Method for the synthesis of molecular sieves

Abstract

The present invention provides a method for the synthesis of MeAPO molecular sieves which includes the following steps: providing a source of alumina, a source of phosphorus, water, and a template suitable for forming a MeAPO molecular sieve; providing a source of metal (Me) including metal particles, the metal particles measuring, in their largest dimension, equal to or less than five nanometers; providing a water soluble organic solvent capable of solubilizing the source of metal; forming a synthesis mixture from the source of alumina, the source of phosphorus, the water, the template, the source of metal, and the solvent; and forming a MeAPO molecular sieve from the synthesis mixture.

What is claimed is:  
     
         1 . A method for making a metalloaluminophosphate (MeAPO) molecular sieve, said process comprising the steps of: 
 providing a source of alumina, a source of phosphorus, water, and a template suitable for forming a MeAPO molecular sieve;    providing a source of metal including metal particles, said metal particles measuring, in their largest dimension, equal to or less than five nanometers;    providing a water soluble organic solvent capable of solubilizing said source of metal;    forming a synthesis mixture from said source of alumina, said source of phosphorus, said water, said template, said source of metal, and said solvent; and    forming a MeAPO molecular sieve from said synthesis mixture.    
     
     
         2 . The method of  claim 1  wherein said source of metal is selected from the group consisting of boron, beryllium, cobalt, gallium, germanium, iron, manganese, magnesium, nickel, silicon, vanadium, zinc and combinations thereof.  
     
     
         3 . The method of  claim 2  wherein said source of metal is selected from the group consisting of monomeric metal compound; oligomeric metal compounds containing metal particles measuring, in their largest dimension, equal to or less than five nanometers; and mixtures thereof.  
     
     
         4 . The method of  claim 3  wherein said source of metal is monomeric metal compound.  
     
     
         5 . The method of  claim 2  wherein said source of metal is selected from the group consisting of tetraalkylorthometallates, colloidal metals, and metal sols.  
     
     
         6 . The method of  claim 5  wherein said source of metal is a tetraalkylorthometallate.  
     
     
         7 . The method of  claim 1  wherein said template is selected from the group consisting of tetraethylammonium hydroxide (TEAOH), tetra-n-propyl-ammonium hydroxide (TPAOH), tri-n-propylamine (Pr 3 N), tetra-n-butylammonium hydroxide (TBAOH) and diethylethanolamine (DEA).  
     
     
         8 . The method of  claim 7  wherein said MeAPO is MeAPO-5.  
     
     
         9 . The method of  claim 1  wherein said template is selected from the group consisting of di-n-propylamine (Pr 2 NH), tetra-n-butylammonium hydroxide (TBAOH) and Pr 2 NH, diisopropylamine (i-Pr 2 NH), di-npropylamine, n-butylethylamine, di-n-butylamine, and di-n-pentylamine.  
     
     
         10 . The method of  claim 9  wherein said MeAPO is MeAPO-11.  
     
     
         11 . The method of  claim 1  wherein said template is selected from the group consisting of tetraethylammonium hydroxide, di-isopropylethylamine and combinations thereof.  
     
     
         12 . The method of  claim 11  wherein said MeAPO is MeAPO-18.  
     
     
         13 . The method of  claim 1  wherein said template is selected from the group consisting of tetramethylammonium-hydroxide pentahydrate (TMAOH.5H 2 O), tetraethylammonium hdyroxide, and pyrrolidine.  
     
     
         14 . The method of  claim 13  wherein said MeAPO is MeAPO-20.  
     
     
         15 . The method of  claim 1  wherein said template is di-n-propylamine and said MeAPO is MeAPO-31.  
     
     
         16 . The method of  claim 1  wherein said template is selected from the group consisting of tetraethyl ammonium salts, cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine, cyclohexylamine, triethyl hydroxyethylamine, morpholine, dipropylamine (DPA), pyridine, isopropylamine and combinations thereof.  
     
     
         17 . The method of  claim 16  wherein said MeAPO is MeAPO-34.  
     
     
         18 . The method of  claim 1  wherein said template is selected from the group consisting of tetramethylammonium hydroxide and tetrapropylammonium hydroxide.  
     
     
         19 . The method of  claim 18  wherein said MeAPO is MeAPO-37.  
     
     
         20 . The method of  claim 1  wherein said template is selected from the group consisting of tetrabutylammonium hydroxide, diethylamine and dipropylamine.  
     
     
         21 . The method of  claim 20  wherein said MeAPO is MeAPO-41  
     
     
         22 . The method of  claim 1  wherein said template is selected from the group consisting of tetramethylammonium hydroxide pentahydrate (TMAOH.5H 2 O) and tetraethylammonium hydroxide.  
     
     
         23 . The method of  claim 22  wherein said MeAPO is MeAPO-42.  
     
     
         24 . The method of  claim 1  wherein said template is cyclohexylamine and said MeAPO is MeAPO-44.  
     
     
         25 . The method of  claim 1  further including the step of providing a morphology modifying agent to said synthesis mixture.  
     
     
         26 . The method of  claim 25  wherein said morphology modifying agent is selected from the group consisting of a surfactant, divalent cations of alkali earth metals, divalent cations of transition metals, trivalent cations, seeds of molecular sieves, and recycled synthesis mixture.  
     
     
         27 . The method of  claim 26  wherein said morphology modifying agent is one or more surfactants selected from the group consisting of: long chain alkylamines, such as hexadecylamine, tetradecylamine, dodecylamine, decylamine, or octylamine; dimethyl alkylamine compounds, such as dimethylhexadecylammine or dimethyloctylamine; and trimethylalkylammonium salts, such as trimethylhexadecylammounium chloride.  
     
     
         28 . The method of  claim 1  wherein said water soluble organic solvent is selected from the group consisting of sulfoxides and C 1  to C 5  oxygenated hydrocarbons.  
     
     
         29 . The method of  claim 28  wherein said water soluble organic solvent is an oxygenated hydrocarbon selected from the group consisting of alcohols, ketones, aldehydes, diols, and acids.  
     
     
         30 . The method of  claim 29  wherein said water soluble organic solvent is an alcohol.  
     
     
         31 . The method of  claim 2  wherein said MeAPO molecular sieve is a SAPO molecular sieve.  
     
     
         32 . The method of  claim 31  where said SAPO is selected from the group consisting of SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-37, SAPO40, SAPO41, SAPO42, SAPO44, and SAPO-47.  
     
     
         33 . The method of  claim 32  wherein said SAPO is SAPO-34.  
     
     
         34 . The method of  claim 31  wherein said source of said metal is selected from the group consisting of tetraalkylorthosilicates, colloidal silica, fumed silica, and silica sols.  
     
     
         35 . The method of  claim 34  wherein said source of said metal is TEOS.  
     
     
         36 . An isocrystalline spheroidal particle comprising a SAPO molecular sieve.  
     
     
         37 . The particle of  claim 36  wherein said particle measures from 0.5 micron to 30 microns in diameter.  
     
     
         38 . The particle of  claim 37  further including crystallites measuring from 0.05 micron to 2.5 microns at their largest dimension.  
     
     
         39 . The particle of  claim 36  made by the process of  claim 1 .  
     
     
         40 . The particle of  claim 36  wherein said SAPO is SAPO-34.  
     
     
         41 . The particle of  claim 40  wherein said particle measures from 0.5 micron to 30 microns in diameter.  
     
     
         42 . The particle of  claim 41  further including crystallites measuring from 0.05 micron to 2.5 microns at their largest dimension.  
     
     
         43 . The particle of  claim 42  made by the process of  claim 1 .  
     
     
         44 . The particle of  claim 36  wherein said SAPO is selected from the group consisting of SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-37, SAPO-40, SAPO41, SAPO42, SAPO44 and SAPO47.