US4681747A
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Process for the preparation of metallosilicates of tetravalent lanthanide and actinide series metals using heterpoly metallates
Assignee: Standard Oil Co
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Filing: 1984-11-16
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Granted: 1987-07-21
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Expires: 2004-11-16
Abstract
Abstract A molecular sieving metallosilicate is disclosed which comprises a complex represented in terms of mole ratios of oxides by the formula: ##STR1## wherein A is an ammonium, alkyl ammonium, alkyl phosphonium or alkyl arsonium ion; D is an alkali or alkaline earth metal ion or a mixture of two or more thereof; E is selected from the group consisting of Al, B, Mo, W, Fe, or a mixture of two or more thereof; M is a tetravalent metal selected from the Lanthanide or Actinide series; a is a number ranging from zero to about 25; b is a number ranging from zero to about 1.5; c is a number ranging from zero to about 0.3; d is a number ranging from about 20 to about 500; e is a number ranging from zero to about 200. The X-ray diffraction pattern for these metallosilicates indicates a ZSM-5 like crystalline structure. A method for making these metallosilicates, and a method for dehydrating and reforming methanol using these metallosilicates are disclosed.
Inventors
- 👤 Michael J. Desmond
- 👤 Janie K. Currie
- 👤 Frederick A. Pesa
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 03:16
CPC Classifications
C; C07; C07C; C07C1/00; C07C1/20; B; B01; B01J; B01J29/00; B01J29/04; C01; C01B; C01B33/00; C01B33/20; C01B33/26; C01B33/28; C01B33/2807; C01B33/2876; C01B35/00; C01B35/08; C01B35/10; C01B35/1009; C07C2529/00; C07C2529/04
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
239 words
A method for preparing a molecular sieving metallosilicate comprising the following steps: (A) providing a mixture comprising: (1) water; (2) an oxide of silicon source; (3) a synthesis directing agent and/or mineralizing agent; and (4) a tetravalent Lanthanide or Actinide series metal containing compound which is a heteropolymetallate of the formula G.sub.f [L.sub.g Q.sub.p J.sub.r O.sub.S ].tH.sub.2 O wherein G is an ion selected from the group consisting of hydrogen, Group I-A, II-A, I-B or II-B metals, ammonium, alkyl ammonium, alkyl phosphonium or alkyl arsonium, or a mixture of two or more thereof; L is P, As, Si, Ge, Al, H or a mixture of two or more thereof; Q is said tetravalent Lanthanide or Actinide series metal; J is Mo, W, V or Nb or a mixture of two or more thereof; f is a number which when multiplied by the charge of G will result in balancing the charge of the complex within the brackets; g is a number ranging from zero to about 20; p is a number ranging from zero to about 20; r is a number ranging from about 1 to about 50; s is a number ranging from about 7 to about 150; and t is a number ranging from zero to about 150: and (B) maintaining said mixture at a temperature in the range of about 80° C. to about 300° C. for an effective period of time to provide said metallosilicate.
Claim 2
Independent Claim
239 words
A method for preparing a molecular sieving metallosilicate comprising the following steps: (A) providing a mixture comprising: (1) water; (2) an oxide of silicon source; (3) a synthesis directing agent and/or mineralizing agent; and (4) a tetravalent Lanthanide or Actinide series metal containing compound which is a heteropolymetallate of the formula G.sub.f [L.sub.g Q.sub.p J.sub.r O.sub.S ].tH.sub.2 O wherein G is an ion selected from the group consisting of hydrogen, Group I-A, II-A, I-B or II-B metals, ammonium, alkyl ammonium, alkyl phosphonium or alkyl arsonium, or a mixture of two or more thereof; L is P, As, Si, Ge, Al, H or a mixture of two or more thereof; Q is said tetravalent Lanthanide or Actinide series metal; J is Mo, W, V or Nb or a mixture of two or more thereof; f is a number which when multiplied by the charge of G will result in balancing the charge of the complex within the brackets; g is a number ranging from zero to about 20; p is a number ranging from zero to about 20; r is a number ranging from about 1 to about 50; s is a number ranging from about 7 to about 150; and t is a number ranging from zero to about 150: and (B) maintaining said mixture at a temperature in the range of about 80° C. to about 300° C. for an effective period of time to provide said metallosilicate.
Claim 3
Dependent Claim
16 words
The method of claim 1 with the step of separating said metallosilicate from its mother liquor.
Claim 4
Dependent Claim
12 words
The method of claim 1 with the step of washing said metallosilicate.
Claim 5
Dependent Claim
20 words
The method of claim 1 with the step of heat treating said metallosilicate in an inert, oxidizing or reducing atmosphere.
Claim 6
Dependent Claim
32 words
The method of claim 4 with step of cation exchanging said heat treated metallosilicate with an ammonium salt or the salt of a catalytically active metal to provide a cation exchanged metallosilicate.
Claim 7
Dependent Claim
22 words
The method of claim 5 with the step of heat treating said cation exchanged metallosilicate in an inert, oxidizing or reducing atmosphere.
Claim 8
Dependent Claim
32 words
The method of claim 1 wherein the mole ratio during step (A) of Si to said tetravalent Lanthanide or Actinide series metal is in the range of about 20 to about 200.
Claim 9
Dependent Claim
27 words
The method of claim 1 wherein the mole ratio during step (A) of OH - to Si is in the range of about 0.1 to about 10.
Claim 10
Dependent Claim
29 words
The method of claim 1 wherein the mole ratio during step (A) of H 2 O to OH - is in the range of about 10 to about 1000.
Claim 11
Dependent Claim
30 words
The method of claim 1 wherein the mole ratio of Si to said synthesis directing agent plus said mineralizing agent is in the range of about 0.1 to about 30.
Claim 12
Dependent Claim
41 words
The method of claim 1 wherein said synthesis directing agent is the cation of an amine or alkanol amine compound, alkyl substituted amine or alkyl substituted alkanol amine compound, ammonium or alkyl ammonium compound, or alkyl phosphonium or alkyl arsonium compound.
Claim 13
Dependent Claim
29 words
The method of claim 11 wherein said alkyl ammonium compound is a mono-, di-, tri- or tetra-alkyl ammonium compound, each alkyl group having up to about six carbon atoms.
Claim 14
Dependent Claim
18 words
The method of claim 1 wherein said synthesis directing agent is a salt or hydroxide of tetrapropyl ammonium.
Claim 15
Dependent Claim
22 words
The method of claim 1 wherein said mineralizing agent is an oxide, hydroxide or salt of an alkali or alkaline earth metal.
Claim 16
Dependent Claim
12 words
The method of claim 1 wherein said mineralizing agent is sodium hydroxide.
Claim 17
Dependent Claim
25 words
The method of claim 1 wherein said mixture is maintained in an enclosed container under at least the vapor pressure of water during step (B).
Claim 18
Dependent Claim
19 words
The method of claim 1 wherein G is a hydrogen, ammonium or alkali metal ion, or a mixture thereof.
Claim 19
Dependent Claim
34 words
The method of claim 1 wherein g is zero; r is 12; s is 42; J is Mo or W; Q is Ce, Th, U, Pr or a mixture thereof; and p is 1.
Claim 20
Dependent Claim
51 words
The method of claim 1 wherein L is P, Ge or a mixture thereof; J is Mo or W; Q is Ce, Pr, Tb, Th, Pa, U, Np, Pu, Am or a mixture of two or more thereof; g is 2; r is 22; p is 1; and s is 78.
Claim 21
Dependent Claim
51 words
The method of claim 1 wherein L is P, Ge or a mixture thereof; g is 4; J is Mo or W; r is 34; Q is Ce, Pr, Tb, Th, Pa, U, Np, Pu, Am or a mixture of two or more thereof; p is 1; and s is 122.
Claim 22
Dependent Claim
23 words
The method of claim 1 wherein the temperature during step (B) is in the range of about 125° C. to about 200° C.
Claim 23
Dependent Claim
21 words
The method of claim 1 wherein the time period for step (B) is from about 4 hours to about 30 days.
Claim 24
Dependent Claim
20 words
The method of claim 1 wherein the time period for step (B) is from about one to about ten days.
Claim 25
Dependent Claim
197 words
The method of claim 1 wherein said metallosilicate can be represented by the formula: ##STR4## wherein A is an ammonium, alkyl ammonium, alkyl phosphonium or alkyl arsoninum ion; D is an alkali or alkaline earth metal ion, or a mixture of two or more thereof; E is selected from the group consisting of Al, B, Mo, W, Fe, or a mixture of two or more thereof; M is a tetravalent metal selected from the Lanthanide or Actinide series; a is a number ranging from zero to about 25; b is a number ranging from zero to about 1.5; c is a number ranging from zero to about 0.3; d is a number ranging from about 20 to about 500; e is a number ranging from zero to about 200; the X-ray diffraction pattern from said metallosilicate as synthesized showing at least the following significant lines: ______________________________________
Interplanar Relative
Spacing d(A) Intensity
______________________________________
11.25 ± 0.2 s.
10.1 ± 0.2 m.-s.
7.55 ± 0.15 w.
6.40 ± 0.10 w.
4.61 ± 0.08 w.
3.84 ± 0.08 s.
3.73 ± 0.05 s.
3.65 ± 0.05 m.-s.
3.05 ± 0.03 w.
2.99 ± 0.02 w.
2.00 ± 0.02 w.
______________________________________
Claim 26
Dependent Claim
17 words
The method of claim 24 wherein a is in the range of from zero to about 12.
Claim 27
Dependent Claim
17 words
The method of claim 1 wherein c is in the range of from zero to about 0.2.
Claim 28
Dependent Claim
18 words
The method of claim 24 wherein d is in the range of from about 30 to about 200.
Claim 29
Dependent Claim
17 words
The method of claim 24 wherein e is in the range of from zero to about 80.
Claim 30
Dependent Claim
25 words
The method of claim 24 wherein M is Ce, Th, U, Pr, Tb, Pa, Np, Pu, Am or a mixture of two or more thereof.
Claim 31
Dependent Claim
20 words
The method of claim 24 wherein M is Ce, Th, Pr, U or a mixture of two or more thereof.
Claim 32
Dependent Claim
9 words
The method of claim 24 wherein A is tetrapropylammonium.
Claim 33
Dependent Claim
9 words
The method of claim 24 wherein D is sodium.
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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) | 1990-07-20 | 1991-01-19 | 1991-07-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-07-20 | 1995-01-19 | 1995-07-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-07-20 | 1999-01-19 | 1999-07-21 | $7700.00 | Window Closed / Lapsed |