# US 10,500,568 B2 · Core-shell structure supported tungsten composite catalyst and preparation method and use thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,500,568 B2 - Document ID: US10500568B2 - Status: Granted - Kind: B2 - Application number: 15/848,821 - Filed: 2017-12-20 - Published: 2019-01-10 - Granted: 2019-12-10 - Earliest claimed: 2017-07-05 - Assignees: Hangzhou Normal University; Zhejiang Benli Technology Co., Ltd. - Applicants: Hangzhou Normal University; Zhejiang Benli Technology Co., Ltd. - Inventors: Pengfei Zhang; Chao Shen; Xiaoling Li; Jun Xu; Haining Gu - Web page: https://patentgrep.com/patent/US10500568B2 ## CPC - B01J 23/888: Tungsten - B01J 35/33: Electric or magnetic properties - B01J 35/397: {Egg shell like} - C07D 215/56: with oxygen atoms in position 4 - B01J 37/342: {of electric, magnetic or electromagnetic fields, e.g. for magnetic separation} - B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts - B01J 2523/41: Silicon - B01J 2523/69: Tungsten - B01J 2523/842: Iron - Y02P 20/584: Recycling of catalysts - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The present invention discloses a core-shell structure supported tungsten composite catalyst and a preparation method and use thereof. Most of the existing synthesis methods of the main ring of quinolone drugs have the defects of many synthesis steps, cumbersome operation, large amount of three wastes, higher costs and the like. The present invention prepares a magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, by preparing Fe3O4 colloid and SiO2/Fe3O4 composite nano-particles. This magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, is used to catalyze and synthesize quinolone compounds. The present invention provides an efficient preparation method of quinolone compounds using a catalyst which can be recovered by magnetic separation and recycled. The catalyst prepared by the present invention can be reused in the preparation of quinolone compounds and still retains the original activity without deactivation, which not only greatly improves the production efficiency, but also reduces the environmental pollution. ## Claims ### Claim 1 A preparation method of a core-shell structure supported tungsten composite catalyst, comprising the steps of: step 1), adding a reducing agent and a base into an aqueous solution of iron compound, heating to 50-80° C. and stirring to obtain Fe3O4 colloid; step 2), adding the Fe3O4 colloid obtained in the step 1), tetraethyl orthosilicate and a hydrolysis catalyst into an appropriate amount of dispersion solvent and allowing to react for 4-8 hours to obtain SiO2/Fe3O4 composite nano-particles; and step 3), adding the SiO2/Fe3O4 composite nano-particles obtained in step 2) into an aqueous solution of ammonium metatungstate, stirring for 8-14 hours and drying at 90-150° C. to obtain a first solid, which is calcined at 450-650° C. for 1-6 hours to obtain a magnetic separable core-shell structure supported tungsten composite catalyst, WO3/SiO2/Fe3O4; wherein the molar ratio of the iron compound: tetraethyl orthosilicate:ammonium metatungstate=1:1-10:0.1-1; and wherein the iron compound is FeCl3, FeCl3.6H2O or ferric triacetylacetonate; the reducing agent is Na2SO3, ascorbic acid or hydrazine hydrate; and the base is aqueous ammonia, sodium hydroxide or sodium acetate. ### Claim 2 (depends on 1) The preparation method according to claim 1, wherein the iron compound is FeCl3. ### Claim 3 (depends on 1) The preparation method according to claim 1, wherein the reducing agent is Na2SO3. ### Claim 4 (depends on 1) The preparation method according to claim 1, wherein the base is aqueous ammonia. ### Claim 5 (depends on 1) The preparation method according to claim 1, wherein in step 1), after heating, polyvinylpyrrolidone is added as a surfactant, the mixture is stirred continuously, then centrifuged and washed with water, and finally dispersed, and water is then removed to obtain Fe3O4 colloid. ### Claim 6 (depends on 1) The preparation method according to claim 1, wherein in step 2), the dispersion solvent is ethanol, and the hydrolysis catalyst is aqueous ammonia. ### Claim 7 (depends on 1) The preparation method according to claim 1, wherein in step 3), the first solid is first ground through a 120-mesh standard sieve and then calcined at 450-650° C. for 1-6 hours. ### Claim 8 (depends on 1) A magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, prepared by the preparation method of claim 1. ### Claim 9 (depends on 2) A magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, prepared by the preparation method of claim 2. ### Claim 10 (depends on 3) A magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, prepared by the preparation method of claim 3. ### Claim 11 (depends on 4) A magnetic separable core-shell supported tungsten composite catalyst, WO3/SiO2/Fe3O4, prepared by the preparation method of claim 4. ### Claim 12 (depends on 8) Use of the magnetic separable core-shell structure supported tungsten composite catalyst, WO3/SiO2/Fe3O4, of claim 8 in the synthesis of quinolone compounds, wherein the reaction steps are as follows: step 1), stirring and mixing ethyl formylacetate sodium salt, a non-polar organic solvent and the WO3/SiO2/Fe3O4 catalyst, introducing an amine compound, adding 2,4-dichloro-5-fluorobenzoyl chloride and allowing to react for 0.5-3 hours; step 2), following step 1), adding a primary amine dropwise while introducing CO2 to control the reaction pressure at 1-5 atmospheres and allowing to react for 0.5-3 hours; step 3), following step 2), adding an alkali metal hydroxide and a non-polar organic solvent, stirring and raising the temperature to 100° C. for half an hour, filtering to recover the catalyst and increasing the pressure to recover the non-polar organic solvent; and step 4), following step 3), adding an appropriate amount of water, raising the temperature to 100° C., adding hydrochloric acid dropwise to adjust the power of hydrogen to control the pH range at 4.8-6.5, precipitating crystals, followed by centrifugation and drying, and obtaining quinolone compounds; wherein the non-polar organic solvent is toluene, xylene or a mixture of the former two; the amine compound is dimethylamine, diethylamine or dicyclohexylamine; the primary amine is cyclopropylamine or S-propylene glycol amine; and the alkali metal hydroxide is sodium hydroxide, lithium hydroxide or potassium hydroxide. ### Claim 13 (depends on 9) Use of the magnetic separable core-shell structure supported tungsten composite catalyst, WO3/SiO2/Fe3O4, of claim 9 in the synthesis of quinolone compounds, wherein the reaction steps are as follows: step 1), stirring and mixing ethyl formylacetate sodium salt, a non-polar organic solvent and the WO3/SiO2/Fe3O4 catalyst, introducing an amine compound, adding 2,4-dichloro-5-fluorobenzoyl chloride and allowing to react for 0.5-3 hours; step 2), following step 1), adding a primary amine dropwise while introducing CO2 to control the reaction pressure at 1-5 atmospheres and allowing to react for 0.5-3 hours; step 3), following step 2), adding an alkali metal hydroxide and a non-polar organic solvent, stirring and raising the temperature to 100° C. for half an hour, filtering to recover the catalyst and increasing the pressure to recover the non-polar organic solvent; and step 4), following step 3), adding an appropriate amount of water, raising the temperature to 100° C., adding hydrochloric acid dropwise to adjust the power of hydrogen to control the pH range at 4.8-6.5, precipitating crystals, followed by centrifugation and drying, and obtaining quinolone compounds; wherein the non-polar organic solvent is toluene, xylene or a mixture of the former two; the amine compound is dimethylamine, diethylamine or dicyclohexylamine; the primary amine is cyclopropylamine or S-propylene glycol amine; and the alkali metal hydroxide is sodium hydroxide, lithium hydroxide or potassium hydroxide. ### Claim 14 (depends on 10) Use of the magnetic separable core-shell structure supported tungsten composite catalyst, WO3/SiO2/Fe3O4, of claim 10 in the synthesis of quinolone compounds, wherein the reaction steps are as follows: step 1), stirring and mixing ethyl formylacetate sodium salt, a non-polar organic solvent and the WO3/SiO2/Fe3O4 catalyst, introducing an amine compound, adding 2,4-dichloro-5-fluorobenzoyl chloride and allowing to react for 0.5-3 hours; step 2), following step 1), adding a primary amine dropwise while introducing CO2 to control the reaction pressure at 1-5 atmospheres and allowing to react for 0.5-3 hours; step 3), following step 2), adding an alkali metal hydroxide and a non-polar organic solvent, stirring and raising the temperature to 100° C. for half an hour, filtering to recover the catalyst and increasing the pressure to recover the non-polar organic solvent; and step 4), following step 3), adding an appropriate amount of water, raising the temperature to 100° C., adding hydrochloric acid dropwise to adjust the power of hydrogen to control the pH range at 4.8-6.5, precipitating crystals, followed by centrifugation and drying, and obtaining quinolone compounds; wherein the non-polar organic solvent is toluene, xylene or a mixture of the former two; the amine compound is dimethylamine, diethylamine or dicyclohexylamine; the primary amine is cyclopropylamine or S-propylene glycol amine; and the alkali metal hydroxide is sodium hydroxide, lithium hydroxide or potassium hydroxide. ### Claim 15 (depends on 11) Use of the magnetic separable core-shell structure supported tungsten composite catalyst, WO3/SiO2/Fe3O4, of claim 11 in the synthesis of quinolone compounds, wherein the reaction steps are as follows: step 1), stirring and mixing ethyl formylacetate sodium salt, a non-polar organic solvent and the WO3/SiO2/Fe3O4 catalyst, introducing an amine compound, adding 2,4-dichloro-5-fluorobenzoyl chloride and allowing to react for 0.5-3 hours; step 2), following step 1), adding a primary amine dropwise while introducing CO2 to control the reaction pressure at 1-5 atmospheres and allowing to react for 0.5-3 hours; step 3), following step 2), adding an alkali metal hydroxide and a non-polar organic solvent, stirring and raising the temperature to 100° C. for half an hour, filtering to recover the catalyst and increasing the pressure to recover the non-polar organic solvent; and step 4), following step 3), adding an appropriate amount of water, raising the temperature to 100° C., adding hydrochloric acid dropwise to adjust the power of hydrogen to control the pH range at 4.8-6.5, precipitating crystals, followed by centrifugation and drying, and obtaining quinolone compounds; wherein the non-polar organic solvent is toluene, xylene or a mixture of the former two; the amine compound is dimethylamine, diethylamine or dicyclohexylamine; the primary amine is cyclopropylamine or S-propylene glycol amine; and the alkali metal hydroxide is sodium hydroxide, lithium hydroxide or potassium hydroxide. ### Claim 16 (depends on 12) The use according to claim 12, wherein the non-polar organic solvent is toluene, the amine compound is dimethylamine, the primary amine is cyclopropylamine, and the alkali metal hydroxide is sodium hydroxide. ### Claim 17 (depends on 13) The use according to claim 13, wherein the non-polar organic solvent is toluene, the amine compound is dimethylamine, the primary amine is cyclopropylamine, and the alkali metal hydroxide is sodium hydroxide. ### Claim 18 (depends on 14) The use according to claim 14, wherein the non-polar organic solvent is toluene, the amine compound is dimethylamine, the primary amine is cyclopropylamine, and the alkali metal hydroxide is sodium hydroxide. ### Claim 19 (depends on 15) The use according to claim 15, wherein the non-polar organic solvent is toluene, the amine compound is dimethylamine, the primary amine is cyclopropylamine, and the alkali metal hydroxide is sodium hydroxide.