US4500651A — Titanium-containing molecular sieves

Claim 1

Independent Claim 174 words

Crystalline molecular sieves comprising pores having nominal diameters of greater than about 3 Angstroms and whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula: mR:(Ti.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 moles of "R" present per mole of (Ti x Al y P z )O 2 has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, 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 the ternary diagram which is FIG. 1 of the drawings, said points A, B, C, D and E representing the following values for "x", "y" and "z": ______________________________________ Mole Fraction Point x y z ______________________________________ A 0.001 0.45 0.549 B 0.88 0.01 0.11 C 0.98 0.01 0.01 D 0.29 0.70 0.01 E 0.001 0.70 0.299. ______________________________________

Claim 2

Dependent Claim 174 words

Crystalline molecular sieves comprising pores having nominal diameters of greater than about 3 Angstroms and whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula: mR:(Ti.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 moles of "R" present per mole of (Ti x Al y P z )O 2 has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, 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 the ternary diagram which is FIG. 1 of the drawings, said points A, B, C, D and E representing the following values for "x", "y" and "z": ______________________________________ Mole Fraction Point x y z ______________________________________ A 0.001 0.45 0.549 B 0.88 0.01 0.11 C 0.98 0.01 0.01 D 0.29 0.70 0.01 E 0.001 0.70 0.299. ______________________________________

Claim 3

Dependent Claim 108 words

The crystalline molecular sieves according to claim 1 wherein the mole fractions of titanium, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is FIG. 2 of the drawings, said ponts a, b, c, d and e of the ternary diagram which is FIG. 2 of the drawings, said points a, b, c, d and e representing the following values for "x", "y" and "z". ______________________________________ Mole Fraction Point x y z ______________________________________ a 0.002 0.499 0.499 b 0.20 0.40 0.40 c 0.20 0.50 0.30 d 0.10 0.60 0.30 e 0.002 0.60 0.398. ______________________________________

Claim 4

Dependent Claim 21 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table V.

Claim 5

Dependent Claim 21 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table VII.

Claim 6

Dependent Claim 21 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table IX.

Claim 7

Dependent Claim 21 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table XI.

Claim 8

Dependent Claim 21 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern set forth in Table XIII.

Claim 9

Dependent Claim 19 words

The crystalline molecular sieve of claims 1 or 2 having the characteristic X-ray powder diffraction pattern of Table XV.

Claim 10

Dependent Claim 14 words

The crystalline molecular sieves of claim 1 wherein the molecular sieves have been calcined.

Claim 11

Dependent Claim 14 words

The crystalline molecular sieves of claim 2 wherein the molecular sieves have been calcined.

Claim 12

Dependent Claim 30 words

The crystalline molecular sieves of claims 9 or 10 having the characteristic X-ray powder diffraction pattern set forth in any one of Tables A, C, E, G, M or O.

Claim 13

Dependent Claim 41 words

The crystalline molecular sieves of claims 9 or 10 wherein such are calcined in air at a temperature between about 200° C. and about 700° C. for a period of time sufficient to remove at least a portion of template R.

Claim 14

Dependent Claim 187 words

Process for preparing a titanium-containing molecular sieve as set forth in claim 1 which comprises forming a reaction mixture containing reactive sources of TiO 2 , Al 2 O 3 , and P 2 O 5 and an organic templating agent, said reaction mixture comprising a composition expressed in terms of molar oxide ratios of: fR.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :gH.sub.2 O wherein "R" is an organic templating agent; "f" has a value large enough to constitute an effective amount of "R"; "g" has a value of from zero to 500; "x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum and phosphorus in the (Ti x Al y P z )O 2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is FIG. 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z": ______________________________________ Mole Fraction Point x y z ______________________________________ h 0.001 0.989 0.01 i 0.001 0.01 0.989 j 0.32 0.24 0.44 k 0.98 0.01 0.01. ______________________________________

Claim 15

Dependent Claim 15 words

Process according to claim 13 wherein "g" has a value of from 2 to 50.

Claim 16

Dependent Claim 183 words

Process according to claim 13 for preparing a titanium-containing molecular sieve which comprises forming a reaction mixture having a composition expressed in terms of molar oxide ratios of: oR.sub.2 O:wM.sub.2 O:(Ti.sub.x Al.sub.y P.sub.z)O.sub.2 :nH.sub.2 O wherein "R" is an organic templating agent; "o" has a value great enough to constitute an effective concentration of "R" and is within the range 0 to 1; "M" is an alkali metal cation; "w" has a value of zero to 2.5; "n" has a value of from zero to 500; "x", "y" and "z" represent the mole fractions, respectively, of titanium, aluminum, and phosphorus in the (Ti x Al y P z )O 2 constituent, and each has a value of at least 0.001 and being within the quatrilateral compositional area defined by points, h, i, j and k which is FIG. 3 of the drawings, said points h, i, j and k representing the following values for "x", "y" and "z": ______________________________________ Mole Fraction Point x y z ______________________________________ h 0.001 0.989 0.01 i 0.001 0.01 0.989 j 0.32 0.24 0.44 k 0.98 0.01 0.01. ______________________________________

Claim 17

Dependent Claim 20 words

Process according to claim 13 or claim 15 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

Claim 18

Dependent Claim 39 words

Process according to claims 13 or 15 wherein the source of aluminum in the reaction mixture is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxide, and the source of phosphorus is orthophosphoric acid.

Claim 19

Dependent Claim 12 words

Process according to claim 16 wherein the aluminum alkoxide is aluminum isopropoxide.

Claim 20

Dependent Claim 51 words

Process according to claims 13 or 15 where the organic templating agent is selected from the group consisting of quaternary ammonium or quaternary phosphonium compounds of the formula R.sub.4 X.sup.+ wherein X is nitrogen or phosphorous and each R is alkyl containing between 1 and about 8 carbon atoms or aryl.

Claim 21

Dependent Claim 84 words

Process according to claims 13 or 15 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; dicyclohexylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diazabicyclo-(2,2,2)octane; 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 and 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt [(C 14 H 32 N 2 )] x wherein x is a value of at least 2.

Claim 22

Dependent Claim 135 words

Crystalline molecular sieves comprising a composition expressed in terms of the mole ratios of oxides in the anhydrous form as: vR:pTiO.sub.2 :qAl.sub.2 O.sub.3 :rP.sub.2 O.sub.5 wherein "R" represents at least one organic templating agent; "v" represents an effective amount of organic templating agent; "p", "q" and "r" represent moles, respectively, of titanium, alumina and phosphorus pentaoxide based on said moles being such that they are within the pentagonal compositional area defined by point A, B, C, D and E of the ternary diagram which is FIG. 1 of the drawings, said points A, B, C, D and E representing the following values for "p", "q" and "r". ______________________________________ Mole Point p q r ______________________________________ A 0.004 1.0 1.22 B 176 1.0 11.0 C 196 1.0 1.0 D 0.828 1.0 0.0143 E 0.003 1.0 0.427. ______________________________________

Claim 23

Dependent Claim 135 words

Crystalline molecular sieves comprising a composition expressed in terms of the mole ratios of oxides in the anhydrous form as: vR:pTiO.sub.2 :qAl.sub.2 O.sub.3 :rP.sub.2 O.sub.5 wherein "R" represents at least one organic templating agent; "v" represents an effective amount of organic templating agent; "p", "q" and "r" represent moles, respectively, of titanium, alumina and phosphorus pentaoxide based on said moles being such that they are within the pentagonal compositional area defined by point A, B, C, D and E of the ternary diagram which is FIG. 1 of the drawings, said points A, B, C, D and E representing the following values for "p", "q" and "r". ______________________________________ Mole Point p q r ______________________________________ A 0.004 1.0 1.22 B 176 1.0 11.0 C 196 1.0 1.0 D 0.828 1.0 0.0143 E 0.003 1.0 0.427. ______________________________________

Claim 24

Dependent Claim 84 words

The crystalline molecular sieves of claim 21 wherein "p", "q" and "r" are preferably within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is FIG. 2 of the drawings, said points a, b, c, d and e representing the following values for "p", "q" and "r": ______________________________________ Mole Point p q r ______________________________________ a 0.008 1.0 1.0 b 1.0 1.0 1.0 c 0.80 1.0 0.60 d 0.333 1.0 0.50 e 0.0067 1.0 0.663. ______________________________________

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1988-02-19	1988-08-20	1989-02-19	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1992-02-19	1992-08-20	1993-02-19	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1996-02-19	1996-08-20	1997-02-19	$7700.00	Window Closed / Lapsed

Titanium-containing molecular sieves

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