CN109574317B - 利用钌酸镧系钙钛矿活化过氧乙酸降解氟喹诺酮抗生素的方法 - Google Patents
利用钌酸镧系钙钛矿活化过氧乙酸降解氟喹诺酮抗生素的方法 Download PDFInfo
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- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 10
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 10
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- 230000003213 activating effect Effects 0.000 title claims abstract description 8
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- 229910052747 lanthanoid Inorganic materials 0.000 title description 5
- 150000002602 lanthanoids Chemical class 0.000 title description 5
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种利用钌酸镧系钙钛矿(LaRuO3)催化剂非均相活化过氧乙酸处理氟喹诺酮类抗生素废水的方法,涉及水处理领域。本发明的目的在于解决现有过氧乙酸催化活化技术效率偏低及会产生二次污染的问题,开发出一种更加高效、经济、环保的方法。该方法首次将钌酸盐系钙钛矿用于活化过氧乙酸,利用二者活化产生的羟基自由基,进一步氧化废水中的氟喹诺酮类抗生素。使用该方法对典型氟喹诺酮类抗生素环丙沙星去除效果明显,在30min去除率即可达到92%左右。该方法具有活化效率高、污染物去除高效快速、pH使用范围宽、LaRuO3也可重复利用降低成本、运行操作方便等优点。
Description
技术领域
本发明涉及水污染控制技术领域,尤其是涉及一种钌酸镧系钙钛矿催化剂非均相活化过一硫酸盐降解水体中氟喹诺酮类抗生素的方法。
背景技术
药物和个人护理用品(PPCPs)是一类新兴污染物,具有浓度低、多样性、难挥发及生物降解缓慢等特性,其包括各种抗生素、处方药和非处方药、护肤品、香料以及麝香等,目前已在环境中被广泛检出。作为一种重要的PPCPs,氟喹诺酮类抗生素(FQs)是一类人工合成的广谱抗菌药,在临床上广泛用于动物和人类的各种感染性疾病的治疗,其中环丙沙星(CIP)在世界范围内广泛使用。FQs生物毒性大,难以生物降解,排放到环境水体中会对细菌、藻类、无脊椎动物和鱼类产生毒害作用,并且有可能通过食物链对人体产生危害,从而引发环境风险或环境问题。
水体中FQs的去除技术主要有常规生物处理技术以及深度处理技术。生物处理虽然运行简单,费用低,但对于氟喹诺酮等有毒难降解的污染物,去除效率很低。而深度处理技术,尤其是基于羟基自由基(HO·)的高级氧化技术,作为20世纪80年代发展起来的一种用于处理难降解有机污染物的新技术在去除抗生素方面有巨大潜力,并已广泛应用于废水和地下水处理中。
HO·是一种无选择性的强氧化剂,具有以下特点:1、较高的氧化还原电位(2.8V),是臭氧的1.35倍、氯的2.06倍,几乎可以与所有有机物和生物大分子发生反应,并通过断键、加成等反应,最终起到氧化降解的目的;2、HO·可以以很快的反应速度进攻有机污染物,反应速率快;3、由于HO·的高氧化活性几乎可以与所有有机污染物和生物体反应,所以它对有机物的降解和微生物的杀灭无选择性。HO·可以快速的与有机体作用,最终氧化降解为CO2,H2O和微量无机盐,无有害副产物生成。
近30年来,过氧乙酸(PAA)在污废水中的应用逐渐引起了人们的关注。活化PAA产生HO·作为一种新型的高级氧化技术已经受到了越来越多的关注。目前所报道的活化PAA的方式主要有紫外活化和过渡金属离子催化剂活化等。由紫外光活化消耗大量的能量使其活化成本比较高,而过渡金属非均相催化技术则可以在常温、常压下快速进行,不需要额外能量,因此被广泛研究。虽然金属钴被认为是最好的活化剂,但它的泄漏存在二次污染问题。因此,急需寻找一种绿色催化剂来活化PAA。
钌(Ru)基催化剂价格低廉、而且抗腐蚀性强,因此在催化、储能、航空材料等各个领域中的应用逐渐成为研究热点。Ru基催化剂的基本组成有载体和活性中心,选择适宜的载体材料,有助于提高Ru纳米颗粒的分散度和稳定性,提高Ru催化剂的利用效率,从而降低生产成本。
发明内容
针对现有技术存在的上述问题,本申请提供了一种利用钌酸镧系钙钛矿活化过氧乙酸降解氟喹诺酮抗生素的方法。本发明主要解决的问题是:过氧乙酸活化效率低,水溶性金属离子作为催化剂易引起二次污染。本发明在常温常压下进行,环境友好,成本低,易于操作,对pH适应范围广,在环境污染治理领域具有很大的应用潜力。
本发明的技术方案如下:
一种活化过氧乙酸降解氟喹诺酮抗生素的方法,包括如下步骤:
(1)向含有环丙沙星的废水中加入过氧乙酸,混合后得到过氧乙酸溶液,调节溶液的pH;
(2)向步骤(1)得到的混合溶液中投加钌酸镧钙钛矿,并置于恒温摇床中搅拌,常温下去除环丙沙星。
所述钌酸镧钙钛矿的制备方法为:
(1)按照摩尔比为La:Ru:CA=1:(1-5):(2-6),分别称取La(NO3)3·6H2O、RuCl3和C6H8O7·H2O在烧杯中混合后加水使其溶解,剧烈搅拌溶液,同时将温度升至65℃,继续加入乙二醇并保持在该温度直至由于水的缓慢蒸发而变成粘性凝胶状物质;
(2)将烧杯转移到加热套中以提供均匀加热,温度升至120℃保持1-4h,此时通过柠檬酸与乙二醇的反应形成3D聚合物结构;
(3)将含有剩余产物的烧杯置于烘箱中在不低于100℃下彻底干燥;
(4)干燥后,将聚合物粉碎后在800-1000℃下煅烧6-9小时,以分解聚合物并得到所需的氧化物相。
本申请所处理废水中环丙沙星浓度<200mg/L,包括但不局限于环丙沙星。
上述处理过程中,过氧乙酸与环丙沙星的质量比控制在1:2-10:1。
上述处理过程中,调节溶液的pH是指用硫酸或氢氧化钠调节溶液pH为3-9。
上述处理过程中,钌酸镧钙钛矿投加量为0.5-2g/L。
上述处理过程中,恒温摇床中搅拌的反应时间为1-30分钟。
本发明有益的技术效果在于:
钙钛矿型复合氧化物的化学通式为ABO3,其中A位是半径较大的碱金属、碱土金属或稀土金属离子,B位是半径比较小的过渡金属离子。由于钙钛矿型氧化物的催化活性强烈地依赖于B位阳离子的性质,在设计或改进钙钛矿型催化剂时,B位阳离子的选择至关重要。因此,将Ru元素引入作为B位阳离子,钙钛矿型复合氧化物作为Ru元素的载体材料,可以完美结合二者的优势,极大的改善催化剂的性能。开发钌酸镧系钙钛矿用以活化过氧乙酸,这在控制水中PPCPs、保障水体安全的研究领域将是一个全新的突破。
本发明采用钌酸镧钙钛矿作为催化剂,钌酸镧钙钛矿在催化过程中不会产生二次污染,催化效率高并且可以多次回收重复利用。本发明以过氧乙酸为氧化剂,相对于其他氧化剂,PAA受有机物质的影响较小,不产生或少产生消毒副产物。本发明提供的方法在近中性环境下即可获得高效的去除效果,在实际处理中可不需加酸加碱调节pH,降低经济成本。
本发明首次开发性的将钌酸镧钙钛矿用作活化过氧乙酸,并应用于处理废水中喹诺酮类抗生素,提高了过氧乙酸的活化效率,获得了高效、快速的环丙沙星降解效果,促进了活化过氧乙酸新兴技术在废水(液)处理方面的推广和应用。
附图说明
图1为图1为应用例对环丙沙星的降解效果示意图。
图中:PAA为过氧乙酸,LaRuO3为钌酸镧钙钛矿;纵坐标C/C0指某一时刻环丙沙星环丙沙星浓度与初始浓度的比值。
具体实施方式
下面结合实施例,对本发明进行具体描述。然而本发明的保护范围不局限于下面所列举的实施例。
实施例1:
(1)按照摩尔比为La:Ru:CA=1:1:2,分别称取La(NO3)3·6H2O、RuCl3和C6H8O7·H2O混合后加水使其溶解,剧烈搅拌溶液,同时将温度升至65℃,继续加入乙二醇并保持在该温度直至由于水的缓慢蒸发而变成粘性凝胶状物质;
(2)将烧杯转移到加热套中以提供均匀加热,温度升至120℃保持1h,此时通过柠檬酸与乙二醇的反应形成3D聚合物结构;
(3)将含有剩余产物的烧杯置于烘箱中(>100℃)彻底干燥;
(4)干燥后,将聚合物粉碎后在800℃下煅烧8小时,以分解聚合物并得到所需的氧化物相。
实施例2:
(1)按照摩尔比为La:Ru:CA=1:5:6,分别称取La(NO3)3·6H2O、RuCl3和C6H8O7·H2O混合后加水使其溶解,剧烈搅拌溶液,同时将温度升至65℃,继续加入乙二醇并保持在该温度直至由于水的缓慢蒸发而变成粘性凝胶状物质;
(2)将烧杯转移到加热套中以提供均匀加热,温度升至120℃保持1h,此时通过柠檬酸与乙二醇的反应形成3D聚合物结构;
(3)将含有剩余产物的烧杯置于烘箱中(>100℃)彻底干燥;
(4)干燥后,将聚合物粉碎后在900℃下煅烧7小时,以分解聚合物并得到所需的氧化物相。
实施例3:
(1)按照摩尔比为La:Ru:CA=1:2:3,分别称取La(NO3)3·6H2O、RuCl3和C6H8O7·H2O混合后加水使其溶解,剧烈搅拌溶液,同时将温度升至65℃,继续加入乙二醇并保持在该温度直至由于水的缓慢蒸发而变成粘性凝胶状物质;
(2)将烧杯转移到加热套中以提供均匀加热,温度升至120℃保持4h,此时通过柠檬酸与乙二醇的反应形成3D聚合物结构;
(3)将含有剩余产物的烧杯置于烘箱中(>100℃)彻底干燥;
(4)干燥后,将聚合物粉碎后在1000℃下煅烧6小时,以分解聚合物并得到所需的氧化物相。
应用例1:
向环丙沙星浓度为10mg/L的废水中投加1.32mM的过氧乙酸得到废水溶液,用2mM硫酸和氢氧化钠溶液调节废水的pH值为7.0。然后向上述溶液中投加0.5g/L实施例1制备得到的钌酸镧钙钛矿,在常温下反应30分钟,结果见图1。从图中可以看到,在钌酸镧钙钛矿活化的PAA体系中,经过30分钟左右系统对环丙沙星的去除率可以达到92%左右,相比较其他活化方法,钌酸镧钙钛矿对PAA的活化效率更加高效。
应用例2:
向环丙沙星浓度为100mg/L的废水中投加1.32mM的过氧乙酸得到废水溶液,用2mM硫酸和氢氧化钠溶液调节废水的pH值为3.0。然后向上述溶液中投加1g/L实施例2制备得到的钌酸镧钙钛矿,在常温下反应30分钟。结果发现经过30分钟的反应之后系统对环丙沙星的去除率达到82%左右。
应用例2:
向环丙沙星浓度为200mg/L的废水中投加1.32mM的过氧乙酸得到废水溶液,用2mM硫酸和氢氧化钠溶液调节废水的pH值为9.0。然后向上述溶液中投加2g/L实施例3制备得到的钌酸镧钙钛矿,在常温下反应30分钟。结果发现经过30分钟的反应之后系统对环丙沙星的去除率达到85%左右,这说明该方法对较高浓度的环丙沙星也表现出较好的去除效果。
Claims (6)
1.一种活化过氧乙酸降解氟喹诺酮抗生素的方法,其特征在于包括如下步骤:
(1)向含有环丙沙星的废水中加入过氧乙酸,混合后得到过氧乙酸溶液,调节溶液的pH;
(2)向步骤(1)得到的混合溶液中投加钌酸镧钙钛矿,并置于恒温摇床中搅拌,常温下去除环丙沙星;
所述钌酸镧钙钛矿的制备方法为:
(1)按照摩尔比为La:Ru:CA=1:(1-5):(2-6),分别称取La(NO3)3·6H2O、RuCl3和C6H8O7·H2O在烧杯中混合后加水使其溶解,剧烈搅拌溶液,同时将温度升至65℃,继续加入乙二醇并保持在该温度直至由于水的缓慢蒸发而变成粘性凝胶状物质;
(2)将烧杯转移到加热套中以提供均匀加热,温度升至120℃保持1-4h,此时通过柠檬酸与乙二醇的反应形成3D聚合物结构;
(3)将含有剩余产物的烧杯置于烘箱中在不低于100℃下彻底干燥;
(4)干燥后,将聚合物粉碎后在800-1000℃下煅烧6-9小时,以分解聚合物并得到所需的氧化物相。
2.根据权利要求1所述的方法,其特征在于废水中环丙沙星浓度<200mg/L,包括但不局限于环丙沙星。
3.根据权利要求1所述的方法,其特征在于所述过氧乙酸与环丙沙星的质量比控制在1:2-10:1。
4.根据权利要求1所述的方法,其特征在于所述调节溶液的pH是指用硫酸或氢氧化钠调节溶液pH为3-9。
5.根据权利要求1所述的方法,其特征在于所述钌酸镧钙钛矿投加量为0.5-2g/L。
6.根据权利要求1所述的方法,其特征在于所述恒温摇床中搅拌的反应时间为1-30分钟。
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