 and 0.6, said process comprising the impregnating steps carried out in any order desired: (a) charging the carrier with rhenium by impregnation with a solution of rhenium carbonyl in acetone; (b) impregnating the carrier with an aqueous solution or water soluble complex of platinum; (c) impregnating sulphur by impregnation of the carrier with a solution of a sulphur containing compound; and (d) after the impregnation steps, drying, heat treating and reducing the impregnated carrier with hydrogen at a temperature between about 300° C. and 550° C. prior to use.
Claim 16
Dependent Claim
12 words
A bimetallic catalyst prepared by the method of claim 1 or 13.
Claim 17
Dependent Claim
54 words
A process of claim 13 for making the catalyst of claim 14 wherein the sulphur is incorporated onto the carrier by pretreatment of the carrier charged with rhenium and platinum in the dehydrocyclization reactor by contact with a sulphur containing compound selected from the group consisting of hydrogen sulphide, dimethyl disulphide, and carbon disulphide.
Claim 18
Dependent Claim
24 words
The process of claim 13 wherein the solution of a sulphur containing compound is selected from the group consisting of sulphates, thiosulphates and sulphites.
Claim 19
Dependent Claim
38 words
The process of claim 13, wherein the carrier is impregnated with a composition selected from the group consisting of hexachloroplatinic acid, tetramine platinum chloride, dinitrodiamino platinum and by exchange of ions with a cationic complex of the platinum.
Claim 20
Dependent Claim
24 words
The method of claim 17 wherein the cationic complex of platinum is in solution of an excess of a salt of the zeolite cation.
Claim 21
Dependent Claim
10 words
A bimetallic catalyst prepared by the method of claim 14.
Claim 22
Dependent Claim
30 words
A dehydrocyclization catalyst according to claim 19, wherein for use at a pressure of about 15 bars to 35 bars the proportion of rhenium is less than that of platinum.
Claim 23
Dependent Claim
28 words
A dehydrocyclization catalyst according to claim 19, wherein for use at low pressure, the content of rhenium is more than that of platinum whereby its stability is maintained.
Claim 24
Dependent Claim
28 words
A catalyst according to claim 19, wherein the carrier is selected from the group consisting of faujasite X, faujasite Y, zeolite L, zeolite omega and zeolite ZSM 4.
Claim 25
Dependent Claim
33 words
A catalyst according to claim 22, wherein the carrier is an exchange zeolite L containing at least one of the alkali metals selected from the group consisting of sodium, potassium, rubidium and cesium.
Claim 26
Dependent Claim
19 words
A catalyst according to claim 19, wherein the carrier is in the shape of small balls, tablets or pastilles.
Claim 27
Dependent Claim
20 words
A catalyst of claim 19 wherein the atomic ratio of platinum to rhenium is from about 3:1 to about 0.87:1.
Claim 28
Dependent Claim
27 words
The process of claim 8, wherein the carrier is charged with rhenium by sublimation of rhenium carbonyl at a pressure of from about 0.01 to 100 tors.
Claim 29
Dependent Claim
27 words
The process of claim 9, wherein the carrier is charged with rhenium by sublimation of rhenium carbonyl at a pressure of from about 0.01 to 100 tors.
Claim 30
Dependent Claim
27 words
The process of claim 10, wherein the carrier is charged with rhenium by sublimation of rhenium carbonyl at a pressure of from about 0.01 to 100 tors.
Claim 31
Dependent Claim
38 words
The process of claim 15, wherein the carrier is impregnated with a composition selected from the group consisting of hexachloroplactinic acid, tetramine platinum chloride, dinitrodiamino platinum and by exchange of ions with a cationic complex of the platinum.
Claim 32
Dependent Claim
24 words
The method of claim 29 wherein the cationic complex of platinum is in solution of an excess of a salt of the zeolite cation.
Claim 33
Dependent Claim
38 words
The process of claim 16, wherein the carrier is impregnated with a composition selected from the group consisting of hexachloroplatinic acid, tetramine platinum chloride, dinitrodiamino platinum and by exchange of ions with a cationic complex of the platinum.
Claim 34
Dependent Claim
24 words
The method of claim 31 wherein the cationic complex of platinum is in solution of an excess of a salt of the zeolite cation.
References Cited (Backward Citations)
US3415737A
Cited
US3775502A
Cited
US3819507A
Cited
US4048058A
Cited
US4104320A
Cited
FR2360540A2
Cited
US4210524A
Cited
US4246095A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-11-21 | 1987-05-23 | 1987-11-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-21 | 1991-05-23 | 1991-11-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-21 | 1995-05-23 | 1995-11-22 | $7700.00 | Window Closed / Lapsed |