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Crystalline microporous solids, such as aluminosilicate zeolites or silica molecular sieves, are grown in a fluoride-containing, substantially non-aqueous medium to form crystals on the order 0.3-3 mm in size. This growth process involves preparing a mixture containing one or more nutrients capable

Crystalline microporous solids, such as aluminosilicate zeolites or silica molecular sieves, are grown in a fluoride-containing, substantially non-aqueous medium to form crystals on the order 0.3-3 mm in size. This growth process involves preparing a mixture containing one or more nutrients capable of forming the crystalline microporous solid, such as a source of silica and a source of alumina; water in a controlled amount; a growth medium comprising hydrogen fluoride and a nitrogen-containing organic base, such as pyridine; and optionally an organic solvent and/or a structure-directing agent; and thereafter heating the resulting mixture for a time sufficient to produce the crystalline microporous solid.

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1. A process of growing a crystalline microporous silica or aluminosilicate solid comprising preparing a mixture containing: (a) one or more nutrients capable of forming the crystalline microporous solid wherein the one or more nutrients are selected from the group consisting of a source of silic

1. A process of growing a crystalline microporous silica or aluminosilicate solid comprising preparing a mixture containing: (a) one or more nutrients capable of forming the crystalline microporous solid wherein the one or more nutrients are selected from the group consisting of a source of silica, a source of alumina, and a source of a charge balancing ion; (b) a growth medium comprising a nitrogen-containing organic base, hydrogen fluoride, and optionally, an organic solvent which does not inhibit the mineralization of the nutrients; the nutrients and growth medium being present in proportions sufficient to provide for the formation of the crystalline microporous solid; and (c) water in an amount such that the molar ratio of water to total framework-forming elements excluding oxygen is no greater than about 6, and such that the ratio of the moles of water to combined moles of nitrogen-containing organic base and optional organic solvent is no greater than 0.6, and heating the resulting mixture for a time sufficient to produce a crystalline microporous silica or aluminosilicate solid. 2. The process of claim 1 wherein the nutrient is a source of silica. 3. The process of claim 1 wherein the nutrients are sources of silica, alumina and a charge balancing cation. 4. The process of claim I wherein the nitrogen-containing organic base is pyridine, a ring-substituted pyridine wherein the substituent is a C 1-10 alkyl moiety; or a primary, secondary or tertiary C 1-10 alkylamine. 5. The process of claim 4 wherein the nitrogen-containing organic base is pyridine or triethylamine. 6. The process of claim 1 wherein the optional organic solvent is employed. 7. The process of claim 1 wherein the molar ratio of water to total framework-forming elements excluding oxygen is in the range from about 2 to about 5. 8. The process of claim 1 wherein the ratio of moles of water to combined moles of nitrogen-containing organic base and optional organic solvent is no greater than about 0.56. 9. The process of claim 1 wherein the temperature of heating is in the range from about 50° C. to about 250° C. 10. The process of claim 1 wherein a structure-directing agent is employed. 11. The process of claim 10 wherein the structure-directing agent is an alkylamine or tetraalkylammonium ion, wherein the alkyl group or groups contain from 1 to 20 carbon atoms. 12. The process of claim 11 wherein the structure-directing agent is propylamine or tetrapropylammonium. 13. The process of claim 1 wherein the molar ratio of fluoride to total framework forming elements excluding oxygen ranges from about 0.7to about 2.0. 14. The process of claim 1 wherein the crystal size of the microporous crystalline solid is between about 0.3 mm and about 3 mm. 15. The process of claim 1 wherein the crystal size of the microporous crystalline solid is between about 1 mm and about 3 mm. 16. A process of growing a microporous crystalline silica wherein the crystal size is between about 0.3 mm and about 3 mm comprising preparing a mixture containing (a) a source of silica, (b) a growth medium comprising hydrogen fluoride, a nitrogen-containing organic base selected from the group consisting of pyridine, ring-substituted pyridines, and primary, secondary, and tertiary alkylamines, and optionally, an organic solvent other than the pyridines and alkylamines mentioned herein which does not hinder the mineralization of the source of silica and (c) water in an amount such that the water/silicon molar ratio is no greater than about 6 and such that the ratio of the moles of water to the combined moles of nitrogen-containing organic base and optional organic solvent is no greater than 0.6; and heating the resulting mixture for a time sufficient to produce a microporous crystalline silica having a crystal size between about 0.3 mm and about 3 mm. 17. The process of claim 16 wherein fumed silica is employed having a surface area in the range from about 100 m 2 /g to about 380 m 2 /g and a particle size in the range from about 7 μm to about 100 μm. 18. A process of growing a crystalline aluminosilicate zeolite having a crystal size between about 0.3 mm and about 3 mm comprising preparing a mixture containing (a) a source of silica, a source of alumina, and a source of a charge balancing cation in amounts sufficient to form an aluminosilicate zeolite, (b) a growth medium comprising hydrogen fluoride, a nitrogen-containing organic base selected from the group consisting of pyridine, ring-substituted pyridines, and primary, secondary, and tertiary alkylamines, and optionally, an organic solvent other than the pyridines and alkylamines mentioned herein which does not hinder the mineralization of the source of silica, alumina, and charge balancing cation, and (c) water in an amount such that the ratio of moles of water to combined moles of silicon and aluminum is no greater than about 6 and such that the ratio of the moles of water to the combines moles of nitrogen-containing organic base and optional organic solvent is no greater than 0.6; and thereafter heating the resulting mixture for a time sufficient to produce a crystalline aluminosilicate zeolite having a crystal size between about 0.3 mm and about 3 mm. 19. The process of claim 18 wherein a fumed silica having a particle size in the range from about 7 82 m to about 100 μm and a boehmite alumina having a particle size in the range from about 7 μm to about 7000 μm are employed. 20. The process of claim 18 wherein a structure-directing agent is employed. 21. A crystalline microporous solid having a crystal size between about 0.3 mm and about 3 mm, the solid being selected from the group consisting of the MOR, MFI, and MTN families of crystalline microporous solids. 22. The crystalline microporous solid of claim 21 wherein the crystal size is between about 1 mm and about 3 mm.