# US 10,118,157 B2 · Preparation method, product, and application of iron-cobalt fenton-like catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,118,157 B2 - Document ID: US10118157B2 - Status: Granted - Kind: B2 - Application number: 15/031,273 - Filed: 2014-10-24 - Published: 2016-09-22 - Granted: 2018-11-06 - Earliest claimed: 2013-10-31 - Assignees: Chinese Research Academy of Environmental Sciences - Applicants: Chinese Research Academy of Environmental Sciences - Inventors: Jinyuan Jiang; Yuexi Zhou - Web page: https://patentgrep.com/patent/US10118157B2 ## CPC - B01J 23/75: Cobalt - B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)} - B01J 37/16: Reducing - C02F 1/66: by neutralisation; pH adjustment (for degassing C02F1/20; using ion-exchange C02F1/42; for flocculation or precipitation of suspended impurities C02F1/52; for removing dissolved compounds C02F1/58) - C02F 1/722: {Oxidation by peroxides} - C02F 1/725: {by catalytic oxidation} - C02F 2103/36: from the manufacture of organic compounds - C02F 2103/365: {from petrochemical industry (e.g. refineries)} - C02F 2103/38: Polymers - C02F 2305/026: Fenton's reagent - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes) ## Abstract A preparation method of an iron-cobalt fenton-like catalyst includes steps of: adopting FeCl2.4H2O and CoCl2.6H2O as reaction precursors, KBH4 as a reaction reducing agent, and polyvinyl pyrrolidone (PVP) as a surface protecting agent; preparing with a liquid phase reduction method; and after aging, suction filtration, washing, and vacuum drying, obtaining a product of the iron-cobalt fenton-like catalyst. The iron-cobalt fenton-like catalyst has a fast reaction, a relatively high treatment efficiency and a relatively wide adaptability. Moreover, an application of the iron-cobalt fenton-like catalyst in an industrial wastewater treatment is provided. ## Claims ### Claim 1 A preparation method of an iron-cobalt fenton-like catalyst, comprising steps of: respectively preparing aqueous solutions of FeCl2.4H2O and CoCl2.6H2O, wherein a molar concentration ratio of Fe2+ to Co2+ is 1:1-10:1; the FeCl2.4H2O and the CoCl7.6H2O serve as reaction precursors; adding 2-10 ml of polyvinyl pyrrolidone (PVP) having a concentration of 5 g/L, so as to obtain a first mixed solution I, wherein the PVP serves as a surface protecting agent; weighing 100 ml of deionized water, adding NaOH into the deionized water for adjusting a pH value of the deinoized water to 11.0-12.0, and then adding 1-5 g of KBH4 to prepare a second mixed solution II, wherein the KBH4 serves as a reaction reducing agent; dropping the second mixed solution II into the first mixed solution I with a reaction temperature controlled at 50±5° C., a dropping speed controlled at 15-50 r/min by a peristaltic pump, and a stirring speed controlled at 400-900 r/min by a mechanical stirrer, and then generating a black precipitate; after finishing dropping the second mixed solution II of the KBH4 and the NaOH, stirring an obtained third mixed solution for 10-40 min, and aging for 0.5-2 h; and, after suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 2 A method for treating industrial wastewater with an iron-cobalt fenton-like catalyst, comprising steps of: (1) collecting a wastewater sample to be treated, and adjusting a pH value of the wastewater sample to 2.0±0.1; (2) adding an H2O2 solution having a content of 30% into the wastewater sample, and then adding the iron-cobalt fenton-like catalyst into the wastewater sample, so as to obtain a mixed solution; (3) fully reacting the mixed solution with a stirring speed controlled at 200-400 r/min for 5-20 min, and controlling a pH value of the mixed solution at a range of 2.0±0.5 during reacting; (4) adjusting a pH value of a reacted solution to being larger than or equal to 10.0, and heating an adjusted solution in a water bath at a temperature of 50° C. for 0.5-1 h; and (5) adjusting a pH value of a heated solution to 7.0, and standing for precipitating, wherein a supernatant of a precipitated solution is a treated effluent. ### Claim 3 (depends on 2) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 2, wherein: in the step (2), a volume ratio of the wastewater sample to the H2O2 solution is 500:1-1000:1, and a mass ratio of the iron-cobalt fenton-like catalyst to the H2O2 solution is 5:1-10:1. ### Claim 4 (depends on 2) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 2, wherein: the industrial wastewater is acrylon wastewater, dye wastewater, petrochemical wastewater, phenol-acetone production wastewater, acrylonitrile butadiene styrene (ABS) synthetic resin wastewater, or acrylic acid production wastewater. ### Claim 5 (depends on 3) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 3, wherein: the industrial wastewater is acrylon wastewater, dye wastewater, petrochemical wastewater, phenol-acetone production wastewater, acrylonitrile butadiene styrene (ABS) synthetic resin wastewater, or acrylic acid production wastewater. ### Claim 6 (depends on 2) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 2, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: adopting FeCl2.4H2O and CoCl2.6H2O as reaction precursors, KBH4 as a reaction reducing agent, and polyvinyl pyrrolidone (PVP) as a surface protecting agent; preparing with a liquid phase reduction method; and after aging, suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 7 (depends on 3) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 3, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: adopting FeCl2.4H2O and CoCl2.6H2O as reaction precursors, KBH4 as a reaction reducing agent, and polyvinyl pyrrolidone (PVP) as a surface protecting agent; preparing with a liquid phase reduction method; and after aging, suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 8 (depends on 4) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 4, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: adopting FeCl2.4H2O and CoCl2.6H2O as reaction precursors, KBH4 as a reaction reducing agent, and polyvinyl pyrrolidone (PVP) as a surface protecting agent; preparing with a liquid phase reduction method; and after aging, suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 9 (depends on 5) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 5, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: adopting FeCl2.4H2O and CoCl2.6H2O as reaction precursors, KBH4 as a reaction reducing agent, and polyvinyl pyrrolidone (PVP) as a surface protecting agent; preparing with a liquid phase reduction method; and after aging, suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 10 (depends on 2) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 2, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: respectively preparing aqueous solutions of FeCl2.4H2O and CoCl2.6H2O, wherein a molar concentration ratio of Fe2+ to Co2+ is 1:1-10:1, and adding 2-10 ml of a surface protecting agent of polyvinyl pyrrolidone (PVP) having a concentration of 5 g/L, so as to obtain a first mixed solution I; weighing 100 ml of deionized water, adding NaOH into the deionized water for adjusting a pH value of the deinoized water to 11.0-12.0, and then adding 1-5 g of KBH4 to prepare a second mixed solution II; dropping the second mixed solution II into the first mixed solution I with a reaction temperature controlled at 50±5° C., a dropping speed controlled at 15-50 r/min by a peristaltic pump, and a stirring speed controlled at 400-900 r/min by a mechanical stirrer, and then generating a black precipitate; after finishing dropping the second mixed solution II of the KBH4 and the NaOH, continue stirring for 10-40 min, and aging for 0.5-2 h; and, after suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 11 (depends on 3) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 3, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: respectively preparing aqueous solutions of FeCl2.4H2O and CoCl2.6H2O, wherein a molar concentration ratio of Fe2+ to Co2+ is 1:1-10:1, and adding 2-10 ml of a surface protecting agent of polyvinyl pyrrolidone (PVP) having a concentration of 5 g/L, so as to obtain a first mixed solution I; weighing 100 ml of deionized water, adding NaOH into the deionized water for adjusting a pH value of the deinoized water to 11.0-12.0, and then adding 1-5 g of KBH4 to prepare a second mixed solution II; dropping the second mixed solution II into the first mixed solution I with a reaction temperature controlled at 50±5° C., a dropping speed controlled at 15-50 r/min by a peristaltic pump, and a stirring speed controlled at 400-900 r/min by a mechanical stirrer, and then generating a black precipitate; after finishing dropping the second mixed solution II of the KBH4 and the NaOH, continue stirring for 10-40 min, and aging for 0.5-2 h; and, after suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 12 (depends on 4) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 4, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: respectively preparing aqueous solutions of FeCl2.4H2O and CoCl2.6H2O, wherein a molar concentration ratio of Fe2+ to Co2+ is 1:1-10:1, and adding 2-10 ml of a surface protecting agent of polyvinyl pyrrolidone (PVP) having a concentration of 5 g/L, so as to obtain a first mixed solution I; weighing 100 ml of deionized water, adding NaOH into the deionized water for adjusting a pH value of the deinoized water to 11.0-12.0, and then adding 1-5 g of KBH4 to prepare a second mixed solution II; dropping the second mixed solution II into the first mixed solution I with a reaction temperature controlled at 50±5° C., a dropping speed controlled at 15-50 r/min by a peristaltic pump, and a stirring speed controlled at 400-900 r/min by a mechanical stirrer, and then generating a black precipitate; after finishing dropping the second mixed solution II of the KBH4 and the NaOH, continue stirring for 10-40 min, and aging for 0.5-2 h; and, after suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst. ### Claim 13 (depends on 5) The method for treating the industrial wastewater with the iron-cobalt fenton-like catalyst, as recited in claim 5, wherein the iron-cobalt fenton-like catalyst is prepared by following steps of: respectively preparing aqueous solutions of FeCl2.4H2O and CoCl2.6H2O, wherein a molar concentration ratio of Fe2+ to Co2+ is 1:1-10:1, and adding 2-10 ml of a surface protecting agent of polyvinyl pyrrolidone (PVP) having a concentration of 5 g/L, so as to obtain a first mixed solution I; weighing 100 ml of deionized water, adding NaOH into the deionized water for adjusting a pH value of the deinoized water to 11.0-12.0, and then adding 1-5 g of KBH4 to prepare a second mixed solution II; dropping the second mixed solution II into the first mixed solution I with a reaction temperature controlled at 50±5° C., a dropping speed controlled at 15-50 r/min by a peristaltic pump, and a stirring speed controlled at 400-900 r/min by a mechanical stirrer, and then generating a black precipitate; after finishing dropping the second mixed solution II of the KBH4 and the NaOH, continue stirring for 10-40 min, and aging for 0.5-2 h; and, after suction filtration, washing, and vacuum drying, obtaining the iron-cobalt fenton-like catalyst.