EP0159624A2 — Molecular sieve compositions

Claim 1

Independent Claim 203 words

Crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , A102, PO 2 , SiO 2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula: 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 (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming stable M-O-P, M-O-A1 or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O" bond dissociation energy greater than about 59 kcal/mole at 298°K; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxides said mole fractions being within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1.

Claim 2

Dependent Claim 203 words

Crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , A102, PO 2 , SiO 2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula: 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 (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming stable M-O-P, M-O-A1 or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O" bond dissociation energy greater than about 59 kcal/mole at 298°K; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxides said mole fractions being within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1.

Claim 3

Dependent Claim 163 words

Crystalline molecular sieves of claim 1 having three-dimensional microporous framework structures of ELO 2 , AlO 2 , SiO 2 and P0 2 tetrahedral oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula: 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 (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3; "EL" represents at least one element capable of forming a framework tetrahedral oxide and is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides said mole fractions being within the pentagonal compositional area defined by points A, B, C, D and E of FIG.I.

Claim 4

Dependent Claim 34 words

The crystalline molecular sieves according to claim 1 wherein the mole fractions "w", "x", "y" and "z" are within the tetragonal compositional area defined by points a, b, c and d of FIG. 2.

Claim 5

Dependent Claim 75 words

The crystalline molecular sieves of claim 1 or claim 2 wherein element "EL" is further characterized as having an electronic orbital configuration selected from the group consisting of d 0 , d 1 , d 2 , d 5 , d 6 , d 7 and d 10 , where the small field crystal stabilization energy of the ligand "-OM", where "M" denominates element(s) "EL", favors tetrahedral coordination of element "EL" with O 2- .

Claim 6

Dependent Claim 40 words

The crystalline molecular sieves of claim 1 or 2 wherein "EL" is an element capable of forming stable oxo or hydroxo species in aqueous solution as evidenced by a first hydrolysis constant, K 11 , greater than 10 -14 .

Claim 7

Dependent Claim 32 words

The crystalline molecular sieves of claim 1 or claim 2 wherein element "EL" is known to occur in crystal structure types geometrically related to the different silicon modifications, quartz, cristobalite and tridymite.

Claim 8

Dependent Claim 46 words

The crystalline molecular sieves of claim 1 or claim 2 wherein element "EL" in its cation form is classified by Pearson as "hard" or "borderline" acids which interact with the "hard" base O 2- to form more stable bonds than the cations classified as "soft" acids.

Claim 9

Dependent Claim 34 words

The crystalline molecular sieves according to claim 2 wherein the mole fracions "w", "x", "y" and "z" are within the tetragonal conpositional area defined by points a, b, c and d of FIG. 2.

Claim 10

Dependent Claim 15 words

The crystalline molecular sieves according to claim 2 wherein "EL" is at least 2 elements.

Claim 11

Dependent Claim 15 words

The crystalline molecular sieves according to claim 2 wherein "EL" is at least 3 elements.

Claim 12

Dependent Claim 15 words

The crystalline molecular sieves according to claim 2 wherein "EL" is at least 4 elements.

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 A.

Claim 14

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 B.

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 C.

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 D.

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 E.

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 F.

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 G.

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 H.

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 J.

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 K.

Claim 23

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-spacings set forth in Table L.

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 M.

Claim 25

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 26

Dependent Claim 28 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 27

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 28

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 29

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 30

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 31

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 32

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 33

Dependent Claim 28 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 34

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 W.

Claim 35

Dependent Claim 31 words

Crystalline molecular sieves according to claim 9, claim 10 or claim 11 wherein element "EL" is selected from the group consisting of beryllium, cobalt, gallium, iron, magnesium, manganese, titanium and zinc.

Claim 36

Dependent Claim 203 words

Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures which comprises providing at an effective temperature and for an effective time a reaction mixture composition expressed in terms of molar oxide ratios as follows: wherein "R" is at least one organic templating agent: "a" is the amount of "R" and is zero or an effective amount greater than zero to about 6; "b" has a value of from zero to about 500, "EL" represents at least one element capable of forming a three-dimensional oxide, "EL" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" has a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/g-atom and "EL" is capable of forming M-O-P. M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O" bond dissociation energy greater than about 59 kcal/mole at 298°K: and "w", "x", "y" and "z" represent mole fractions, respectively, of "EL", aluminum and phosphorus and silicon in the (EL w Al x P y Si 2 )O 2 constituent, and each has a value of at least 0.01, whereby the molecular sieves of claim 1 or claim 2 are prepared.

Claim 37

Dependent Claim 16 words

Process of claim 30 wherein "a" is an effective amount greater than zero to about 6.

Claim 38

Dependent Claim 17 words

Process according to claim 35 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

Claim 39

Dependent Claim 36 words

Process according to claim 35 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 of pseudo-boehmite and aluminum alkoxide.

Claim 40

Dependent Claim 12 words

Process according to claim 38 wherein the aluminum alkoxide is aluminum isopropoxide.

Claim 41

Dependent Claim 12 words

Process according to claim 35 wherein the source of silicon is silica.

Claim 42

Dependent Claim 29 words

Process according to claim 35 wherein the source of "EL" is selected from the group consisting of oxides, hydroxides, alkoxides, nitrates, halides, sulfates, carboxylates, organometallic compounds and mixtures thereof.

Claim 43

Dependent Claim 44 words

Process according to claim 35 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula - wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.

Claim 44

Dependent Claim 13 words

Process according to claim 35 wherein the organic templating agent is an amine.

Claim 45

Dependent Claim 85 words

Process according to claim 35 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-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diazabicyclo-(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 46

Dependent Claim 35 words

Crystalline molecular sieves prepared by calcining the compositions of claim 1 or claim 2, at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system.

Claim 47

Dependent Claim 75 words

Process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture of molecular species with a molecular seive of claim 1 or claim 2 having pore diameters large enough to adsorb at least one of the more polar molecular species, said molecular sieve being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

Claim 48

Dependent Claim 71 words

Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a molecular seive of claim 1 or claim 2 having pore diameters large enough to adsorb at least one but not all molecular species of said mixture, said molecular seive being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof.

Claim 49

Dependent Claim 13 words

Process according to claim 46 wherein the more polar molecular species is water.

Claim 50

Dependent Claim 24 words

Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular seive of claim 1 or claim 2.

Claim 51

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is cracking.

Claim 52

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is hydrocracking.

Claim 53

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon convetsion process is hydrogenation.

Claim 54

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is polymerization.

Claim 55

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is alkylation.

Claim 56

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is reforming.

Claim 57

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is hydrotreating.

Claim 58

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is isomerization.

Claim 59

Dependent Claim 13 words

Process according to claim 57 wherein the isomerization conversion process is xylene isomerization.

Claim 60

Dependent Claim 12 words

Process according to claim 49 wherein the hydrocarbon conversion process is dehydrocyclization.

Claim 61

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents arsenic.

Claim 62

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents beryllium.

Claim 63

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents boron.

Claim 64

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents chromium.

Claim 65

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents gallium.

Claim 66

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents germanium.

Claim 67

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents lithium.

Claim 68

Dependent Claim 12 words

The crystalline molecular sieve according to claim 1 wherein "EL" represents vanadium.

Molecular sieve compositions

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