Synthesis of crystalline porous solids in ammonia

• US 5,599,520 A
• Filed: 11/03/1994
• Issued: 02/04/1997
• Est. Priority Date: 11/03/1994
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Howard, Kevin E., Millar, Dean M., Garc es, Juan M.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): NOT, DEFINED
• Application Number:
  US08/333,670
• Time in Patent Office: 824 Days
• Field of Search: 423/700, 423/701, 423/702, 423/703, 423/704, 423/705, 423/326, 423/328.2, 423/330.1
• US Class Current: 423/700
• CPC Class Codes: C01B 37/02 Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
• CPC Class Codes: C01B 39/48 using at least one organic template directing agent
• CPC Class Codes: Y10S 423/27 Beta, e.g. NU-2

Abstract

A process of preparing a crystalline porous solid selected from silicas and metallosilicates, such as, aluminosilicate zeolites or clathrasils. The process involves preparing a reaction mixture containing ammonia; water in a controlled concentration; a (hydrocarbyl)ammonium polysilicate hydrate salt; a mineralizer, such as ammonium fluoride; optionally, a source of a metal oxide, such as aluminum nitride; and optionally, a source of a charge-balancing cation or a structure directing agent; and maintaining the mixture at a temperature and for a time so as to produce the crystalline porous solid. A novel silica which is isostructural with zeolite P1 is prepared. Also prepared are a novel silica which is isostructural with zeolite beta and a novel TMA sodalite having a silica/alumina molar ratio between 12 and about 20.

Claims

1. A process of preparing a crystalline porous solid selected from the group consisting of silicas and metallosilicates, the process comprising preparing a mixture containing:

(a) ammonia,

(b) water in an amount such that the molar ratio of ammonia to water is greater than about 4 and less than about 26,

(c) one or more nutrients comprising a (hydrocarbyl)ammonium polysilicate hydrate salt, and optionally, a source of a metal oxide which is reactive in the reaction mixture, and optionally, a source of an additional cation which is reactive in the reaction mixture, the relative amounts of the nutrients being sufficient to form the crystalline porous solid, and

(d) a mineralizer in an amount sufficient to mineralize the nutrient(s);

and maintaining the resulting mixture at a temperature and for a time sufficient to produce the crystalline porous silica or metallosilicate.

2. The process of claim 1 wherein the crystalline porous solid is selected from the group consisting of clathrasils, felspars, layered aluminosilicates, aluminosilicate molecular sieves, and silica molecular sieves.

3. The process of claim 1 wherein the molar ratio of ammonia to silicon ranges between about 10 and about 1000.

4. The process of claim 1 wherein the mineralizer is a fluoride ion.

5. The process of claim 4 wherein the fluoride is obtained from a source of fluoride selected from the group consisting of ammonium fluoride, hydrogen fluoride, sodium fluoride, sodium bifluoride, and ammonium hexafluorosilicate.

6. The process of claim 1 wherein the molar ratio of mineralizer to silica ranges between about 0.04 and about 0.50.

7. The process of claim 1 wherein the metal oxide is selected from the group consisting of the oxides of aluminum, gallium, titanium, magnesium, boron, iron, nickel, cobalt, vanadium, zirconium, phosphorus, and mixtures thereof.

8. The process of claim 1 wherein the metal oxide is alumina which is obtained from a source of alumina selected from the group consisting of aluminum metal, aluminum nitride, aluminum hydride, aluminum alkoxides, aluminum halides, aluminum phosphates, amorphous and crystalline aluminas, aluminate, and aluminosilicates.

9. The process of claim 1 wherein a source of an additional cation is employed as a charge-balancing cation or as a structure-directing agent.

10. The process of claim 1 wherein the ammonia/water molar ratio is greater than about 6 and less than about 26.

11. The process of claim 10 wherein the ammonia/water molar ratio ranges between about 7 and less than about 26.

12. The process of claim 1 wherein a secondary source of silica is present and is selected from the group consisting of crystalline and amorphous silicas, metallosilicates, amorphous and crystalline aluminosilicates, and aluminosilicate molecular sieves.

13. The process of claim 12 wherein the aluminosilicate molecular sieve is selected from the group consisting of zeolites X, Y, A, mordenite, ferrierite, and beta.

14. The process of claim 1 wherein the temperature ranges between about 0°

C. and about 200°

C.

15. The process of claim 14 wherein the temperature ranges between about 100°

C. and about 180°

C.

16. The process of claim 1 wherein a seed crystal is added to the reaction mixture.

17. A process for the formation of a crystalline porous silica comprising preparing a mixture containing:

(a) ammonia,

(b) water in an amount such that the molar ratio of ammonia to water is greater than about 5 and less than about 26,

(c) a (hydrocarbyl)ammonium polysilicate hydrate salt in an amount sufficient to prepare the crystalline porous silica, and

(d) a fluoride mineralizer in an amount sufficient to mineralize the polysilicate salt,

and maintaining the resulting mixture at a temperature ranging between about 100°

C. and about 180°

C. for a time sufficient to produce the crystalline porous silica.

18. A process for the formation of a crystalline porous aluminosilicate comprising preparing a mixture containing:

(a) ammonia, and

(b) water in an amount such that the molar ratio of ammonia to water is greater than about 5 and less than about 26,

(c) nutrients comprising a (hydrocarbyl)ammonium polysilicate hydrate salt, aluminum nitride, and optionally, a charge-balancing cation, in relative amounts sufficient to form the crystalline porous aluminosilicate; and

(d) a fluoride ion mineralizer in an amount sufficient to mineralize the nutrients,

and maintaining the resulting mixture at a temperature ranging between about 100°

C. and about 180°

C. for a time sufficient to produce the crystalline porous aluminosilicate.

19. A process of preparing a crystalline porous solid selected from the group consisting of silicas and metallosilicates, the process comprising preparing a mixture containing:

(a) ammonia,

(b) water in an amount such that the molar ratio of ammonia to water is greater than about 4 and less than about 26,

(c) one or more nutrients comprising a (hydrocarbyl)ammonium polysilicate hydrate salt wherein the polysilicate ion is selected from the group consisting of Si₆ O₁₅^-6, Si₈ O₂₀^-8, and Si₁₀ O₂₅^-10, and optionally, a source of a metal oxide which is reactive in the reaction mixture, and optionally, a source of an additional cation which is reactive in the reaction mixture, the relative amounts of the nutrients being sufficient to form the crystalline porous solid, and

(d) a mineralizer in an amount sufficient to mineralize the nutrient(s); and

maintaining the resulting mixture at a temperature and for a time sufficient to produce the crystalline porous silica or metallosilicate.

20. A process of preparing a crystalline porous solid selected from the group consisting of silicas and metallosilicates, the process comprising preparing a mixture containing:

(a) ammonia,

(b) water in an amount such that the molar ratio of ammonia to water is greater than about 4 and less than about 26,

(c) one or more nutrients comprising a (hydrocarbyl)ammonium polysilicate hydrate salt, aluminum nitride, and optionally, a source of an additional cation which is reactive in the reaction mixture, the relative amounts of the nutrients being sufficient to form the crystalline porous solid, and

(d) a mineralizer in an amount sufficient to mineralize the nutrient(s); and

maintaining the resulting mixture at a temperature and for a time sufficient to produce the crystalline porous silica or metallosilicate.