CN104609636B - A kind of method of utilizing ferrimanganic two-phase doped graphene to activate incretion interferent in single persulfate removal water - Google Patents
A kind of method of utilizing ferrimanganic two-phase doped graphene to activate incretion interferent in single persulfate removal water Download PDFInfo
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Abstract
Description
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
内分泌干扰物(Endocrinedisruptingchemicals,EDCs)是通过未经完全处理的生活污水、制药废水或牲畜水产业粪肥径流进入水环境，且在水体中富集后浓度会增加上百倍。而即使是痕量级别的EDCs亦会对长期暴露其中的人体及生物体产生致癌、致突变及干扰生殖系统与激素分泌等危害。由于上述物质被频繁地使用并进入环境水体中，导致其形成“假持续”(pseudo-persistent)现象，进而对人体健康以及整个生态系统构成长期潜在危害。Endocrine disrupting chemicals (EDCs) enter the water environment through incompletely treated domestic sewage, pharmaceutical wastewater or livestock and aquaculture manure runoff, and the concentration will increase hundreds of times after being enriched in water. Even trace levels of EDCs can cause carcinogenicity, mutagenesis, and interference with reproductive system and hormone secretion to humans and organisms exposed to them for a long time. Since the above-mentioned substances are frequently used and enter the environmental water body, they form a "pseudo-persistent" phenomenon, which in turn constitutes a long-term potential hazard to human health and the entire ecosystem.
目前处理水中微量有机污染物(内分泌干扰物、抗生素等)主要应用氯化、臭氧及高级氧化工艺，而这些方法处理水中的内分泌干扰物效果不佳且设置多段工艺将导致处理成本增加。At present, chlorination, ozone and advanced oxidation processes are mainly used to treat trace organic pollutants in water (endocrine disruptors, antibiotics, etc.), but these methods are not effective in treating endocrine disruptors in water, and setting up multi-stage processes will lead to increased treatment costs.
发明内容Contents of the invention
本发明的目的是要解决现有方法去除水中内分泌干扰物的去除效率低，成本高的问题，而提供一种利用铁锰双相掺杂石墨烯激活单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 problem of low removal efficiency and high cost of the existing method for removing endocrine disruptors in water, and provide a method for using iron-manganese dual-phase doped graphene to activate monopersulfate to remove endocrine disruptors in water .
一种利用铁锰双相掺杂石墨烯激活单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 iron-manganese dual-phase doped graphene to activate monopersulfate to remove endocrine disruptors in water is completed according to the following steps:
一、将单过硫酸盐与预处理的水混合：将单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，得到单过硫酸盐和预处理的水的混合溶液；1. Mix monopersulfate with pretreated water: mix monopersulfate 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 A mixed solution of monopersulfate and pretreated water;
步骤一中所述的单过硫酸盐为单过硫酸钾、单过硫酸铵、单过硫酸钠和单过硫酸钙中的一种或其中几种的混合物；The monopersulfate described in step 1 is one of potassium monopersulfate, ammonium monopersulfate, sodium monopersulfate and calcium monopersulfate or a mixture of several thereof;
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;
步骤一中所述的单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 monopersulfate 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的氢氧化钠溶液将单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值后的单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 persulfate and pretreated water is adjusted to 6.5 to 7.5 to obtain a mixed solution of monopersulfate and pretreated water after adjusting the pH value;
三、制备铁锰双相掺杂石墨烯：3. Preparation of iron-manganese dual-phase doped graphene:
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MnCl2·6H2O，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，得到含有铁锰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 FeCl 3 6H 2 O, urea and MnCl 2 6H 2 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 iron and manganese;
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 FeCl 3 .6H 2 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 FeCl 3 ·6H 2 O to urea described in Step 3 ② is (0.01-100):1;
步骤三②中所述的FeCl3·6H2O与MnCl2·6H2O的质量比为(0.01～1000):1；The mass ratio of FeCl 3 6H 2 O to MnCl 2 6H 2 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锰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 and manganese 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锰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 and ethylene glycol containing iron and manganese 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，得到铁锰双相掺杂石墨烯；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~15°C for 24h~48h to obtain iron-manganese dual-phase doped graphene;
四、投加铁锰双相掺杂石墨烯：将铁锰双相掺杂石墨烯加入到调节pH值后的单过硫酸盐和预处理的水的混合溶液中，反应时间为15min～240min，得到含有铁锰双相掺杂石墨烯的水；4. Add iron-manganese dual-phase doped graphene: Add iron-manganese dual-phase doped graphene to the mixed solution of monopersulfate and pretreated water after adjusting the pH value, and the reaction time is 15min to 240min. Obtain water containing iron-manganese dual-phase doped graphene;
步骤四中所述的铁锰双相掺杂石墨烯的投加量为1mg/L～200mg/L；The dosage of the iron-manganese dual-phase doped graphene described in step 4 is 1mg/L～200mg/L;
五、采用外磁场分离铁锰双相掺杂石墨烯：采用外磁场对含有铁锰双相掺杂石墨烯的水进行分离，回收铁锰双相掺杂石墨烯，再使用孔径为0.45μm的玻璃纤维膜对回收的铁锰双相掺杂石墨烯进行过滤，再将过滤后的铁锰双相掺杂石墨烯在温度为50℃～75℃下干燥12h～48h，得到再生后的铁锰双相掺杂石墨烯和去除水中内分泌干扰物的水。5. Use external magnetic field to separate iron-manganese dual-phase doped graphene: use external magnetic field to separate water containing iron-manganese dual-phase doped graphene, recover iron-manganese dual-phase doped graphene, and then use a 0.45 μm pore size The glass fiber membrane is used to filter the recovered iron-manganese dual-phase doped graphene, and then the filtered iron-manganese dual-phase doped graphene is dried at a temperature of 50°C-75°C for 12h-48h to obtain regenerated iron-manganese Biphasic doping of graphene and water for removal of endocrine disruptors in water.
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锰将与单过硫酸盐中的HSO5 -或SO5 2-发生电子转移，从而使得单过硫酸根被裂解为·SO4 -与OH-；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，表面大量的有氧官能团，如羧基所具有的多电子基团会进一步激活单过硫酸盐，生成·SO4 -与H2O，从而加速目标有机物的氧化降解。In the present invention, the active metal iron and manganese present on the surface of graphene oxide will undergo electron transfer with HSO 5 - or SO 5 2- in the monopersulfate, so that the monopersulfate is split into SO 4 - and OH - ; On the other hand, graphene oxide has a huge specific surface area, which can adsorb target organic substances, and at the same time, a large number of aerobic functional groups on the surface, such as carboxyl groups with many electrons, will further activate monopersulfate and generate SO 4 - with H 2 O, thereby accelerating the oxidative degradation of the target organic matter.
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，制备的铁锰双相掺杂石墨烯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 iron-manganese dual-phase doped graphene can exist stably at normal temperature and pressure;
三、本发明所合成的铁锰双相掺杂石墨烯反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The iron-manganese dual-phase doped graphene synthesized by the present invention has a fast reaction speed, and the by-products are non-toxic, and can effectively remove endocrine disruptors in water;
四、本发明所合成的铁锰双相掺杂石墨烯能够较容易回收及再生；4. The iron-manganese dual-phase doped graphene synthesized by the present invention can be recovered 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85％～96％。5. The removal rate of endocrine disruptors in water by using the method of the present invention can reach 85%-96%.
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铁锰双相掺杂石墨烯激活单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：Specific embodiment one: this embodiment is a kind of method that utilizes iron-manganese dual-phase doped graphene to activate monopersulfate to remove endocrine disruptors in water, and it is completed according to the following steps:
一、将单过硫酸盐与预处理的水混合：将单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，得到单过硫酸盐和预处理的水的混合溶液；1. Mix monopersulfate with pretreated water: mix monopersulfate 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 A mixed solution of monopersulfate and pretreated water;
步骤一中所述的单过硫酸盐为单过硫酸钾、单过硫酸铵、单过硫酸钠和单过硫酸钙中的一种或其中几种的混合物；The monopersulfate described in step 1 is one of potassium monopersulfate, ammonium monopersulfate, sodium monopersulfate and calcium monopersulfate or a mixture of several thereof;
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;
步骤一中所述的单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 monopersulfate 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的氢氧化钠溶液将单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值后的单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 persulfate and pretreated water is adjusted to 6.5 to 7.5 to obtain a mixed solution of monopersulfate and pretreated water after adjusting the pH value;
三、制备铁锰双相掺杂石墨烯：3. Preparation of iron-manganese dual-phase doped graphene:
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MnCl2·6H2O，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，得到含有铁锰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 FeCl 3 6H 2 O, urea and MnCl 2 6H 2 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 iron and manganese;
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 FeCl 3 .6H 2 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 FeCl 3 ·6H 2 O to urea described in Step 3 ② is (0.01-100):1;
步骤三②中所述的FeCl3·6H2O与MnCl2·6H2O的质量比为(0.01～1000):1；The mass ratio of FeCl 3 6H 2 O to MnCl 2 6H 2 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锰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 and manganese 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锰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 and ethylene glycol containing iron and manganese 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，得到铁锰双相掺杂石墨烯；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~15°C for 24h~48h to obtain iron-manganese dual-phase doped graphene;
四、投加铁锰双相掺杂石墨烯：将铁锰双相掺杂石墨烯加入到调节pH值后的单过硫酸盐和预处理的水的混合溶液中，反应时间为15min～240min，得到含有铁锰双相掺杂石墨烯的水；4. Add iron-manganese dual-phase doped graphene: Add iron-manganese dual-phase doped graphene to the mixed solution of monopersulfate and pretreated water after adjusting the pH value, and the reaction time is 15min to 240min. Obtain water containing iron-manganese dual-phase doped graphene;
步骤四中所述的铁锰双相掺杂石墨烯的投加量为1mg/L～200mg/L；The dosage of the iron-manganese dual-phase doped graphene described in step 4 is 1mg/L～200mg/L;
五、采用外磁场分离铁锰双相掺杂石墨烯：采用外磁场对含有铁锰双相掺杂石墨烯的水进行分离，回收铁锰双相掺杂石墨烯，再使用孔径为0.45μm的玻璃纤维膜对回收的铁锰双相掺杂石墨烯进行过滤，再将过滤后的铁锰双相掺杂石墨烯在温度为50℃～75℃下干燥12h～48h，得到再生后的铁锰双相掺杂石墨烯和去除水中内分泌干扰物的水。5. Use external magnetic field to separate iron-manganese dual-phase doped graphene: use external magnetic field to separate water containing iron-manganese dual-phase doped graphene, recover iron-manganese dual-phase doped graphene, and then use a 0.45 μm pore size The glass fiber membrane is used to filter the recovered iron-manganese dual-phase doped graphene, and then the filtered iron-manganese dual-phase doped graphene is dried at a temperature of 50°C-75°C for 12h-48h to obtain regenerated iron-manganese Biphasic doping of graphene and water for removal of endocrine disruptors in water.
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锰将与单过硫酸盐中的HSO5 --或SO5 2-发生电子转移，从而使得单过硫酸根被裂解为·SO4 -与OH-；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，表面大量的有氧官能团，如羧基所具有的多电子基团会进一步激活单过硫酸盐，生成·SO4 -与H2O，从而加速目标有机物的氧化降解。In this embodiment, the active metal iron and manganese present on the surface of graphene oxide will undergo electron transfer with HSO 5 -- or SO 5 2- in the monopersulfate, so that the monopersulfate is split into SO 4 - and OH - ; 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 aerobic functional groups on the surface, such as the multi-electron groups of carboxyl groups, will further activate monopersulfate and generate · SO 4 - and H 2 O, thereby accelerating the oxidative degradation of target organic matter.
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，制备的铁锰双相掺杂石墨烯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 iron-manganese dual-phase doped graphene can exist stably at normal temperature and pressure;
三、本实施方式所合成的铁锰双相掺杂石墨烯反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The iron-manganese dual-phase doped graphene synthesized in this embodiment has a fast reaction speed, and the by-products are non-toxic, and can effectively remove endocrine disruptors in water;
四、本实施方式所合成的铁锰双相掺杂石墨烯能够较容易回收及再生；4. The iron-manganese dual-phase doped graphene 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85％～96％。5. The removal rate of endocrine disruptors in water by using the method of this embodiment can reach 85%-96%.
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：步骤一中所述的单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: The difference between this embodiment and Embodiment 1 to 4 is that the mass ratio of the monopersulfate 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：步骤一中所述的单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 monopersulfate 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：步骤四中所述的铁锰双相掺杂石墨烯的投加量为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 iron-manganese dual-phase doped graphene described in step 4 is 0.02 mg/L-10 mg/L. Other 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：步骤四中所述的铁锰双相掺杂石墨烯的投加量为10mg/L～100mg/L。其他步骤与具体实施方式一至七相同。Embodiment 8: The difference between this embodiment and Embodiments 1 to 7 is that the dosage of the iron-manganese dual-phase doped graphene 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：步骤四中所述的铁锰双相掺杂石墨烯的投加量为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 iron-manganese dual-phase doped graphene 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:
试验一：一种利用铁锰双相掺杂石墨烯激活单过硫酸盐去除水中内分泌干扰物的方法Experiment 1: A method for removing endocrine disruptors in water by activating monopersulfate using iron-manganese biphasic doped graphene
一、将单过硫酸盐与预处理的水混合：将单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，得到单过硫酸盐和预处理的水的混合溶液；1. Mix monopersulfate with pretreated water: mix monopersulfate with pretreated water, then stir for 30min at room temperature and at a stirring speed of 180r/min to obtain monopersulfate and pretreated water Mixed solution of treated water;
步骤一中所述的单过硫酸盐为单过硫酸钾；The monopersulfate described in step 1 is potassium monopersulfate;
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;
步骤一中所述的单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 monopersulfate 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的氢氧化钠溶液将单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值后的单过硫酸盐和预处理的水的混合溶液；Two, adjust the reaction pH value: use the perchloric acid of 0.1mol/L and the sodium hydroxide solution of 0.1mol/L under the condition of 180r/min to make the mixed solution of monopersulfate and pretreated water The pH value is adjusted to 6.5 to obtain a mixed solution of monopersulfate and pretreated water after adjusting the pH value;
三、制备铁锰双相掺杂石墨烯：3. Preparation of iron-manganese dual-phase doped graphene:
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MnCl2·6H2O，再在室温和磁力搅拌速度为200r/min的条件下磁力搅拌2h，得到含有铁锰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 FeCl 3 6H 2 O, urea and MnCl 2 6H 2 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-manganese-containing sodium citrate and ethylenedi 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 FeCl 3 .6H 2 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 FeCl 3 ·6H 2 O and urea described in step 3 ② is 50:1;
步骤三②中所述的FeCl3·6H2O与MnCl2·6H2O的质量比为5:1；The mass ratio of FeCl 3 6H 2 O to MnCl 2 6H 2 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含有铁锰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 and manganese 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，得到铁锰双相掺杂石墨烯；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 iron-manganese dual-phase doped graphene;
四、投加铁锰双相掺杂石墨烯：将铁锰双相掺杂石墨烯加入到调节pH值后的单过硫酸盐和预处理的水的混合溶液中，反应时间为60min，得到含有铁锰双相掺杂石墨烯的水；Four, add iron-manganese dual-phase doped graphene: iron-manganese dual-phase doped graphene is added to the mixed solution of monopersulfate and pretreated water after the pH value is adjusted, and the reaction time is 60min to obtain a mixture containing Iron-manganese dual-phase doped graphene water;
步骤四中所述的铁锰双相掺杂石墨烯的投加量为10mg/L；The dosage of the iron-manganese dual-phase doped graphene 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、采用外磁场分离铁锰双相掺杂石墨烯：采用外磁场对含有铁锰双相掺杂石墨烯的水进行分离，回收铁锰双相掺杂石墨烯，再使用孔径为0.45μm的玻璃纤维膜对回收的铁锰双相掺杂石墨烯进行过滤，再将过滤后的铁锰双相掺杂石墨烯在温度为50℃下干燥24h，得到再生后的铁锰双相掺杂石墨烯和去除水中内分泌干扰物的水。5. Use external magnetic field to separate iron-manganese dual-phase doped graphene: use external magnetic field to separate water containing iron-manganese dual-phase doped graphene, recover iron-manganese dual-phase doped graphene, and then use a 0.45 μm pore size Filter the recycled iron-manganese dual-phase doped graphene with a glass fiber membrane, and then dry the filtered iron-manganese dual-phase doped graphene at a temperature of 50°C for 24 hours to obtain regenerated iron-manganese dual-phase doped graphite ene and water that removes endocrine disruptors from 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45％；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 45%;
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，制备的铁锰双相掺杂石墨烯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 iron-manganese dual-phase doped graphene can exist stably at normal temperature and pressure;
三、本试验所合成的铁锰双相掺杂石墨烯反应速度快，副产物无毒性，能够有效去除水中内分泌干扰物；3. The iron-manganese dual-phase doped graphene synthesized in this experiment has a fast reaction speed, and the by-products are non-toxic, which can effectively remove endocrine disruptors in water;
四、本试验所合成的铁锰双相掺杂石墨烯能够较容易回收及再生；4. The iron-manganese dual-phase doped graphene synthesized in this experiment can be recovered 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95％。5. The removal rate of endocrine disruptors in water by using the method of this test can reach 95%.
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 H 2 O 2 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250uW/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 H 2 O 2 with a concentration of 10mmol/L to the pretreated water, and irradiate the pretreated water with ultraviolet light with an ultraviolet light intensity of 250uW/cm 2 for 0.5h 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 H 2 O 2 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95％，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 H 2 O 2 in test 3, and by sodium persulfate in test 4 were respectively 53%, 68% and 9%, while the removal rate of test 1 was 95%, which proved that test 1 had an excellent effect on removing endocrine disruptors in pretreatment water.
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