技术领域technical field
本发明涉及一种去除水中内分泌干扰物的方法。The invention relates to a method for removing endocrine disruptors in water.
背景技术Background technique
近年来，由于水源水质的严重恶化，大量有毒有害污染物在水中不断被检出，持久性有机污染物、三致物、内分泌干扰物等，在众多的有机污染物中，内分泌干扰物以其危害表现不同而作为一个独立的环境问题被提出，此类污染物在水的循环和利用过程中会产生生物放大效应，常规水处理工艺对其处理能力十分有限，很难达到国家制定的饮用水标准。而且随着工业和农业的发展，含有大量内分泌干扰物的废水排放量逐年增加，种类逐年增多，未经妥善处理而排入水中造成了更为严重的污染，因此对此类工业废水必须进行处理。In recent years, due to the serious deterioration of water quality, a large number of toxic and harmful pollutants have been continuously detected in water, persistent organic pollutants, three-cause substances, endocrine disruptors, etc. Among many organic pollutants, endocrine disruptors are the most important The hazard performance is different and it is proposed as an independent environmental problem. Such pollutants will produce biomagnification effects in the process of water circulation and utilization. The conventional water treatment process is very limited in its treatment capacity, and it is difficult to meet the national drinking water requirements. standard. Moreover, with the development of industry and agriculture, the discharge of wastewater containing a large amount of endocrine disruptors is increasing year by year, and the types are increasing year by year. If it is discharged into the water without proper treatment, it will cause more serious pollution. Therefore, this type of industrial wastewater must be treated. .
目前国内外去除水环境中的EDCs常用的方法包括生物法、物化法、电化学法及薄膜过滤法。由于EDCs对生物的毒性作用，使得未经特殊驯化的微生物对其去除作用十分有限；电化学法对该类物质的去除较为高效，但由于成本较高也难以大规模使用；膜技术作为21世纪最有前景的水处理技术，虽被广泛应用于饮用水处理，然而较高的膜组件设备和运行成本使其难以在大规模去除特定有机污染物中使用；物化法中的氧化和吸附，由于操作简单，去除效率高、成本可控而在饮用水处理中得到了广泛应用，然而单独氧化工艺或吸附工艺存在的成本较高，副产物较多，吸附剂难回收等问题，使其在应用研究中仍具有一定局限性。At present, the commonly used methods to remove EDCs in water environment at home and abroad include biological method, physicochemical method, electrochemical method and membrane filtration method. Due to the toxic effect of EDCs on organisms, the removal of microorganisms without special domestication is very limited; the removal of such substances by electrochemical methods is more efficient, but it is difficult to be used on a large scale due to high costs; Although the most promising water treatment technology is widely used in drinking water treatment, the high membrane module equipment and operating costs make it difficult to use it in large-scale removal of specific organic pollutants; oxidation and adsorption in physicochemical methods are due to The operation is simple, the removal efficiency is high, and the cost is controllable, so it has been widely used in drinking water treatment. However, the cost of a single oxidation process or adsorption process is high, there are many by-products, and the adsorbent is difficult to recover. There are still some limitations in the research.
发明内容Contents of the invention
本发明的目的是要解决现有去除水中内分泌干扰物的方法去除效果不佳，成本高和副产物多的问题，而提供一种利用金属铈协同磁性氧化还原石墨烯催化激活过硫酸盐去除水中内分泌干扰物的方法。The purpose of the present invention is to solve the problems of poor removal effect, high cost and many by-products of the existing methods for removing endocrine disruptors in water, and to provide a method for using metal cerium to cooperate with magnetic redox graphene to catalyze and activate persulfate to remove water Approaches to endocrine disruptors.
一种利用金属铈协同磁性氧化还原石墨烯催化激活过硫酸盐去除水中内分泌干扰物的方法，是按以下步骤完成的：A method for utilizing metal cerium to cooperate with magnetic redox graphene to catalyze and activate persulfate to remove endocrine disruptors in water is completed according to the following steps:
一、将过硫酸盐与预处理的水混合：将过硫酸盐与预处理的水混合，再在室温下和搅拌速度为160r/min～250r/min的条件下搅拌20min～45min，得到过硫酸盐和预处理的水的混合溶液；1. Mix persulfate with pretreated water: mix persulfate with pretreated water, then stir for 20min to 45min at room temperature and at a stirring speed of 160r/min to 250r/min to obtain persulfuric acid Mixed solution of salt and pretreated water;
步骤一中所述的过硫酸盐为过硫酸钾、过硫酸铵、过硫酸钠和过硫酸钙中的一种或其中几种的混合物；The persulfate described in step 1 is one or a mixture of several of them in potassium persulfate, ammonium persulfate, sodium persulfate and calcium persulfate;
步骤一中所述的预处理的水中内分泌干扰物的浓度为0.02mg/L～100mg/L；The concentration of endocrine disruptors in the pretreated water described in step 1 is 0.02 mg/L-100 mg/L;
步骤一中所述的过硫酸盐的质量与预处理的水的质量比为1:(1000～10000)；The mass ratio of the quality of persulfate described in step 1 and the pretreated water is 1:(1000～10000);
二、调节反应pH值：在搅拌速度为150r/min～200r/min的条件下使用0.1mol/L～100mol/L的高氯酸和0.1mol/L～100mol/L的氢氧化钠溶液将过硫酸盐和预处理的水的混合溶液的pH值调节至6.5～7.5，得到调节pH值后的过硫酸盐和预处理的水的混合溶液；2. Adjust the pH value of the reaction: use 0.1mol/L～100mol/L perchloric acid and 0.1mol/L～100mol/L sodium hydroxide solution under the condition that the stirring speed is 150r/min～200r/min. The pH value of the mixed solution of sulfate and pretreated water is adjusted to 6.5 to 7.5 to obtain a mixed solution of persulfate and pretreated water after the pH value has been adjusted;
三、制备金属铈/磁性氧化还原石墨烯复合材料：3. Preparation of metallic cerium/magnetic redox graphene composites:
①、将氧化石墨烯加入到质量分数为97％～99％的乙二醇溶液中，再使用超声波震荡仪震荡分散3h～4h，得到氧化石墨烯和乙二醇的混合溶液；①. Add graphene oxide to the ethylene glycol solution with a mass fraction of 97% to 99%, and then use an ultrasonic oscillator to oscillate and disperse for 3h to 4h to obtain a mixed solution of graphene oxide and ethylene glycol;
步骤三①中所述的氧化石墨烯的质量与质量分数为97％～99％的乙二醇溶液的体积比为(0.001g～10g):1mL；The mass of the graphene oxide described in step 3. and the mass fraction are 97%～99% The volume ratio of the ethylene glycol solution is (0.001g～10g): 1mL;
②、将柠檬酸钠和乙二醇的混合溶液在温度为60℃～75℃下加热20min～45min，得到加热后的柠檬酸钠和乙二醇的混合溶液；再向加热后的柠檬酸钠和乙二醇的混合溶液中加入FeCl3·6H2O、尿素和CeCl2·6H2O，再在室温和磁力搅拌速度为100r/min～250r/min的条件下磁力搅拌2h～4h，得到含有铁铈的柠檬酸钠和乙二醇的混合溶液；②. Heat the mixed solution of sodium citrate and ethylene glycol at a temperature of 60°C to 75°C for 20min to 45min to obtain a mixed solution of heated sodium citrate and ethylene glycol; then add the heated sodium citrate FeCl3 6H2 O, urea and CeCl2 6H2 O are added to the mixed solution of ethylene glycol, and then magnetically stirred at room temperature and at a magnetic stirring speed of 100r/min to 250r/min for 2h to 4h to obtain A mixed solution of sodium citrate and ethylene glycol containing ferric cerium;
步骤三②中所述的柠檬酸钠和乙二醇的混合溶液中柠檬酸钠的浓度为60mg/mL～200mg/mL；The concentration of sodium citrate in the mixed solution of sodium citrate and ethylene glycol described in step 3.2 is 60mg/mL～200mg/mL;
步骤三②中所述的加热后的柠檬酸钠和乙二醇的混合溶液的体积与FeCl3·6H2O的质量比为(1mL～1000mL):1g；The mass ratio of the volume of the heated mixed solution of sodium citrate and ethylene glycol to FeCl3 .6H2 O in step 3 ② is (1mL-1000mL): 1g;
步骤三②中所述的FeCl3·6H2O与尿素的质量比为(0.01～100):1；The mass ratio of FeCl3 ·6H2 O to urea described in Step 3 ② is (0.01-100):1;
步骤三②中所述的FeCl3·6H2O与CeCl2·6H2O的质量比为(0.01～1000):1；The mass ratio of FeCl3 6H2 O to CeCl2 6H2 O described in Step 3 ② is (0.01-1000):1;
③、将氧化石墨烯和乙二醇的混合溶液与含有铁铈的柠檬酸钠和乙二醇的混合溶液混合，再加入到内衬为聚四氟乙烯的不锈钢高压反应釜中，再将不锈钢高压反应釜密封，再将密封的不锈钢高压反应釜在温度为200℃～230℃下反应12h～48h，再自然冷却至室温，得到黑色悬浊液；③. Mix the mixed solution of graphene oxide and ethylene glycol with the mixed solution of sodium citrate containing iron cerium and ethylene glycol, and then add it to a stainless steel autoclave lined with polytetrafluoroethylene, and then put the stainless steel The autoclave is sealed, and the sealed stainless steel autoclave is reacted at a temperature of 200°C to 230°C for 12h to 48h, and then naturally cooled to room temperature to obtain a black suspension;
步骤三③中所述的氧化石墨烯和乙二醇的混合溶液与含有铁铈的柠檬酸钠和乙二醇的混合溶液的体积比为(0.1～50):1；The volume ratio of the mixed solution of graphene oxide and ethylene glycol described in step 3. and the mixed solution of sodium citrate containing iron cerium and ethylene glycol is (0.1～50):1;
④、将黑色悬浊液在离心速度为6500r/min～8000r/min下进行离心分离10min～30min，得到离心分离后的沉淀物质；分别使用甲醇和去离子水清洗离心分离后的沉淀物质5次～10次，再在温度为-18℃～15℃下干燥24h～48h，得到金属铈/磁性氧化还原石墨烯复合材料；④. Centrifuge the black suspension at a centrifugal speed of 6500r/min to 8000r/min for 10min to 30min to obtain the precipitated substance after centrifugation; wash the precipitated substance after centrifugation with methanol and deionized water for 5 times respectively ~10 times, and then dried at a temperature of -18°C to 15°C for 24h to 48h to obtain a metal cerium/magnetic redox graphene composite material;
四、投加金属铈/磁性氧化还原石墨烯复合材料：将金属铈/磁性氧化还原石墨烯复合材料加入到调节pH值后的过硫酸盐和预处理的水的混合溶液中，反应时间为15min～240min，得到含有金属铈/磁性氧化还原石墨烯复合材料的水；4. Add metal cerium/magnetic redox graphene composite material: add metal cerium/magnetic redox graphene composite material to the mixed solution of persulfate and pretreated water after adjusting the pH value, and the reaction time is 15min ~240min to obtain water containing metal cerium/magnetic redox graphene composite material;
步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为1mg/L～200mg/L；The dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 1mg/L～200mg/L;
五、采用外磁场分离金属铈/磁性氧化还原石墨烯复合材料：采用外磁场对含有金属铈/磁性氧化还原石墨烯复合材料的水进行分离，回收金属铈/磁性氧化还原石墨烯复合材料，再使用孔径为0.45μm的玻璃纤维膜对回收的金属铈/磁性氧化还原石墨烯复合材料进行过滤，再将过滤后的金属铈/磁性氧化还原石墨烯复合材料在温度为50℃～75℃下干燥12h～48h，得到再生后的金属铈/磁性氧化还原石墨烯复合材料和去除水中内分泌干扰物的水。5. Use external magnetic field to separate metal cerium/magnetic redox graphene composite material: use external magnetic field to separate water containing metal cerium/magnetic redox graphene composite material, recycle metal cerium/magnetic redox graphene composite material, and then Use a glass fiber membrane with a pore size of 0.45 μm to filter the recovered metal cerium/magnetic redox graphene composite, and then dry the filtered metal cerium/magnetic redox graphene composite at a temperature of 50°C to 75°C After 12h to 48h, the regenerated metal cerium/magnetic redox graphene composite material and water from which endocrine disruptors have been removed are obtained.
本发明的原理：Principle of the present invention:
本发明中在氧化石墨烯表面存在的活泼金属铁和铈将与过硫酸盐中的过硫键发生电子转移，破坏过硫双键的结构，从而发生激活反应，生成·SO4-，而活泼金属金属铁和铈自身则得到氧化；另一方面氧化石墨烯具有巨大的比表面积，其能够吸附目标有机物的同时，表面大量有氧官能团，如羧基所具有的多电子基团会进一步激活过硫酸盐，生成·SO4-与HSO4-，从而加速水中内分泌干扰物的氧化降解。In the present invention, the active metal iron and cerium existing on the surface of graphene oxide will undergo electron transfer with the persulfur bond in the persulfate, destroying the structure of the persulfur double bond, thereby causing an activation reaction to generate SO4- , and the active Metal iron and cerium are oxidized by themselves; on the other hand, graphene oxide has a huge specific surface area, which can adsorb target organic matter, and at the same time, a large number of oxygen functional groups on the surface, such as carboxyl groups with many electrons, will further activate persulfate. salt to generate ·SO4- and HSO4- , thus accelerating the oxidative degradation of endocrine disruptors in water.
本发明的优点：Advantages of the present invention:
一、本发明方法操作简单，成本低廉，与其他去除水中内分泌干扰物的方法相比，降低了成本40％～60％；1. The method of the present invention is simple in operation and low in cost. Compared with other methods for removing endocrine disruptors in water, the cost is reduced by 40% to 60%;
二、本发明具有较低的挥发性，反应前后色度和嗅味不会发生变化，制备的金属铈/磁性氧化还原石墨烯复合材料在常温常压下能够稳定存在；2. The present invention has lower volatility, and the chromaticity and smell will not change before and after the reaction, and the prepared metal cerium/magnetic redox graphene composite material can exist stably at normal temperature and pressure;
三、本发明所合成的金属铈/磁性氧化还原石墨烯复合材料反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The metal cerium/magnetic redox graphene composite material synthesized by the present invention has a fast reaction speed, non-toxic by-products, and can effectively remove endocrine disruptors in water;
四、本发明所合成的金属铈/磁性氧化还原石墨烯复合材料能够较容易回收及再生；Four, the synthesized metal cerium/magnetic redox graphene composite material of the present invention can be recycled and regenerated more easily;
五、使用本发明的方法去除水中内分泌干扰物的去除率可达89％～95％。5. The removal rate of endocrine disruptors in water by using the method of the present invention can reach 89%-95%.
本发明可以去除水中残余内分泌干扰物。The invention can remove residual endocrine disruptors in water.
具体实施方式detailed description
具体实施方式一：本实施方式是一种利用金属铈协同磁性氧化还原石墨烯催化激活过硫酸盐去除水中内分泌干扰物的方法是按以下步骤完成的：Embodiment 1: This embodiment is a method of utilizing metal cerium to cooperate with magnetic redox graphene to catalyze and activate persulfate to remove endocrine disruptors in water, which is completed in the following steps:
一、将过硫酸盐与预处理的水混合：将过硫酸盐与预处理的水混合，再在室温下和搅拌速度为160r/min～250r/min的条件下搅拌20min～45min，得到过硫酸盐和预处理的水的混合溶液；1. Mix persulfate with pretreated water: mix persulfate with pretreated water, then stir for 20min to 45min at room temperature and at a stirring speed of 160r/min to 250r/min to obtain persulfuric acid Mixed solution of salt and pretreated water;
步骤一中所述的过硫酸盐为过硫酸钾、过硫酸铵、过硫酸钠和过硫酸钙中的一种或其中几种的混合物；The persulfate described in step 1 is one or a mixture of several of them in potassium persulfate, ammonium persulfate, sodium persulfate and calcium persulfate;
步骤一中所述的预处理的水中内分泌干扰物的浓度为0.02mg/L～100mg/L；The concentration of endocrine disruptors in the pretreated water described in step 1 is 0.02 mg/L-100 mg/L;
步骤一中所述的过硫酸盐的质量与预处理的水的质量比为1:(1000～10000)；The mass ratio of the quality of persulfate described in step 1 and the pretreated water is 1:(1000～10000);
二、调节反应pH值：在搅拌速度为150r/min～200r/min的条件下使用0.1mol/L～100mol/L的高氯酸和0.1mol/L～100mol/L的氢氧化钠溶液将过硫酸盐和预处理的水的混合溶液的pH值调节至6.5～7.5，得到调节pH值后的过硫酸盐和预处理的水的混合溶液；2. Adjust the pH value of the reaction: use 0.1mol/L～100mol/L perchloric acid and 0.1mol/L～100mol/L sodium hydroxide solution under the condition that the stirring speed is 150r/min～200r/min. The pH value of the mixed solution of sulfate and pretreated water is adjusted to 6.5 to 7.5 to obtain a mixed solution of persulfate and pretreated water after the pH value has been adjusted;
三、制备金属铈/磁性氧化还原石墨烯复合材料：3. Preparation of metallic cerium/magnetic redox graphene composites:
①、将氧化石墨烯加入到质量分数为97％～99％的乙二醇溶液中，再使用超声波震荡仪震荡分散3h～4h，得到氧化石墨烯和乙二醇的混合溶液；①. Add graphene oxide to the ethylene glycol solution with a mass fraction of 97% to 99%, and then use an ultrasonic oscillator to oscillate and disperse for 3h to 4h to obtain a mixed solution of graphene oxide and ethylene glycol;
步骤三①中所述的氧化石墨烯的质量与质量分数为97％～99％的乙二醇溶液的体积比为(0.001g～10g):1mL；The mass of the graphene oxide described in step 3. and the mass fraction are 97%～99% The volume ratio of the ethylene glycol solution is (0.001g～10g): 1mL;
②、将柠檬酸钠和乙二醇的混合溶液在温度为60℃～75℃下加热20min～45min，得到加热后的柠檬酸钠和乙二醇的混合溶液；再向加热后的柠檬酸钠和乙二醇的混合溶液中加入FeCl3·6H2O、尿素和CeCl2·6H2O，再在室温和磁力搅拌速度为100r/min～250r/min的条件下磁力搅拌2h～4h，得到含有铁铈的柠檬酸钠和乙二醇的混合溶液；②. Heat the mixed solution of sodium citrate and ethylene glycol at a temperature of 60°C to 75°C for 20min to 45min to obtain a mixed solution of heated sodium citrate and ethylene glycol; then add the heated sodium citrate FeCl3 6H2 O, urea and CeCl2 6H2 O are added to the mixed solution of ethylene glycol, and then magnetically stirred at room temperature and at a magnetic stirring speed of 100r/min to 250r/min for 2h to 4h to obtain A mixed solution of sodium citrate and ethylene glycol containing ferric cerium;
步骤三②中所述的柠檬酸钠和乙二醇的混合溶液中柠檬酸钠的浓度为60mg/mL～200mg/mL；The concentration of sodium citrate in the mixed solution of sodium citrate and ethylene glycol described in step 3.2 is 60mg/mL～200mg/mL;
步骤三②中所述的加热后的柠檬酸钠和乙二醇的混合溶液的体积与FeCl3·6H2O的质量比为(1mL～1000mL):1g；The mass ratio of the volume of the heated mixed solution of sodium citrate and ethylene glycol to FeCl3 .6H2 O in step 3 ② is (1mL-1000mL): 1g;
步骤三②中所述的FeCl3·6H2O与尿素的质量比为(0.01～100):1；The mass ratio of FeCl3 ·6H2 O to urea described in Step 3 ② is (0.01-100):1;
步骤三②中所述的FeCl3·6H2O与CeCl2·6H2O的质量比为(0.01～1000):1；The mass ratio of FeCl3 6H2 O to CeCl2 6H2 O described in Step 3 ② is (0.01-1000):1;
③、将氧化石墨烯和乙二醇的混合溶液与含有铁铈的柠檬酸钠和乙二醇的混合溶液混合，再加入到内衬为聚四氟乙烯的不锈钢高压反应釜中，再将不锈钢高压反应釜密封，再将密封的不锈钢高压反应釜在温度为200℃～230℃下反应12h～48h，再自然冷却至室温，得到黑色悬浊液；③. Mix the mixed solution of graphene oxide and ethylene glycol with the mixed solution of sodium citrate containing iron cerium and ethylene glycol, and then add it to a stainless steel autoclave lined with polytetrafluoroethylene, and then put the stainless steel The autoclave is sealed, and the sealed stainless steel autoclave is reacted at a temperature of 200°C to 230°C for 12h to 48h, and then naturally cooled to room temperature to obtain a black suspension;
步骤三③中所述的氧化石墨烯和乙二醇的混合溶液与含有铁铈的柠檬酸钠和乙二醇的混合溶液的体积比为(0.1～50):1；The volume ratio of the mixed solution of graphene oxide and ethylene glycol described in step 3. and the mixed solution of sodium citrate containing iron cerium and ethylene glycol is (0.1～50):1;
④、将黑色悬浊液在离心速度为6500r/min～8000r/min下进行离心分离10min～30min，得到离心分离后的沉淀物质；分别使用甲醇和去离子水清洗离心分离后的沉淀物质5次～10次，再在温度为-18℃～15℃下干燥24h～48h，得到金属铈/磁性氧化还原石墨烯复合材料；④. Centrifuge the black suspension at a centrifugal speed of 6500r/min to 8000r/min for 10min to 30min to obtain the precipitated substance after centrifugation; wash the precipitated substance after centrifugation with methanol and deionized water for 5 times respectively ~10 times, and then dried at a temperature of -18°C to 15°C for 24h to 48h to obtain a metal cerium/magnetic redox graphene composite material;
四、投加金属铈/磁性氧化还原石墨烯复合材料：将金属铈/磁性氧化还原石墨烯复合材料加入到调节pH值后的过硫酸盐和预处理的水的混合溶液中，反应时间为15min～240min，得到含有金属铈/磁性氧化还原石墨烯复合材料的水；4. Add metal cerium/magnetic redox graphene composite material: add metal cerium/magnetic redox graphene composite material to the mixed solution of persulfate and pretreated water after adjusting the pH value, and the reaction time is 15min ~240min to obtain water containing metal cerium/magnetic redox graphene composite material;
步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为1mg/L～200mg/L；The dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 1mg/L～200mg/L;
五、采用外磁场分离金属铈/磁性氧化还原石墨烯复合材料：采用外磁场对含有金属铈/磁性氧化还原石墨烯复合材料的水进行分离，回收金属铈/磁性氧化还原石墨烯复合材料，再使用孔径为0.45μm的玻璃纤维膜对回收的金属铈/磁性氧化还原石墨烯复合材料进行过滤，再将过滤后的金属铈/磁性氧化还原石墨烯复合材料在温度为50℃～75℃下干燥12h～48h，得到再生后的金属铈/磁性氧化还原石墨烯复合材料和去除水中内分泌干扰物的水。5. Use external magnetic field to separate metal cerium/magnetic redox graphene composite material: use external magnetic field to separate water containing metal cerium/magnetic redox graphene composite material, recycle metal cerium/magnetic redox graphene composite material, and then Use a glass fiber membrane with a pore size of 0.45 μm to filter the recovered metal cerium/magnetic redox graphene composite, and then dry the filtered metal cerium/magnetic redox graphene composite at a temperature of 50°C to 75°C After 12h to 48h, the regenerated metal cerium/magnetic redox graphene composite material and water from which endocrine disruptors have been removed are obtained.
本实施方式的原理：The principle of this implementation mode:
本实施方式中在氧化石墨烯表面存在的活泼金属铁和铈将与过硫酸盐中的过硫键发生电子转移，破坏过硫双键的结构，从而发生激活反应，生成·SO4-，而活泼金属金属铁和铈自身则得到氧化；另一方面氧化石墨烯具有巨大的比表面积，其能够吸附目标有机物的同时，表面大量有氧官能团，如羧基所具有的多电子基团会进一步激活过硫酸盐，生成·SO4-与HSO4-，从而加速水中内分泌干扰物的氧化降解。In this embodiment, the active metal iron and cerium present on the surface of graphene oxide will transfer electrons to the persulfur bond in the persulfate, destroying the structure of the persulfur double bond, thereby causing an activation reaction to generate SO4- , and The active metals, iron and cerium, are oxidized; on the other hand, graphene oxide has a huge specific surface area, which can adsorb target organic compounds, and at the same time, a large number of oxygen functional groups on the surface, such as carboxyl groups, will further activate the super-electron groups. Sulfate generates SO4- and HSO4- , thereby accelerating the oxidative degradation of endocrine disruptors in water.
本实施方式的优点：The advantage of this implementation mode:
一、本实施方式方法操作简单，成本低廉，与其他去除水中内分泌干扰物的方法相比，降低了成本40％～60％；1. The method of this embodiment is simple to operate and low in cost, compared with other methods for removing endocrine disruptors in water, the cost is reduced by 40% to 60%;
二、本实施方式具有较低的挥发性，反应前后色度和嗅味不会发生变化，制备的金属铈/磁性氧化还原石墨烯复合材料在常温常压下能够稳定存在；Two, the present embodiment has lower volatility, and the chromaticity and smell will not change before and after the reaction, and the prepared metal cerium/magnetic redox graphene composite material can exist stably at normal temperature and pressure;
三、本实施方式所合成的金属铈/磁性氧化还原石墨烯复合材料反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The metal cerium/magnetic redox graphene composite material synthesized in this embodiment has a fast reaction speed, non-toxic by-products, and can effectively remove endocrine disruptors in water;
四、本实施方式所合成的金属铈/磁性氧化还原石墨烯复合材料能够较容易回收及再生；4. The metal cerium/magnetic redox graphene composite material synthesized by this embodiment can be recovered and regenerated more easily;
五、使用本实施方式的方法去除水中内分泌干扰物的去除率可达89％～95％。5. The removal rate of endocrine disruptors in water by using the method of this embodiment can reach 89%-95%.
本实施方式可以去除水中残余内分泌干扰物。This embodiment can remove residual endocrine disruptors in water.
具体实施方式二：本实施方式与具体实施方式一不同点是：步骤一中所述的内分泌干扰物为雌酮、17α-乙炔基雌二醇、17α-雌二醇、17β-雌二醇、雌三醇、己烯雌酚、壬基酚、双酚A和辛基酚中的一种或其中几种的混合物。其他步骤与具体实施方式一相同。Specific embodiment 2: The difference between this embodiment and specific embodiment 1 is that the endocrine disruptors described in step 1 are estrone, 17α-ethinyl estradiol, 17α-estradiol, 17β-estradiol, One or a mixture of estriol, diethylstilbestrol, nonylphenol, bisphenol A and octylphenol. Other steps are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二之一不同点是：步骤三①中所述的超声波震荡仪的功率为100W～1000W。其他步骤与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the power of the ultrasonic oscillator described in Step 3 ① is 100W-1000W. Other steps are the same as those in Embodiment 1 or 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同点是：步骤四中所述的外磁场强度为0.01T～1T。其他步骤与具体实施方式一至三相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the strength of the external magnetic field described in Step 4 is 0.01T-1T. Other steps are the same as those in Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同点是：步骤一中所述的过硫酸盐的质量与预处理的水的质量比为1:(1000～5000)。其他步骤与具体实施方式一至四相同。Embodiment 5: This embodiment differs from Embodiment 1 to Embodiment 4 in that the mass ratio of the persulfate described in step 1 to the pretreated water is 1:(1000-5000). Other steps are the same as those in Embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同点是：步骤一中所述的过硫酸盐的质量与预处理的水的质量比为1:(5000～8000)。其他步骤与具体实施方式一至五相同。Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the mass ratio of the persulfate described in step 1 to the pretreated water is 1:(5000-8000). Other steps are the same as those in Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同点是：步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为0.02mg/L～10mg/L其他步骤与具体实施方式一至六相同。Embodiment 7: The difference between this embodiment and Embodiments 1 to 6 is that the dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 0.02mg/L～10mg/L. Others The steps are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同点是：步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为10mg/L～100mg/L。其他步骤与具体实施方式一至七相同。Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that the dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 10 mg/L-100 mg/L. Other steps are the same as those in Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同点是：步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为100mg/L～200mg/L。其他步骤与具体实施方式一至八相同。Embodiment 9: The difference between this embodiment and Embodiments 1 to 8 is that the dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 100 mg/L-200 mg/L. Other steps are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同点是：步骤三①中所述的氧化石墨烯的粒径为15nm～500nm。其他步骤与具体实施方式一至九相同。Embodiment 10: This embodiment differs from Embodiments 1 to 9 in that: the particle size of the graphene oxide described in Step 3 ① is 15nm-500nm. Other steps are the same as those in Embodiments 1 to 9.
采用以下试验验证本发明的有益效果：Adopt following test to verify beneficial effect of the present invention:
试验一：一种利用金属铈协同磁性氧化还原石墨烯催化激活过硫酸盐去除水中内分泌干扰物的方法是按以下步骤完成的：Experiment 1: A method for removing endocrine disruptors in water by using metal cerium to cooperate with magnetic redox graphene to catalyze and activate persulfate is completed in the following steps:
一、将过硫酸盐与预处理的水混合：将过硫酸盐与预处理的水混合，再在室温下和搅拌速度为180r/min的条件下搅拌30min，得到过硫酸盐和预处理的水的混合溶液；1. Mix persulfate with pretreated water: mix persulfate with pretreated water, then stir for 30min at room temperature and at a stirring speed of 180r/min to obtain persulfate and pretreated water mixed solution;
步骤一中所述的过硫酸盐为过硫酸钠；The persulfate described in step 1 is sodium persulfate;
步骤一中所述的内分泌干扰物为雌三醇；The endocrine disruptor described in step 1 is estriol;
步骤一中所述的预处理的水中内分泌干扰物的浓度为5mg/L；The concentration of the endocrine disruptor in the pretreated water described in step 1 is 5mg/L;
步骤一中所述的过硫酸盐的质量与预处理的水的质量比为1:1500；The mass ratio of the quality of persulfate described in step 1 and the pretreated water is 1:1500;
二、调节反应pH值：在搅拌速度为180r/min的条件下使用0.1mol/L的高氯酸和0.1mol/L的氢氧化钠溶液将过硫酸盐和预处理的水的混合溶液的pH值调节至6.5，得到调节pH值后的过硫酸盐和预处理的水的混合溶液；Two, adjust the pH value of the reaction: use 0.1mol/L perchloric acid and 0.1mol/L sodium hydroxide solution to adjust the pH of the mixed solution of persulfate and pretreated water under the condition of 180r/min stirring speed Value is adjusted to 6.5, obtains the mixed solution of the persulfate and pretreated water after adjusting the pH value;
三、金属铈/磁性氧化还原石墨烯复合材料：3. Metal cerium/magnetic redox graphene composite material:
①、将氧化石墨烯加入到质量分数为99％的乙二醇溶液中，再使用超声波震荡仪震荡分散3h，得到氧化石墨烯和乙二醇的混合溶液；①. Add graphene oxide to the ethylene glycol solution with a mass fraction of 99%, and then use an ultrasonic oscillator to oscillate and disperse for 3 hours to obtain a mixed solution of graphene oxide and ethylene glycol;
步骤三①中所述的氧化石墨烯的粒径为25nm；The particle diameter of the graphene oxide described in step 3. 1. is 25nm;
步骤三①中所述的氧化石墨烯的质量与质量分数为99％的乙二醇溶液的体积比为0.005g:1mL；Step 3. The mass of graphene oxide described in 1. and the mass fraction are that the volume ratio of the ethylene glycol solution of 99% is 0.005g: 1mL;
步骤三①中所述的超声波震荡仪的功率为200W；The power of the ultrasonic oscillator described in step 3.1 is 200W;
②、将50mL柠檬酸钠和乙二醇的混合溶液在温度为60℃下加热20min，得到加热后的柠檬酸钠和乙二醇的混合溶液；再向加热后的柠檬酸钠和乙二醇的混合溶液中加入FeCl3·6H2O、尿素和CeCl2·6H2O，再在室温和磁力搅拌速度为200r/min的条件下磁力搅拌2h，得到含有铁铈的柠檬酸钠和乙二醇的混合溶液；②. Heat 50mL of the mixed solution of sodium citrate and ethylene glycol at a temperature of 60°C for 20 minutes to obtain a mixed solution of heated sodium citrate and ethylene glycol; then add the heated sodium citrate and ethylene glycol FeCl3 6H2 O, urea and CeCl2 6H2 O were added to the mixed solution, and then magnetically stirred for 2 hours at room temperature and at a magnetic stirring speed of 200r/min to obtain iron-cerium-containing sodium citrate and ethylene diacetate Alcohol mixed solution;
步骤三②中所述的柠檬酸钠和乙二醇的混合溶液中柠檬酸钠的浓度为60mg/mL；The concentration of sodium citrate in the mixed solution of sodium citrate and ethylene glycol described in step 3. 2. is 60mg/mL;
步骤三②中所述的加热后的柠檬酸钠和乙二醇的混合溶液的体积与FeCl3·6H2O的质量比为50mL:1g；The mass ratio of the volume of the heated mixed solution of sodium citrate and ethylene glycol to FeCl3 .6H2 O in step 3 ② is 50mL:1g;
步骤三②中所述的FeCl3·6H2O与尿素的质量比为50:1；The mass ratio of FeCl3 ·6H2 O and urea described in step 3 ② is 50:1;
步骤三②中所述的FeCl3·6H2O与CeCl2·6H2O的质量比为5:1；The mass ratio of FeCl3 .6H2 O to CeCl2 .6H2 O described in Step 3 ② is 5:1;
③、将50mL氧化石墨烯和乙二醇的混合溶液与50mL含有铁铈的柠檬酸钠和乙二醇的混合溶液混合，再加入到内衬为聚四氟乙烯的不锈钢高压反应釜中，再将不锈钢高压反应釜密封，再将密封的不锈钢高压反应釜在温度为200℃下反应12h，再自然冷却至室温，得到黑色悬浊液；③. Mix 50mL of the mixed solution of graphene oxide and ethylene glycol with 50mL of the mixed solution of sodium citrate containing iron cerium and ethylene glycol, and then add it to a stainless steel autoclave lined with polytetrafluoroethylene, and then Seal the stainless steel autoclave, then react the sealed stainless steel autoclave at a temperature of 200°C for 12h, and then naturally cool to room temperature to obtain a black suspension;
④、将黑色悬浊液在离心速度为6500r/min下进行离心分离10min，得到离心分离后的沉淀物质；分别使用甲醇和去离子水清洗离心分离后的沉淀物质6次，再在温度为-18℃下冷冻干燥24h，得到金属铈/磁性氧化还原石墨烯复合材料；④. Centrifuge the black suspension at a centrifugal speed of 6500r/min for 10 minutes to obtain the centrifuged precipitated substance; use methanol and deionized water to wash the centrifuged precipitated substance 6 times respectively, and then wash the precipitated substance at a temperature of - Freeze-drying at 18°C for 24 hours to obtain a metal cerium/magnetic redox graphene composite material;
四、投加金属铈/磁性氧化还原石墨烯复合材料：将金属铈/磁性氧化还原石墨烯复合材料加入到调节pH值后的过硫酸盐和预处理的水的混合溶液中，反应时间为60min，得到含有金属铈/磁性氧化还原石墨烯复合材料的水；4. Add metal cerium/magnetic redox graphene composite material: Add metal cerium/magnetic redox graphene composite material to the mixed solution of persulfate and pretreated water after adjusting the pH value, and the reaction time is 60min , to obtain water containing metal cerium/magnetic redox graphene composite material;
步骤四中所述的金属铈/磁性氧化还原石墨烯复合材料的投加量为10mg/L；The dosage of the metal cerium/magnetic redox graphene composite material described in step 4 is 10mg/L;
步骤四中所述的外磁场强度为0.03T；The external magnetic field strength described in step 4 is 0.03T;
五、采用外磁场分离金属铈/磁性氧化还原石墨烯复合材料：采用外磁场对含有金属铈/磁性氧化还原石墨烯复合材料的水进行分离，回收金属铈/磁性氧化还原石墨烯复合材料，再使用孔径为0.45μm的玻璃纤维膜对回收的金属铈/磁性氧化还原石墨烯复合材料进行过滤，再将过滤后的金属铈/磁性氧化还原石墨烯复合材料在温度为50℃下干燥24h，得到再生后的金属铈/磁性氧化还原石墨烯复合材料和去除水中内分泌干扰物的水。5. Use external magnetic field to separate metal cerium/magnetic redox graphene composite material: use external magnetic field to separate water containing metal cerium/magnetic redox graphene composite material, recycle metal cerium/magnetic redox graphene composite material, and then Filter the recovered metal cerium/magnetic redox graphene composite material with a glass fiber membrane with a pore size of 0.45 μm, and then dry the filtered metal cerium/magnetic redox graphene composite material at a temperature of 50° C. for 24 h to obtain Regenerated metallic cerium/magnetic redox graphene composite and water removal of endocrine disruptors in water.
本试验的优点：Advantages of this test:
一、本试验方法操作简单，成本低廉，与其他去除水中内分泌干扰物的方法相比，降低了成本40％；1. This test method is simple to operate and low in cost. Compared with other methods for removing endocrine disruptors in water, the cost is reduced by 40%;
二、本试验具有较低的挥发性，反应前后色度和嗅味不会发生变化，制备的金属铈/磁性氧化还原石墨烯复合材料在常温常压下能够稳定存在；2. This test has low volatility, and the chromaticity and smell will not change before and after the reaction, and the prepared metal cerium/magnetic redox graphene composite material can exist stably at normal temperature and pressure;
三、本试验所合成的金属铈/磁性氧化还原石墨烯复合材料反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The metal cerium/magnetic redox graphene composite material synthesized in this experiment has a fast reaction speed, non-toxic by-products, and can effectively remove endocrine disruptors in water;
四、本试验所合成的金属铈/磁性氧化还原石墨烯复合材料能够较容易回收及再生；4. The metal cerium/magnetic redox graphene composite material synthesized in this experiment can be recycled and regenerated more easily;
五、使用本试验的方法去除水中内分泌干扰物的去除率可达93％。5. The removal rate of endocrine disruptors in water by using the method of this test can reach 93%.
试验二：使用活性炭去除水中内分泌干扰物的对比试验，具体是按以下步骤完成的：Test 2: A comparative test of using activated carbon to remove endocrine disruptors in water, specifically completed according to the following steps:
使用粒径为4nm～100nm的煤质颗粒活性炭吸附预处理水中的内分泌干扰物24h，得到去除水中内分泌干扰物的水；Use coal-based granular activated carbon with a particle size of 4nm to 100nm to adsorb endocrine disruptors in pretreated water for 24 hours to obtain water from which endocrine disruptors have been removed;
所述的预处理水中内分泌干扰物为雌三醇，雌三醇的浓度为5mg/L。The endocrine disruptor in the pretreated water is estriol, and the concentration of estriol is 5 mg/L.
试验二中使用粒径为4nm～100nm的煤质颗粒活性炭吸附去除预处理水中内分泌干扰物的去除率为53％。In the second test, coal-based granular activated carbon with a particle size of 4nm to 100nm was used to adsorb and remove endocrine disruptors in pretreated water, and the removal rate was 53%.
试验三：使用紫外光和H2O2去除水中内分泌干扰物的对比试验，具体是按以下步骤完成的：Test 3: A comparative test of using ultraviolet light and H2 O2 to remove endocrine disruptors in water, specifically completed according to the following steps:
向预处理的水中投加浓度为10mmol/L的H2O2，在紫外光强250μW/cm2的紫外光照射预处理的水0.5h，得到去除水中内分泌干扰物的水；Add H2 O2 with a concentration of 10 mmol/L to the pretreated water, and irradiate the pretreated water with ultraviolet light with an ultraviolet light intensity of 250 μW/cm2 for 0.5 h to obtain water from which endocrine disruptors have been removed;
所述的预处理水中内分泌干扰物为雌三醇，雌三醇的浓度为5mg/L；The endocrine disruptor in the pretreatment water is estriol, and the concentration of estriol is 5 mg/L;
试验三使用紫外光和H2O2去除预处理水中内分泌干扰物的去除率为68％。Trial 3 used ultraviolet light and H2 O2 to remove endocrine disruptors in pretreated water with a removal rate of 68%.
试验四：使用过硫酸钠去除水中内分泌干扰物的对比试验，具体是按以下步骤完成的：Test 4: A comparative test of using sodium persulfate to remove endocrine disruptors in water, specifically completed according to the following steps:
向预处理水中投加2mg/L的过硫酸钠，反应2h，得到去除水中内分泌干扰物的水；Add 2 mg/L sodium persulfate to the pretreated water, react for 2 hours, and obtain water from which endocrine disruptors have been removed;
所述的预处理水中内分泌干扰物为雌三醇，雌三醇的浓度为5mg/L；The endocrine disruptor in the pretreatment water is estriol, and the concentration of estriol is 5 mg/L;
试验四使用过硫酸钠去除预处理水中内分泌干扰物的去除率为9％。In Test 4, the removal rate of endocrine disruptors in pretreated water using sodium persulfate was 9%.
试验二使用煤质颗粒活性炭去除预处理水中内分泌干扰物、试验三使用紫外光和H2O2去除预处理水中内分泌干扰物和试验四使用过硫酸钠去除预处理水中内分泌干扰物的去除率分别为53％、68％和9％，而试验一的去除率为93％，证明试验一对于去除预处理水中内分泌干扰物效果极佳。The removal rates of endocrine disruptors in pretreated water by using coal-based granular activated carbon in test 2, by using ultraviolet light and H2 O2 in test 3, and by sodium persulfate in test 4 were respectively 53%, 68% and 9%, while the removal rate of test 1 was 93%, which proved that test 1 had an excellent effect on removing endocrine disruptors in pretreated water.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510073688.0ACN104628211B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative magnetic oxygenated reduced graphene catalyzing activation persulfate of metallic cerium to remove incretion interferent in water |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510073688.0ACN104628211B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative magnetic oxygenated reduced graphene catalyzing activation persulfate of metallic cerium to remove incretion interferent in water |
| Publication Number | Publication Date |
|---|---|
| CN104628211A CN104628211A (en) | 2015-05-20 |
| CN104628211Btrue CN104628211B (en) | 2016-05-11 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510073688.0AExpired - Fee RelatedCN104628211B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative magnetic oxygenated reduced graphene catalyzing activation persulfate of metallic cerium to remove incretion interferent in water |
| Country | Link |
|---|---|
| CN (1) | CN104628211B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082483A (en)* | 2017-05-02 | 2017-08-22 | 四川大学 | The method that a kind of utilization persulfate and carbon based nano-material remove water pollutant |
| CN111252848A (en)* | 2020-02-25 | 2020-06-09 | 中国电建集团成都勘测设计研究院有限公司 | Using CeO2Method for removing tetracycline hydrochloride in water by catalytically activating sodium persulfate under visible light of composite BiOI material |
| CN113041997A (en)* | 2021-03-05 | 2021-06-29 | 佛山科学技术学院 | Modified magnetic biochar and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550003A (en)* | 2009-04-22 | 2009-10-07 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
| CN103030208A (en)* | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN103342405A (en)* | 2013-07-23 | 2013-10-09 | 哈尔滨工业大学 | Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3944707B2 (en)* | 2002-02-18 | 2007-07-18 | Ｊｓｒ株式会社 | Endocrine disruptor removal agent and method of use thereof. |
| WO2011005794A1 (en)* | 2009-07-06 | 2011-01-13 | Halosource, Inc. | Dual polymer system for water recovery and separation of suspended solids from aqueous media |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550003A (en)* | 2009-04-22 | 2009-10-07 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
| CN103030208A (en)* | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
| CN103342405A (en)* | 2013-07-23 | 2013-10-09 | 哈尔滨工业大学 | Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate |
| Title |
|---|
| 二氧化钛光催化降解环境内分泌干扰物技术的研究进展;银洲等;《水处理技术》;20130110;第39卷(第1期);第24-28页* |
| Publication number | Publication date |
|---|---|
| CN104628211A (en) | 2015-05-20 |
| Publication | Publication Date | Title |
|---|---|---|
| CN104667870B (en) | Method for removing endocrine disrupter in water by utilizing persulfate and ferro-manganese loaded dual-phase compound graphene oxide | |
| CN106807376B (en) | A kind of magnetic nanocomposite catalyst and its preparation method and application | |
| CN105731624B (en) | Method for treating reverse osmosis concentrated water by utilizing heterogeneous Fenton-like reaction catalytic oxidation | |
| CN105964256B (en) | A kind of preparation method of hud typed ferroso-ferric oxide/graphene oxide composite nano catalyst | |
| CN108609714B (en) | A method for removing endocrine disruptors in water by catalytically activating persulfate using carbon-based magnetic metal composites | |
| CN107008326A (en) | A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material | |
| CN107935102A (en) | A kind of method that water removal moderate resistance life element is removed using persulfuric acid hydrogen salt and magnetic bismuth oxyiodide visible light catalytic | |
| CN113083238B (en) | Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof | |
| CN104667869B (en) | A kind of single persulfate and load ferro-cobalt two-phase combined oxidation Graphene is utilized to remove the method for incretion interferent in water | |
| CN112121822A (en) | Preparation method of biochar/pyrite composite granular Fenton oxidation catalyst | |
| CN111974404A (en) | Photo-assisted BiFe1-xCuxO3Method for treating residual ciprofloxacin in water body by activated peroxymonosulfate | |
| CN113003648A (en) | Method for treating heavy metal/organic matter composite polluted wastewater by solid waste biomass carbonized material | |
| CN106045130A (en) | Method for catalyzing persulfate to degrade organic wastewater by virtue of bayan obo ores | |
| CN104628211B (en) | A kind of method of utilizing the collaborative magnetic oxygenated reduced graphene catalyzing activation persulfate of metallic cerium to remove incretion interferent in water | |
| CN112076721A (en) | A kind of adsorption activation multifunctional composite material and its application | |
| CN104609636B (en) | A kind of method of utilizing ferrimanganic two-phase doped graphene to activate incretion interferent in single persulfate removal water | |
| CN107552052B (en) | A kind of treatment method of refractory organic wastewater | |
| CN104667871B (en) | Method for eliminating endocrine disrupter in water by activating monopersulfate with ferro-cerium dual-phase loaded graphene oxide | |
| CN108640248B (en) | Method for removing estrogen in water by activating peroxymonosulfate based on carbon-based magnetic iron-cobalt bimetallic material | |
| CN104609607B (en) | A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water | |
| CN111977873B (en) | Method for using photoactivated sepiolite Si-OH for adsorption and photodegradation of water-soluble organic pollutants | |
| CN104475024B (en) | Heavy metal absorbent and its application prepared by a kind of utilization water hyacinth | |
| CN107754807A (en) | A kind of method that estrogen in water removal is removed using sodium peroxydisulfate and magnetic photocatalyst | |
| CN108015270B (en) | Composite iron powder and preparation method and application thereof | |
| CN113244945B (en) | Preparation method of heterogeneous Fenton catalyst for wastewater treatment |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information | Inventor after:Guo Hongguang Inventor after:Zhang Yongli Inventor after:Liang Dashan Inventor after:Cheng Xin Inventor before:Guo Hongguang Inventor before:Shi Bi Inventor before:Zhang Yongli Inventor before:Liang Dashan Inventor before:Cheng Xin | |
| COR | Change of bibliographic data | Free format text:CORRECT: INVENTOR; FROM: GUO HONGGUANG SHI BI ZHANG YONGLI LIANG DASHAN CHENG XIN TO: GUO HONGGUANG ZHANG YONGLI LIANG DASHAN CHENG XIN | |
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20160511 Termination date:20180211 |