US4686093A
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US
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Molecular sieve compositions with aluminum, phosphorus and at least two other elements
Assignee: Katalistiks International Inc
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Filing: 1984-04-13
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Granted: 1987-08-11
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Expires: 2004-04-13
Abstract
Abstract Crystalline molecular sieves having three-dimensional microporous framework structure of MO2, AlO2, and PO2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis are expressed by the formula: mR:(MxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2; "M" represents at least two elements capable of forming framework tetrahedral oxides and selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and 37 z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is disclosed.
Inventors
- 👤 Edith M. Flanigen
- 👤 Brent M. T. Lok
- 👤 Robert L. Patton
- 👤 Stephen T. Wilson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 16:20
CPC Classifications
C; C07; C07C; C07C5/00; C07C5/32; C07C5/373; C07C5/393; C07C5/41; B; B01; B01J; B01J29/00; B01J29/82; B01J29/84; C01; C01B; C01B37/00; C01B37/06; C07C2/00; C07C2/02; C07C2/04; C07C2/06; C07C2/08; C07C2/12; C07C2/54; C07C5/02; C07C5/22; C07C5/2206; C07C5/2226; C07C5/224; C07C5/27; C07C5/2702; C07C5/271; C07C5/2716; C07C2527/00; C07C2527/14; C07C2527/16; C07C2527/167; C07C2527/173; C07C2529/00; C07C2529/82; C07C2529/84
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
206 words
Crystalline molecular sieves having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of Tables A to H and J to V herein.
Claim 2
Dependent Claim
206 words
Crystalline molecular sieves having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of Tables A to H and J to V herein.
Claim 3
Dependent Claim
38 words
Molecular sieves according to claim 1 wherein the mole fractions of "M", aluminum and phosphorus present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
Claim 4
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table A.
Claim 5
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table B.
Claim 6
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table C.
Claim 7
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table D.
Claim 8
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table E.
Claim 9
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table F.
Claim 10
Dependent Claim
27 words
The crystalline molecular sieves of claim 1 or 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table G.
Claim 11
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table H.
Claim 12
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table J.
Claim 13
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table K.
Claim 14
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffractions pattern which contains at least the d-spacing set forth in Table L.
Claim 15
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table M.
Claim 16
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table N.
Claim 17
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table O.
Claim 18
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table P.
Claim 19
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table Q.
Claim 20
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table R.
Claim 21
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table S.
Claim 22
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table T.
Claim 23
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table U.
Claim 24
Dependent Claim
27 words
The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V.
Claim 25
Dependent Claim
13 words
The molecular sieves according to claim 1 wherein "M" is arsenic and germanium.
Claim 26
Dependent Claim
12 words
Molecular sieves according to claim 1 wherein "M" is beryllium and germanium.
Claim 27
Dependent Claim
12 words
Molecular sieves according to claim 1 wherein "M" is chromium and gallium.
Claim 28
Dependent Claim
13 words
The molecular sieves according to claim 1 wherein "M" is arsenic and beryllium.
Claim 29
Dependent Claim
14 words
The molecular sieves according to claim 1 wherein "M" is arsenic, vanadium and beryllium.
Claim 30
Dependent Claim
12 words
The molecular sieves of claim 1 wherein "M" is germanium and boron.
Claim 31
Dependent Claim
26 words
The molecular sieves of claim 1 wherein "M" is at least two elements selected from the group consisting of boron, chromium, vanadium, arsenic, germanium and gallium.
Claim 32
Dependent Claim
133 words
Process for preparing the crystalline molecular sieves of claim 1 which comprises providing a reaction mixture composition expressed in terms of molar oxide ratios as follows: aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O wherein "R" is an organic templating agent: "a" is the amount of "R" and is an effective amount greater than zero: "b" has a value of from zero to about 500, "M" represents at least two elements capable of forming framework tetrahedral oxides and selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; "x", "y" and "z" represent the mole fractions, respectively, of "M", aluminum and phosphorus in the (M x Al y P z )O 2 constituent, and each has a value of at least 0.01, whereby the molecular sieves of claim 1 are prepared.
Claim 33
Dependent Claim
33 words
The process of claim 31 where "x", "y" and "z" are within the hexagonal compositional area defined by points F, G, H, I, J and K which is FIG. 3 of the drawings.
Claim 34
Dependent Claim
18 words
Process according to claim 31 wherein "a" is an effective amount from greater than zero to about 6.
Claim 35
Dependent Claim
17 words
Process according to claim 31 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
Claim 36
Dependent Claim
37 words
Process according to claim 31 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudoboehmite and aluminum alkoxide.
Claim 37
Dependent Claim
12 words
Process according to claim 35 wherein the aluminum alkoxide is aluminum isopropoxide.
Claim 38
Dependent Claim
25 words
Process according to claim 35 wherein the source of "M" is selected from the group consisting of chlorides, bromide, iodides, sulfates, nitrates, acetates and formates.
Claim 39
Dependent Claim
45 words
Process according to claim 31 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula: R.sub.4 X.sup.+ wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
Claim 40
Dependent Claim
13 words
Process according to claim 31 wherein the organic templating agent is an amine.
Claim 41
Dependent Claim
85 words
Process according to claim 31 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine' N,N-dimethylbenzylamine; N,N-diethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C 14 H 32 N 2 )(OH) 2 ] x wherein x is a value of at least 2.
Claim 42
Dependent Claim
34 words
Molecular sieve prepared by calcining the composition of claim 1 or claim 2 at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.
Claim 43
Dependent Claim
175 words
Crystalline molecular sieves having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01.
Claim 44
Dependent Claim
175 words
Crystalline molecular sieves having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01.
Claim 45
Dependent Claim
39 words
Crystalline molecular sieves according to claim 42 wherein the mole fractions of "M", aluminum and phosphorus present as tetrahedral oxides are within the tetragonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
Claim 46
Dependent Claim
142 words
Process for preparing crystalline molecular sieves of claim 42 having three-dimensional framework structures wherein the process comprises providing at an effective temperature and for an effective time a reaction mixture composition expressed in terms of molar oxide ratios as follows: aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O wherein "R" is an organic templating agent; "a" is an effective amount of "R" greater than zero; "b" has a value of from zero to about 500; "M" represents at least two elements capable of forming tetrahedral oxides and selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; "x", "y" and "z" represent the mole fractions, respectively, of "M", aluminum and phosphorus in the (M x Al y P z )O 2 constituent, and each has a value of at least 0.01, whereby molecular sieves according to claim 64 are prepared.
Claim 47
Dependent Claim
33 words
Molecular sieve prepared by calcining the compositions of claim 42 or 43 at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1990-08-10 | 1991-02-09 | 1991-08-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-08-10 | 1995-02-09 | 1995-08-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-08-10 | 1999-02-09 | 1999-08-11 | $7700.00 | Window Closed / Lapsed |