US5164170A — Synthesis of zeolite Beta

Claim 1

Independent Claim 216 words

A method of synthesizing a crystalline synthetic zeolite comprising a large crystal zeolite Beta which ranges in size from 0.1 to 3.0 microns having a silica to alumina ratio of at least 20 to about 200 which is substantially free of amorphous materials and having the structure of zeolite Beta prepared by: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, an oxide of silicon, water and an oxide of aluminum and having reaction mixture in terms of mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 120 OH.sup.- /SiO.sub.2 = 0.1 to about 0.5 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 20.6 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 0.22 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta wherein said large crystal zeolite beta is substantially free of amorphous materials and has a silica-to-alumina ratio ranging from about 20 to about 200; and (c) recovering the crystalline zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanoloamine.

Claim 2

Independent Claim 216 words

A method of synthesizing a crystalline synthetic zeolite comprising a large crystal zeolite Beta which ranges in size from 0.1 to 3.0 microns having a silica to alumina ratio of at least 20 to about 200 which is substantially free of amorphous materials and having the structure of zeolite Beta prepared by: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, an oxide of silicon, water and an oxide of aluminum and having reaction mixture in terms of mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 120 OH.sup.- /SiO.sub.2 = 0.1 to about 0.5 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 20.6 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 0.22 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta wherein said large crystal zeolite beta is substantially free of amorphous materials and has a silica-to-alumina ratio ranging from about 20 to about 200; and (c) recovering the crystalline zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanoloamine.

Claim 3

Dependent Claim 31 words

The method of claim 1 in which the source of oxide of silicon of the reaction mixture is selected from the group consisting of colloidal silica, precipitated silica and silica precursor.

Claim 4

Dependent Claim 28 words

The method of claim 2 in which the source of oxide of silicon is the precipitated silica or silica precursor and the reaction mixture further comprises crystalline zeolite

Claim 5

Dependent Claim 41 words

The method of claim 1 in which the organic cation represented by R and the triethanoloamine represented by X of the zeolite Beta recovered in step (b) are converted into the hydrogen form at least in part by calcining and exhange.

Claim 6

Dependent Claim 27 words

The method of claim 1 in which maintaining the reaction mixture under conditions sufficient to crystallize the zeolite includes temperatures ranging from 70° C. to 175° C.

Claim 7

Dependent Claim 21 words

The method of claim 3 in which the zeolite Beta seeds are prepared by the synthesis as described in claim 1.

Claim 8

Dependent Claim 26 words

The method of claim 1 in which the organic cation source is selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium halide and a combination thereof.

Claim 9

Dependent Claim 25 words

The method of claim 7 in which the tetraethylammmonium halide source is selected from the group consisting of tetraethylammonium bromide, tetraethylammonium chloride, and tetraethylammonium fluoride.

Claim 10

Dependent Claim 209 words

A process for the production of large crystal zeolite Beta having a crystal size ranging from 0.1 to 3.0 microns and a silica-to-alumina mole ratio of about 200 to about 1000 which is substantially free of amorphous materials comprising the steps of: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, water, a source of aluminum, and a silica source which is an oxide of silicon and having a reaction mixture in terms of mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = greater than 70 OH.sup.- /SiO.sub.2 = 0.2 to 0.4 R/SiO.sub.2 = 0.3 to 0.9 H.sub.2 O/SiO.sub.2 = 5 to 15 M.sup.2 /SiO.sub.2 = 0.01 to 0.07 X/SiO.sub.2 = 0.2 to 0.8 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine, the reaction mixture also containing a plurality of zeolite beta seeds; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite to produce a large crystal zeolite beta having a crystal size ranging from 0.1 to 3.0 microns which is substantially free of amorphous materials and which is substantially free of contaminants; and (c) recovering the crystalline zeolite beta.

Claim 11

Dependent Claim 209 words

A process for the production of large crystal zeolite Beta having a crystal size ranging from 0.1 to 3.0 microns and a silica-to-alumina mole ratio of about 200 to about 1000 which is substantially free of amorphous materials comprising the steps of: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, water, a source of aluminum, and a silica source which is an oxide of silicon and having a reaction mixture in terms of mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = greater than 70 OH.sup.- /SiO.sub.2 = 0.2 to 0.4 R/SiO.sub.2 = 0.3 to 0.9 H.sub.2 O/SiO.sub.2 = 5 to 15 M.sup.2 /SiO.sub.2 = 0.01 to 0.07 X/SiO.sub.2 = 0.2 to 0.8 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine, the reaction mixture also containing a plurality of zeolite beta seeds; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite to produce a large crystal zeolite beta having a crystal size ranging from 0.1 to 3.0 microns which is substantially free of amorphous materials and which is substantially free of contaminants; and (c) recovering the crystalline zeolite beta.

Claim 12

Dependent Claim 41 words

The process of claim 9 in which the organic cation represented by R and the triethanolamine represented by X of the zeolite Beta recovered in step (b) are converted at least in part into the hydrogen form by calcining and exchange.

Claim 13

Dependent Claim 27 words

The process of claim 9 in which maintaining the reaction mixture under conditions sufficient to crystallize the zeolite includes temperatures ranging from 70° C. to 175° C.

Claim 14

Dependent Claim 26 words

The process of claim 9 in which the organic cation source is selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium halide and a combination thereof.

Claim 15

Dependent Claim 25 words

The process of claim 12 in which the tetraethylammonium halide source is selected from the group consisting of tetraethylammonium bromide, tetraethylammonium chloride and tetraethylammonium fluoride.

Claim 16

Dependent Claim 20 words

The process of claim 9 in which the silica source has a solids content of greater than about 78 wt.%.

Claim 17

Dependent Claim 14 words

The process of claim 9 which includes the step of agitating the reaction mixture.

Claim 18

Dependent Claim 207 words

A process for the production of zeolite Beta having a silica-to-alumina mole ratio of at least about 465 which is substantially free of amorphous materials comprising the steps of: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, water, and a silica source and having a reaction mixture in terms of mole ratios within the following ranges: ______________________________________ OH.sup.- /SiO.sub.2 = 0.2 to 0.4 R/SiO.sub.2 = 0.3 to 0.9 H.sub.2 O/SiO.sub.2 = 5 to 15 M.sup.2 /SiO.sub.2 = 0.01 to 0.07 X/SiO.sub.2 = 0.2 to 0.8 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine, the reaction mixture also containing a plurality of zeolite beta seeds which are highly silicious and high purity; (b) agitating the reaction mixture under conditions of temperature, ranging from about 70° C. to about 140° C. and time ranging from about 16 hours to 10 days, sufficient to crystallize the zeolite to produce zeolite beta which is substantially free of amorphous materials wherein said triethanolamine facilitates fluidization of the reaction mixture to produce the zeolite beta which is substantially free of contaminants; and (c) recovering the crystalline zeolite beta.

Claim 19

Dependent Claim 207 words

A process for the production of zeolite Beta having a silica-to-alumina mole ratio of at least about 465 which is substantially free of amorphous materials comprising the steps of: (a) preparing a reaction mixture which contains one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, triethanolamine, water, and a silica source and having a reaction mixture in terms of mole ratios within the following ranges: ______________________________________ OH.sup.- /SiO.sub.2 = 0.2 to 0.4 R/SiO.sub.2 = 0.3 to 0.9 H.sub.2 O/SiO.sub.2 = 5 to 15 M.sup.2 /SiO.sub.2 = 0.01 to 0.07 X/SiO.sub.2 = 0.2 to 0.8 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine, the reaction mixture also containing a plurality of zeolite beta seeds which are highly silicious and high purity; (b) agitating the reaction mixture under conditions of temperature, ranging from about 70° C. to about 140° C. and time ranging from about 16 hours to 10 days, sufficient to crystallize the zeolite to produce zeolite beta which is substantially free of amorphous materials wherein said triethanolamine facilitates fluidization of the reaction mixture to produce the zeolite beta which is substantially free of contaminants; and (c) recovering the crystalline zeolite beta.

Claim 20

Dependent Claim 41 words

The process of claim 16 in which the organic cation represented by R and the triethanolamine represented by X of the zeolite Beta recovered in step (b) are converted at least in part into the hydrogen form by calcining and exchange.

Claim 21

Dependent Claim 26 words

The process of claim 16 in which the organic cation source is selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium halide and a combination thereof.

Claim 22

Dependent Claim 25 words

The process of claim 18 in which the tetraethylammonium halide source is selected from the group consisting of tetraethylammonium bromide, tetraethylammonium chloride and tetraethylammonium fluoride.

Claim 23

Dependent Claim 21 words

The process of claim 16 in which the silica source has a solids content ranging from 30 wt.% to 90 wt.%.

Claim 24

Dependent Claim 19 words

The process of claim 20 in which the silica source has a solids content of at least 87 wt.%.

Claim 25

Dependent Claim 20 words

The process of claim 16 in which the zeolite beta seeds have a silica-to-alumina mole ratio of at least 70.

Claim 26

Dependent Claim 17 words

The process of claim 22 in which the zeolite beta seed are substantially free of amorphous materials.

Claim 27

Dependent Claim 103 words

The process of claim 23 in which the zeolite beta seeds are made from a reaction mixture which comprises one or more sources of alkali metal cations, organic cation which is a tetraethylammonium cation, an oxide of silicon, water and an oxide of aluminum and having a reaction mixture in terms of mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 70 to about 1000 OH.sup.- /SiO.sub.2 = 0.2 to 0.4 R/SiO.sub.2 = 0.3 to 0.9 H.sub.2 O/SiO.sub.2 = 5.0 to 15 M/SiO.sub.2 = 0.01 to 0.07 ______________________________________ where R is the organic cation and M is the alkali metal cation.

Claim 28

Dependent Claim 33 words

The process of claim 24 in which the reaction mixture for the zeolite beta seeds includes triethanolamine, represented by X, in a mole ratio of X/SiO 2 ranging from about 0.2 to 0.8.

Claim 29

Dependent Claim 207 words

In a process for the production of zeolite beta by preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water and an oxide of aluminum wherein the improvement comprises preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water, an oxide of aluminum and triethanolamine, said reaction mixture having mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 120 OH.sup.- /SiO.sub.2 = 0.1 to about 0.5 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 20.6 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 0.22 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta having a large crystal size which ranges from 0.1 to 3.0 microns which is substantially free of amorphous materials, said large crystal zeolite Beta having a silica to alumina ratio of at least 20 to about 200; and (c) recovering the zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanolamine.

Claim 30

Dependent Claim 207 words

In a process for the production of zeolite beta by preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water and an oxide of aluminum wherein the improvement comprises preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water, an oxide of aluminum and triethanolamine, said reaction mixture having mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 120 OH.sup.- /SiO.sub.2 = 0.1 to about 0.5 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 20.6 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 0.22 ______________________________________ where R is the organic cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta having a large crystal size which ranges from 0.1 to 3.0 microns which is substantially free of amorphous materials, said large crystal zeolite Beta having a silica to alumina ratio of at least 20 to about 200; and (c) recovering the zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanolamine.

Claim 31

Dependent Claim 41 words

The process of claim 26 in which the organic cation represented by R and the triethanolamine represented by X of the zeolite Beta recovered in step (b) are converted at least in part into the hydrogen form by calcining and exchange.

Claim 32

Dependent Claim 27 words

The process of claim 26 in which maintaining the reaction mixture under conditions sufficient to crystallize the zeolite includes temperatures ranging from 70° C. to 175° C.

Claim 33

Dependent Claim 26 words

The process of claim 26 in which the organic cation source is selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium halide and a combination thereof.

Claim 34

Dependent Claim 25 words

The process of claim 29 in which the tetraethylammonium halide source is selected from the group consisting of tetraethylammonium bromide, tetraethylammonium chloride or tetraethylammonium fluoride.

Claim 35

Dependent Claim 20 words

The process of claim 26 in which the zeolite beta has a silica-to-alumina mole ratio of 20 to about 100.

Claim 36

Dependent Claim 21 words

The process of claim 1 in which the zeolite beta has a silica-to-alumina mole ratio ranging from 20 to about 100.

Claim 37

Dependent Claim 209 words

In a process for the production of zeolite beta by preparing a liquid synthesis mixture from which zeolite beta crystallizes which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water and an oxide of aluminum wherein the improvement comprises preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, oxide of silicon, water, oxide of aluminum and triethanolamine, said reaction mixture having mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 1000 OH.sup.- /SiO.sub.2 = 0.1 to about 0.8 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 40.0 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 1.0 ______________________________________ where R is the tetraethylammonium cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta which is substantially free of amorphous materials, said zeolite Beta having a silica to alumina ratio of at least 20 to about 1000; and (c) recovering the zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanolamine, said zeolite having a crystal size ranging from 0.1 to 3.0 microns.

Claim 38

Dependent Claim 209 words

In a process for the production of zeolite beta by preparing a liquid synthesis mixture from which zeolite beta crystallizes which includes one or more sources of alkali metal cations, tetraethylammonium cation, an oxide of silicon, water and an oxide of aluminum wherein the improvement comprises preparing a reaction mixture which includes one or more sources of alkali metal cations, tetraethylammonium cation, oxide of silicon, water, oxide of aluminum and triethanolamine, said reaction mixture having mole ratios within the following ranges: ______________________________________ SiO.sub.2 /Al.sub.2 O.sub.3 = 20 to about 1000 OH.sup.- /SiO.sub.2 = 0.1 to about 0.8 R/SiO.sub.2 = 0.3 to about 1.0 H.sub.2 O/SiO.sub.2 = 5.0 to about 40.0 M/SiO.sub.2 = 0.01 to about 0.2 X/SiO.sub.2 = 0.1 to about 1.0 ______________________________________ where R is the tetraethylammonium cation, M is the alkali metal cation and X is the triethanolamine; (b) maintaining the reaction mixture under conditions sufficient to crystallize the zeolite Beta which is substantially free of amorphous materials, said zeolite Beta having a silica to alumina ratio of at least 20 to about 1000; and (c) recovering the zeolite Beta from step (b), the recovered zeolite containing at least one organic cation and the triethanolamine, said zeolite having a crystal size ranging from 0.1 to 3.0 microns.

Claim 39

Dependent Claim 41 words

The process of claim 33 in which the organic cation represented by R and the triethanolamine represented by X of the zeolite Beta recovered in step (b) are converted at least in part into the hydrogen form by calcining and exchange.

Claim 40

Dependent Claim 27 words

The process of claim 33 in which maintaining the reaction mixture under conditions sufficient to crystallize the zeolite includes temperatures ranging from 70° C. to 175° C.

Claim 41

Dependent Claim 26 words

The process of claim 33 in which the organic cation source is selected from the group consisting of tetraethylammonium hydroxide, tetraethylammonium halide and a combination thereof.

Claim 42

Dependent Claim 25 words

The process of claim 36 in which the tetraethylammonium halide source is selected from the group consisting of tetraethylammonium bromide, tetraethylammonium chloride or tetraethylammonium fluoride.

Claim 43

Dependent Claim 16 words

The process of claim 33 in which the source of oxide of silicon is colloidal silica.

Claim 44

Dependent Claim 23 words

The process of claim 33 in which the source of silica is selected from the group consisting of precipitated silica and silica precursor.

Claim 45

Dependent Claim 27 words

The process of claim 39 wherein the improvement further comprises as a source of silica zeolite beta seeds having a silica-to-alumina mole ratio of at least 70.

Claim 46

Dependent Claim 19 words

The process of claim 40 in which the zeolite beta seeds are made by the process of claim 33.

Claim 47

Dependent Claim 64 words

A crystalline zeolite beta comprising the as-synthesized composition identified in terms of mole ratios of oxides in the anhydrous state: (3 to 60)R 2 O:(0.5 to 12)M 2/n O:Al 2 O 3 :(200 to 1000)SiO 2 where M is an alkali metal cation and R represents a tetraethylammonium cations and triethanolamine, said zeolite beta having a crystal size ranging from 0.1 to 3.0 microns.

Claim 48

Dependent Claim 64 words

A crystalline zeolite beta comprising the as-synthesized composition identified in terms of mole ratios of oxides in the anhydrous state: (3 to 60)R 2 O:(0.5 to 12)M 2/n O:Al 2 O 3 :(200 to 1000)SiO 2 where M is an alkali metal cation and R represents a tetraethylammonium cations and triethanolamine, said zeolite beta having a crystal size ranging from 0.1 to 3.0 microns.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1995-11-17	1996-05-18	1996-11-17	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1999-11-17	2000-05-18	2000-11-17	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2003-11-17	2004-05-18	2004-11-17	$7700.00	Window Closed / Lapsed

Synthesis of zeolite Beta

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