# US 8,540,956 B2 · Method for preparing titanium-silicalite molecular sieve and method for preparing cyclohexanone oxime using titanium-silicalite molecular sieve > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,540,956 B2 - Document ID: US8540956B2 - Status: Granted - Kind: B2 - Application number: 12/748,932 - Filed: 2010-03-29 - Published: 2011-06-16 - Granted: 2013-09-24 - Earliest claimed: 2009-12-11 - Assignees: China Petrochemical Development Corporation - Applicants: Pin-To Yao; Cheng-Fa Hsieh; Shih-Yao Chao; Yang-Min Liang - Inventors: Pin-To Yao; Cheng-Fa Hsieh; Shih-Yao Chao; Yang-Min Liang - Web page: https://patentgrep.com/patent/US8540956B2 ## CPC - C01B 39/023: {Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48} - B01J 29/405: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead} - C01B 37/005: {Silicates, i.e. so-called metallosilicalites or metallozeosilites} - C01B 39/04: using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract The present invention provides a method for preparing large particles of titanium-silicalite molecular sieves. The method of the present invention includes the steps of preparing a dispersion solution of a primary crystalline molecular sieve; forming an aggregated particle solution by adding a flocculating agent and a coagulating agent into the dispersion solution; mixing the aggregated particle solution with a synthesis gel to form a mixture; and heat-treating the mixture. The average diameter of the titanium-silicalite molecular sieves in the present invention is more than 5 μm. In the preparation of cyclohexanone oxime using the molecular sieve of the present invention as the catalyst, the selectivity and conversion rate of cyclohexanone oxime are high, the usage of hydrogen peroxide is enhanced, and the catalyst is easy to be recovered. ## Claims ### Claim 1 A method for preparing a titanium-silicalite molecular sieve, comprising the steps of: preparing a dispersion solution of a primary crystalline molecular sieve; forming an aggregated particle solution by adding a flocculating agent and a coagulating agent into the dispersion solution; mixing the aggregated particle solution with a synthesis gel comprising a titanium source and a silicon source to form a mixture; and heat-treating the mixture. ### Claim 2 (depends on 1) The method of claim 1, wherein the primary crystalline molecular sieve is one selected from the group consisting of an uncalcined titanium-silicalite molecular sieve powder, a silicon molecular sieve powder and a combination thereof. ### Claim 3 (depends on 1) The method of claim 1, wherein the flocculating agent is one selected from the group consisting of a cationic flocculating agent, an anionic flocculating agent, an ampholytic agent and a combination thereof. ### Claim 4 (depends on 1) The method of claim 1, wherein the flocculating agent is at least one selected from the group consisting of dimethyl diallyl ammonium chloride polymers, poly(trimethylaminoethyl methacrylate) polymers, polyvinyl ammonium, polyvinyl pyridine, copolymers of sodium polyacrylate and acrylamide, copolymers of sodium acrylate and acrylamide, and copolymers of quaternary ammonium acrylate and sodium acrylate, and an average molecular weight of the flocculating agent is of more than 100,000. ### Claim 5 (depends on 1) The method of claim 1, wherein an amount of the flocculating agent used for 100 g of the synthesis gel is in a range of from 0.0001 to 0.05 g. ### Claim 6 (depends on 1) The method of claim 1, wherein the flocculating agent is a flocculating solution in a concentration ranging from 0.1 to 1 wt %. ### Claim 7 (depends on 1) The method of claim 1, wherein the coagulating agent is at least one selected from the group consisting of silicate, polyethoxysilane and a silicon dioxide gel solution, and an amount of the coagulating agent used for 100 g of the synthesis gel is in a range of from 0.1 to 6 g. ### Claim 8 (depends on 1) The method of claim 1, wherein a weight ratio of the primary crystalline molecular sieve to the synthesis gel is in a range of from 1:10 to 1:800. ### Claim 9 (depends on 1) The method of claim 1, wherein the synthesis gel is formed by the steps of: providing a titanium source in a nitrogen-sealed reactor; providing a solvent in the nitrogen-sealed reactor; dropping a silicon source in the nitrogen-sealed reactor at constant pressure; dropping a templating agent in the nitrogen-sealed reactor at constant pressure; and removing the solvent to form the synthesis gel. ### Claim 10 (depends on 9) The method of claim 9, wherein the titanium source is tetraalkyl titanate, and the silicon source is tetraalkyl silicate. ### Claim 11 (depends on 9) The method of claim 9, wherein the solvent is anhydrous isopropanol, and the templating agent is tetrapropyl ammonium hydroxide. ### Claim 12 (depends on 11) The method of claim 11, wherein a molar ratio of the anhydrous isopropanol to the silicon source is in a range of from 1:1 to 4.5:1. ### Claim 13 (depends on 9) The method of claim 9, wherein a molar ratio of the titanium source to the silicon source is in a range of from 0.005:1 to 0.06:1, and a molar ratio of the templating agent to the silicon source is in a range of from 0.1:1 to 0.5:1. ### Claim 14 (depends on 1) The method of claim 1, wherein the step of heat-treating is performed at a temperature in a range of from 100 to 220° C. for 72 to 240 hours. ### Claim 15 (depends on 1) The method of claim 1, further comprising the steps of water washing, drying and calcining after the step of heat treating. ### Claim 16 (depends on 1) The method of claim 1, wherein an average diameter of the titanium-silicalite molecular sieve is more than 5 □m.