US4297243A
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Molybdenum-exchanged crystalline aluminosilicate zeolite
Assignee: Honeywell UOP LLC
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Filing: 1979-10-02
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Granted: 1981-10-27
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Expires: 1999-10-02
Abstract
Abstract Molybdenum is ion exchanged into a crystalline aluminosilicate zeolite, replacing metals such as sodium, calcium, and potassium, by contacting the zeolite with an aqueous solution containing molybdenyl cations (i.e., MoO22+) and having a pH below 7.0 but higher than that which would substantially affect the crystallinity of the zeolite. The resulting zeolite, when calcined or sulfided, is useful as a catalyst for hydrocarbon conversion reactions, particularly with respect to the hydrodealkylation of toluene to benzene and methane.
Inventors
- 👤 Eric L. Moorehead
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 06:35
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/70; B01J29/78; B01J29/7823; B01J29/076; B01J29/08; B01J29/16; B01J29/166; B01J29/60; B01J29/64
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
250 words
A crystalline aluminosilicate zeolite having a composition expressed in molar ratios of oxides as: ##EQU3## where cM 2/n O represents the sum of all components, on a per mole of Al 2 O 3 in the crystal framework basis, required to balance that portion of the charge on the crystal framework not balanced by molybdenum constituents, with the valence of M being represented by n, and where MoO 3 represents all molybdenum constituents balancing a charge on the crystal framework, and c, b, x, and y represent the moles of M 2/n O, MoO 3 , SiO 2 , and the water of hydration, H 2 O, respectively, present in the zeolite to each mole of Al 2 O 3 in the crystal framework, x being between 2 and 100, y being a non-negative number, c being 0 or a positive number less than 1, and b being a positive number no greater than 1, with c+b being a positive number no greater than 1.0, said zeolite being characterized by the ion exchange of molybdenum-containing cations from the zeolite when the zeolite is immersed for at least one hour in an aqueous sodium salt solution having a temperature in the range of 20° to 80° C. and an initial pH between 6.0 and 8.5, said solution containing sodium ions in a concentration between 1.0 and 15.0% by weight, calculated as Na, and said immersion being such that the weight ratio of zeolite to solution is between about 1:4 and 1:12.
Claim 2
Dependent Claim
250 words
A crystalline aluminosilicate zeolite having a composition expressed in molar ratios of oxides as: ##EQU3## where cM 2/n O represents the sum of all components, on a per mole of Al 2 O 3 in the crystal framework basis, required to balance that portion of the charge on the crystal framework not balanced by molybdenum constituents, with the valence of M being represented by n, and where MoO 3 represents all molybdenum constituents balancing a charge on the crystal framework, and c, b, x, and y represent the moles of M 2/n O, MoO 3 , SiO 2 , and the water of hydration, H 2 O, respectively, present in the zeolite to each mole of Al 2 O 3 in the crystal framework, x being between 2 and 100, y being a non-negative number, c being 0 or a positive number less than 1, and b being a positive number no greater than 1, with c+b being a positive number no greater than 1.0, said zeolite being characterized by the ion exchange of molybdenum-containing cations from the zeolite when the zeolite is immersed for at least one hour in an aqueous sodium salt solution having a temperature in the range of 20° to 80° C. and an initial pH between 6.0 and 8.5, said solution containing sodium ions in a concentration between 1.0 and 15.0% by weight, calculated as Na, and said immersion being such that the weight ratio of zeolite to solution is between about 1:4 and 1:12.
Claim 3
Dependent Claim
13 words
A zeolite as defined in claim 1 wherein x is greater than 3.
Claim 4
Dependent Claim
14 words
A zeolite as defined in claim 1 wherein x is between 3 and 6.
Claim 5
Dependent Claim
90 words
A molybdenum-containing crystalline alumino-silicate zeolite characterized by the ion exchange of molybdenum-containing cations from the zeolite when the zeolite is immersed for at least one hour in an aqueous sodium salt solution having a temperature in the range of 20° to 80° C. and an initial pH in the range of 6.0 to 8.5, said solution containing sodium ions in a concentration between 1.0 and 15.0% by weight, calculated as Na, and said immersion being such that the weight ratio of zeolite to solution is between about 1:4 and 1:12.
Claim 6
Dependent Claim
90 words
A molybdenum-containing crystalline alumino-silicate zeolite characterized by the ion exchange of molybdenum-containing cations from the zeolite when the zeolite is immersed for at least one hour in an aqueous sodium salt solution having a temperature in the range of 20° to 80° C. and an initial pH in the range of 6.0 to 8.5, said solution containing sodium ions in a concentration between 1.0 and 15.0% by weight, calculated as Na, and said immersion being such that the weight ratio of zeolite to solution is between about 1:4 and 1:12.
Claim 7
Dependent Claim
31 words
A zeolite as defined in claim 4 wherein said molybdenum-containing cations are present in a proportion of at least 0.10 equivalent per gram atom of aluminum in the electronegative crystal framework.
Claim 8
Dependent Claim
19 words
A zeolite as defined in claim 5 wherein essentially all of said molybdenum-containing cations consist of molybdenum and oxygen.
Claim 9
Dependent Claim
40 words
A zeolite as defined in claim 6 wherein that proportion of the electronegative crystal framework not balanced by said molybdenum-containing cations are balanced essentially completely by cations selected from the group consisting of hydrogen ions, sodium ions, and mixtures thereof.
Claim 10
Dependent Claim
107 words
A molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure and containing ion-exchangeable molybdenum-containing cations prepared by the method of contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 ions, said solution having sufficient of an organic base added thereto to maintain the pH of the solution during said contacting below 7.0 but higher than that which would substantially affect the crystalline structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite.
Claim 11
Dependent Claim
107 words
A molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure and containing ion-exchangeable molybdenum-containing cations prepared by the method of contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 ions, said solution having sufficient of an organic base added thereto to maintain the pH of the solution during said contacting below 7.0 but higher than that which would substantially affect the crystalline structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite.
Claim 12
Dependent Claim
27 words
A zeolite as defined in claim 8 wherein said aqueous solution initially contains, as essentially the only inorganic cations therein, H + and MoO 2 +2 .
Claim 13
Dependent Claim
37 words
A zeolite as defined in claim 8 wherein said zeolite contacted with the aqueous solution is selected from the group consisting of Zeolite Y, Zeolite L, Zeolite ZSM-4, Zeolite ZSM-5, Zeolite T, Zeolite Omega, erionite, and faujasite.
Claim 14
Dependent Claim
30 words
A zeolite as defined in claim 10 wherein the resulting molybdenum-containing cation content of the zeolite is at least 0.10 equivalent per gram atom of aluminum in the crystal framework.
Claim 15
Dependent Claim
15 words
A zeolite as defined in claim 8 or 10 wherein said organic base is pyridine.
Claim 16
Dependent Claim
28 words
A zeolite as defined in claim 8 or 10 wherein said zeolite contacted with the aqueous solution initially contains alkali metal cations as the major exchangeable cations therein.
Claim 17
Dependent Claim
120 words
A catalyst composition comprising a molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure prepared by the method comprising (1) contacting a crystalline aluminosilicate zeolite having a substantially ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution below 7.0 but higher than that which would substantially affect the crystalline structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite, and (2) subsequently calcining the zeolite containing the molybdenum-containing cations in an oxygen-containing oxidizing atmosphere.
Claim 18
Dependent Claim
120 words
A catalyst composition comprising a molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure prepared by the method comprising (1) contacting a crystalline aluminosilicate zeolite having a substantially ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution below 7.0 but higher than that which would substantially affect the crystalline structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite, and (2) subsequently calcining the zeolite containing the molybdenum-containing cations in an oxygen-containing oxidizing atmosphere.
Claim 19
Dependent Claim
55 words
A catalyst prepared by the method of claim 14 including the further step of contacting the calcined zeolite obtained in step (2) with one or more components selected from the group consisting of sulfur and its compounds under conditions sufficient to convert at least some of the contained molybdenum to compounds of sulfur and molybdenum.
Claim 20
Dependent Claim
146 words
A catalyst composition comprising a molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure prepared by the method comprising: (1) contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution below 7.0 but higher than that which would substantially affect the crystal structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite, and (2) subsequently exposing the zeolite to an atmosphere containing one or more components selected from the group consisting of sulfur and its compounds under conditions sufficient to convert at least some of the molybdenum-containing cations to components containing sulfur and molybdenum.
Claim 21
Dependent Claim
146 words
A catalyst composition comprising a molybdenum-containing crystalline aluminosilicate zeolite having an ordered crystalline structure prepared by the method comprising: (1) contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution below 7.0 but higher than that which would substantially affect the crystal structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in the zeolite with molybdenum-containing cations and increase the molybdenum-containing cation content of the zeolite, and (2) subsequently exposing the zeolite to an atmosphere containing one or more components selected from the group consisting of sulfur and its compounds under conditions sufficient to convert at least some of the molybdenum-containing cations to components containing sulfur and molybdenum.
Claim 22
Dependent Claim
40 words
A catalyst as defined in claim 14, 15, or 16 wherein said zeolite contacted with the aqueous solution is selected from the group consisting of Zeolite Y, Zeolite L, Zeolite ZSM-4, Zeolite ZSM-5, Zeolite T, Zeolite Omega, erionite, and faujasite.
Claim 23
Dependent Claim
13 words
A catalyst as defined in claim 17 wherein said organic base is pyridine.
Claim 24
Dependent Claim
36 words
A catalyst as defined in claim 17 wherein the resulting molybdenum-containing cation content of the zeolite at the end of step (1) is at least 0.10 equivalent per gram atom of aluminum in the crystal framework.
Claim 25
Dependent Claim
22 words
A catalyst as defined in claim 17 wherein said organic base is selected from the group consisting of aliphatic and aromatic amines.
Claim 26
Independent Claim
106 words
A method for ion-exchanging molybdenum-containing cations into a crystalline aluminosilicate zeolite having an ordered crystalline structure comprising contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution during said contacting below 7.0 but higher than that which would substantially affect the crystal structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in said zeolite with molybdenum-containing cations, and recovering the zeolite containing the molybdenum-containing cations from said solution.
Claim 27
Independent Claim
106 words
A method for ion-exchanging molybdenum-containing cations into a crystalline aluminosilicate zeolite having an ordered crystalline structure comprising contacting a crystalline aluminosilicate zeolite having an ordered crystalline structure with an aqueous solution containing a precursor of MoO 2 +2 cations, said solution having sufficient of an organic base added thereto to maintain the pH of the solution during said contacting below 7.0 but higher than that which would substantially affect the crystal structure of the zeolite, said contacting being under conditions sufficient to replace at least some of the cations in said zeolite with molybdenum-containing cations, and recovering the zeolite containing the molybdenum-containing cations from said solution.
Claim 28
Dependent Claim
30 words
A method as defined in claim 21 wherein the resulting molybdenum-containing cation content of the zeolite is at least 0.10 equivalent per gram atom of aluminum in the crystal framework.
Claim 29
Dependent Claim
29 words
A method as defined in claim 21 wherein essentially all the ion exchange capacity of the zeolite prior to contact with said aqueous solution is satisfied with metal cations.
Claim 30
Independent Claim
39 words
A method as defined in claims 21 or 23 wherein said zeolite contacted with the aqueous solution is selected from the group consisting of Zeolite Y, Zeolite L, Zeolite T, Zeolite ZSM-4, Zeolite ZSM-5, Zeolite Omega, erionite, and faujasite.
Claim 31
Dependent Claim
13 words
A method as defined in claim 24 wherein said organic base is pyridine.
Claim 32
Dependent Claim
24 words
A method as defined in claim 24 wherein the recovered zeolite contains at least 0.10 equivalent per gram atom of aluminum of molybdenum-containing cations.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-10-26 | 1985-04-27 | 1985-10-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-10-26 | 1989-04-27 | 1989-10-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-10-26 | 1993-04-27 | 1993-10-27 | $7700.00 | Window Closed / Lapsed |