CN110255695B - 一种非金属催化的有机类芬顿反应试剂及其应用 - Google Patents
一种非金属催化的有机类芬顿反应试剂及其应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
本发明公开了一种非金属催化的有机类芬顿反应试剂及其应用,该试剂由过氧化物溶液和活化剂组成,在缺氧环境下,可利用紫外光辐照苯甲酸及其衍生物与过氧化物的混合溶液,从而促进过氧化物快速分解产生大量羟基自由基;本发明建立的UV/苯甲酸类衍生物/缺氧体系,分解过氧化氢的速率是UV/H2O2法的数十倍,羟基自由基产率是其500倍以上,且相比于常规的芬顿体系,适用溶液pH范围宽,不需要含有过渡金属离子,不产生污泥等二次污染问题,同时,本方法对于过氧化氢、过氧乙酸、过硫酸盐等过氧化物均具有显著的促进分解效果,大大拓展了类芬顿反应的范畴;在有机污染物降解、酚类物质制备领域具有广阔的应用前景。
Description
技术领域
本发明涉及水处理领域,特别是涉及一种非金属催化的有机类芬顿反应试剂及其应用。
背景技术
过氧化物是指一类含有过氧键(-O-O-)的化合物,具有强氧化性,由于其含有的过氧键能较小,很容易通过外源能量输入导致其键断裂产生(·OH)和其他活性粒子,故目前利用过氧化物的高级氧化法(AOPs)在水和废水处理中已得到广泛的应用。常见的过氧化物,如过氧化氢(H2O2)、过一硫酸盐(PMS)、过二硫酸盐(PDS)和过氧乙酸等已被广泛应用于AOPs中的自由基前体研究中。
芬顿(Fenton)和类芬顿反应一直被用于高效生产·OH(“水处理高级氧化技术研究进展.”赵丽红等.科学技术与工程,2019,19,1-9)。该类试剂的反应原理是以H2O2为前驱体,以过渡金属为催化剂进行链式反应生成大量的·OH(羟基自由基),常见的金属催化剂有Fe2+、Fe3+、含Fe矿物以及其他一些过渡金属如Co、Cd、Cu、Ag、Mn、Ni等。·OH具有极高的氧化性,可将很多难降解有机污染物氧化为无机态。因此,芬顿反应在环境水处理,生物医疗等领域有很广泛的应用(“芬顿氧化技术处理废水中难降解有机物的应用进展”胡德皓等.山东化工,2019,48,60-62+65)。但是该反应非常剧烈,反应过程不易控制,反应溶液pH为强酸性(2-4),且需要外源投加过渡金属作为催化剂,使得设备易腐蚀,产泥量很高,存在严重的环境健康风险等问题(“芬顿氧技术处理难降解有机废水的研究进展”.李翠翠.广东化工,2019,10,97-99),从而限制了该类试剂的应用领域范围。此外,通过紫外光(UV)辐照过氧化物分解的UV/H2O2和UV/PMS等工艺,也作为一种常见的高级氧化技术被广泛应用于水处理中(“UV/H2O2工艺降解水中污染物的动力学研究进展”连军锋等.水处理技术,2019,45,6-10;“UV/PMS降解水中罗丹明B的动力学及反应机理”田东凡等,环境科学学报,2018,38,1868-1876)。然而,由于这些过氧化物的摩尔消光系数很低,使得其光子利用率很低。
苯甲酸及其衍生物是一类具有羧基与苯环直接相连的结构的芳香羧酸化合物。常见的苯甲酸类物质有苯甲酸、水杨酸、对苯二甲酸、对羟基苯甲酸等。这类物质可作为防腐剂、抗菌剂、成核剂、化学合成中间体,在食品、化妆品、卫生和医药产品,化工等领域(“苯甲酸的结晶精制与在调味品中的应用研究”陈高伟等,中国食品添加剂.2017,08,170-175;“苯甲酸的提纯新工艺研究”吴骏,武汉工程大学,2014)。世界上90%以上的苯酚是以异丙苯为基础的三步反应过程制成。该技术能耗高,工艺流程复杂,中间有大量的副产物和爆炸性中间体(异丙苯过氧化氢)的产生,从而导致苯酚的一次收率很低(约5%)。目前,未见有利用苯甲酸类物质促进过氧化物分解,快速产生羟基自由基的方法及应用的相关报道。
发明内容
针对现有芬顿类试剂反应剧烈、以过渡金属作为催化剂、应用领域窄的问题,本发明提供了一种非金属催化的有机类芬顿反应的试剂及其应用,该试剂能够快速、高效地将过氧化物分解,产生大量羟基自由基和酚类物质。在水处理高级氧化技术、光化学合成酚、光动力治疗等多个领域具有良好的应用前景。
具体而言,本申请是通过如下技术方案实现的:
首先,本发明提供了一种非金属催化的有机类芬顿反应试剂,由过氧化物溶液和活化剂组成,所述活化剂包括苯甲酸或苯甲酸衍生物中的至少一种;
上述过氧化物是指含有过氧键的化合物,包括过氧化氢、过氧乙酸、过氧丙酸等过氧有机物,或者过硫酸盐等无机过氧化物中的至少一种。
上述苯甲酸衍生物包括1,3-苯二甲酸,1,4-苯二甲酸,4-羟基苯甲酸,4-甲基苯甲酸,4-氯苯甲酸等官能团取代的苯甲酸,或者是苯甲酸钠,苯甲酸钾,1,3-苯二甲酸钠等苯甲酸盐化合物,其他羧基与苯环直接相连的芳香羧酸化合物中的至少一种。
进一步而言,上述非金属催化的有机类芬顿反应试剂中,过氧化物与活化剂的摩尔比优选小于1(如过氧化物与活化剂的摩尔比为4:5),以确保反应中过氧化物完全分解。
其次,本发明还提供了上述非金属催化的有机类芬顿反应试剂在水处理领域降解去除有机污染物的应用。其具体步骤如下:
将非金属催化的有机类芬顿反应试剂与含有有机污染物(如香豆素,抗生素,杀虫剂等)的溶液混合后获得混合溶液,以常规酸碱(如氢氧化钠,氢氧化钾,盐酸,高氯酸等)调节混合溶液pH为3-11,然后将溶液置于缺氧条件下,然后置于紫外光源下,即可迅速产生大量的羟基自由基,以实现有机污染物的去除;混合溶液中,优选过氧化物浓度大于有机污染物浓度,以确保反应完全。
第三,本发明还提供了一种制备酚类物质、生产羟基自由基的方法,其具体步骤如下:
采用常规酸碱(氢氧化钠,氢氧化钾,盐酸,高氯酸等)试剂调节非金属催化的有机类芬顿反应试剂的pH为3-11,然后将该试剂置于缺氧条件下,于紫外光源下,即可迅速产生大量的羟基自由基,这些羟基自由基与苯甲酸类活化剂反应,同时实现酚类物质的制备。
本申请中,“缺氧条件”是通过常规排氧操作(如曝氮气,曝氩气等),使得溶液中溶解氧的浓度低于2mg/L(含2mg/L),从而屏蔽溶解氧的竞争反应,防止氧气双氧水竞争反应,导致双氧水不能有效的分解。排氧操作可使用本领域任何常规方式,如文献“水体氧动态对氮磷地球化学行为的影响.古小治等.环境科学研究.2015,10,1524-1530”、“低基质浓度下pH和DO对厌氧氨氧化反应效能的影响.张黎等.环境工程.2015,06,59-62”中公开的排氧操作方法。
本申请中,紫外光源使得苯甲酸类物质引发离子化,产生有机自由基,进而与过氧化物反应,在紫外光强度较低条件下,离子化过程较慢,故紫外光源强度优选大于0.1mW/cm2,辐照时间不超过10min,一般而言,紫外光源强度越大,反应速率越快。
上述“紫外光源”是指能够发射波长为200-400nm光子的光源,如低压汞灯,中压汞灯等。
本申请中,所产生的酚类物质是指苯甲酸经过羟基化过程,产生的加羟基产物和脱羧基后加羟基的酚类物质,如苯酚,2-羟基苯甲酸,3-羟基苯甲酸,4-羟基苯甲酸等。这些酚类物质后期可通过常规方法进行分离,应用于化工,医药,食品等各个行业。
本发明通过引入紫外光辐照苯甲酸类物质缺氧水溶液,建立了一种新型的无金属催化的有机芬顿反应,该反应通过紫外光引发苯甲酸类物质离子化,产生苯甲酸类有机自由基,并与H2O2迅速反应,产生OH自由基。由于苯甲酸类物质的摩尔消光系数很高,可以有效的利用光子。其羟基自由基的产量是相同条件下的UV/H2O2体系的500倍以上。该方法相比传统芬顿反应技术,无需投加过渡金属,反应过程容易控制,pH适用范围宽等优点。在水处理,化学合成,光动力治疗等领域具有极大的应用潜力。具体而言,本申请具有以下有益效果:
1、与传统金属催化介导的芬顿反应不同,本发明提供了一种非金属催化的有机类芬顿反应,该方法不含有毒的金属离子,不产生污泥,不需要调节溶液呈酸性。该反应体系分解双氧水的速率是UV/H2O2法的数十倍,羟基自由基产率是UV/H2O2的500倍以上。该技术可应用于环境水处理,降解目标污染物。也可利用该方法促进细胞组织内的双氧水快速分解,产生活性粒子,杀死癌细胞,在光动力治疗方面具有一定的应用前景。
2、本发明采用苯甲酸或其衍生物为促进剂,在快速促进双氧水分解的同时,苯甲酸类物质快速转化为羟基化产物,形成大量酚类物质。该方法可以一步合成酚类化合物,符合环境友好、清洁生产的要求,为光化学合成酚提供了新的思路,具有极大的发展潜力。
附图说明
图1为实施例不同苯甲酸类物质促进双氧水分解的浓度变化示意图;
图2为实施例对苯二甲酸促进过氧乙酸,过一硫酸盐分解的浓度变化示意图;
图3为实施例UV/对苯二甲酸/缺氧体系促进香豆素降解的浓度变化示意图;
图4为实施例UV/对苯二甲酸/缺氧体系降解香豆素过程中羟基化产物的浓度变化示意图;
图5为实施例UV/苯甲酸/缺氧体系中羟基化产物的浓度变化示意图;
图6为实施例UV/对苯二甲酸/缺氧体系中酚类物质的浓度变化示意图。
具体实施方式
(1)实施例涉及试剂
以下实施例中所使用的苯甲酸、对苯二甲酸、间苯二甲酸,对羟基苯甲酸,对氯苯甲酸,对甲基苯甲酸,香豆素,7-羟基香豆素,苯酚,邻羟基苯甲酸,间羟基苯甲酸,双氧水(H2O2),过一硫酸钠均为分析纯级,其中苯甲酸、对苯二甲酸、间苯二甲酸,对羟基苯甲酸由上海麦克林生化科技有限公司提供,过氧乙酸(浓度40%)由北京四环卫生药械厂有限公司提供。其余的药品由南京化学试剂厂有限公司提供。
(2)反应装置
光反应装置由北京泊菲莱科技有限公司提供,型号为PCX-50C多通道光化学反应系统。该装置所用的光源为5W的汞灯,底部受光,可实现1-9个反应位的平行实验。50ml底部透光的可密封的反应瓶用来盛放反应溶液。在反应过程中汞灯旋转,保证各反应瓶受光均匀。
(3)检测方法
以下实施例溶液中过氧化氢和过氧乙酸含量均通过文献(N,N-二乙基对苯二胺/辣根过氧化物酶法测定过氧化氢浓度时臭氧干扰的消除.皮运正等.分析化学.2005.10.1516)中描述的显色法进行测量,所有的样品均为分析纯级,且样品分析在1h之内完成。溶液中过一硫酸盐通过文献(Formation of brominated disinfectionbyproducts from natural organic matter isolates and model compounds in asulfate radical-based oxidation process.Wang et al.Environmental science&technology,2014,48,14534-14542.)。溶液中苯甲酸衍生物含量及酚类物质的含量测定通过高效液相色谱仪(Waters 1525,美国)进行测定。测定方法依据文献(NonnegligibleGeneration of Hydroxyl Radicals from UVC Photolysis of Aqueous NitrousOxide.Zhang et al.Environmental Science&Technology,2018,52,9785-9792.Assessing the contribution of free hydroxyl radical in organic matter-sensitized photohydroxylation reactions.Page et al.Environmental Science andTechnology,2011,45,2818-2825.)。
预曝氮气的方法为采用将纯度为99.999%的氮气钢瓶中的氮气(南京天泽气体有限责任公司)通过导管引入到反应瓶中,以25L/h的气体流量持续曝气30min至溶液的溶解氧浓度低于2mg/L。具体方式可参见以公开文献(Nonnegligible Generation of HydroxylRadicals from UVC Photolysis of Aqueous Nitrous Oxide.Zhang etal.Environmental Science&Technology,2018,52,9785-9792.)。
(4)过氧化物分解率计算
以下各实施例中的过氧化物分解率是指在光照10min后,分解掉的过氧化物的含量占原始过氧化物投加量的百分比。具体计算方式为:
分解率=(原始过氧化物投加量-光照10min后溶液中剩余的过氧化物含量)/原始过氧化物投加量*100%
实施例1
分别配置苯甲酸/双氧水,对氯苯甲酸/双氧水,对甲基苯甲酸/双氧水,对羟基苯甲酸/双氧水,间苯二甲酸/双氧水,对苯二甲酸/双氧水,共计6种混合溶液。混合溶液中苯甲酸及其衍生物的浓度为50μM,双氧水浓度为40μM,过氧化物与活化剂的摩尔比为4:5;采用NaOH试剂(1mM)调节溶液pH=9.0,预曝氮气30min至氧气浓度低于2mg/L后,倒入光反应装置的反应管中密封。在低压汞灯(10W,GPH212T5L,贺利氏)辐照下10min(0.1mW/cm2)。利用显色法测定溶液中的双氧水含量,检测结果如图1所示,可见,双氧水的分解率分别为:57%;68%;80%。89%;90%;100%。
以上实验结果证明苯甲酸类的物质在缺氧条件下,经过紫外光辐照,可作为活化剂,迅速的分解双氧水。其中对苯二甲酸的促进效果最好,10min后,即可分解完全。
实施例2
分别配置对苯二甲酸/过一硫酸盐,对苯二甲酸/过氧乙酸,共计2种混合溶液,混合溶液中对苯二甲酸的浓度为50μM,过一硫酸盐的浓度为40μM,过氧乙酸的浓度为40μM.调节pH=9.0,预曝氮气30min至氧气浓度低于2mg/L后,倒入光反应装置的反应管中密封。在低压汞灯(10W,GPH212T5L,贺利氏)辐照下10min(0.1mW/cm2)。
分别利用显色法测定溶液中的过一硫酸盐,检测结果如图2所示,可见过氧乙酸的含量分别为:0.32μM;3.9μM;计算得到过一硫酸盐和过氧乙酸的分解率分别为:99%;90%。
以上实验结果证明对苯二甲酸不仅对于过氧化氢(参见实施例1)具有快速的促进效果,对于含有过氧键的有机过氧化物:过氧乙酸和无机过氧化物:过一硫酸盐均具有显著的促进分解的效果。说明了该方法对于含有过氧键化合物促进其分解的普适性。
实施例3
分别配置对苯二甲酸/过氧化氢3组混合溶液,三组混合溶液中对苯二甲酸的浓度均为20μM,过氧化氢的浓度分别为:2μM,5μM,20μM。三组混合溶液均调节pH=9.0,预曝氮气30min至氧气浓度低于2mg/L后,倒入光反应装置的反应管中密封。在低压汞灯(10W,GPH212T5L,贺利氏)辐照下5min(0.2mW/cm2)。分别利用显色法测定溶液中的过氧化氢,计算得到过氧化氢的分解率分别为:100%,100%,100%。
本实施例中,过氧化物与活化剂的摩尔比分别为1:10;1:4;1:1,光照5min后,均可实现反应中过氧化物完全分解。因此只要确保过氧化物与活化剂的摩尔比小于1,均可实现分解过氧化物之目的。
实施例4
分别配置50μM的香豆素溶液两份(A组和B组);向含有浓度为50μM的香豆素的水中投加40μM的双氧水和50μM的对苯二甲酸得到混合溶液一份(C组),均调节pH=9.0。A组和C组预曝氮气30min,然后倒入光反应装置的反应管中密封。B组不进行曝气,直接放入光反应管中。三组均采用低压汞灯辐照10min(0.1mW/cm2)。采用高效液相色谱仪(Waters 1525,美国)同时检测香豆素和7-羟基香豆素,检测结果如图3、图4所示,可见,A组和B组的香豆素去除率分别为3%;4%。C组的香豆素去除率为40%,并且产生7-羟基香豆素为:0.4μM。
以上实验说明对苯二甲酸体系可以有效的降解香豆素,在具体实施中,为确保反应完全,混合溶液中过氧化物浓度优选大于有机物浓度;并且通过产物发现,羟基化产物7-羟基香豆素会迅速产生。说明反应体系中是羟基自由基在其主要的活性粒子。说明了该方法是以促进双氧水分解产生羟基自由基为主要特征,考虑到羟基自由基的强氧化性,说明该本实施例提供的反应体系可以氧化其他有机污染物(如抗生素,有机磷农药,难降解药物等),具有普适性。
实施例5
向含有浓度为50μM苯甲酸的水中投加40μM的双氧水,得到混合溶液,pH=9预曝氮气30min,然后倒入光反应装置的反应管中密封。采用低压汞灯辐照10min(0.2mW/cm2)。
采用高效液相色谱仪(Waters 1525,美国)同时检测羟基化产物,检测结果如图5所示,可见反应获得苯酚1.3μM;邻羟基苯甲酸1.7μM;间羟基苯甲酸2.5μM。
实施例6
向含有浓度为50μM对苯二甲酸的水中投加40μM的双氧水,得到混合溶液,pH=9.0。预曝氮气30min,然后倒入光反应装置的反应管中密封。采用低压汞灯辐照5min。采用高效液相色谱仪(Waters 1525,美国)进行检测,并且以标准品来定量,检测结果如图6所示,可见,本实施例反应获得2-羟基对苯二甲酸5.5μM;对羟基苯甲酸3μM。两者产率分别为:20%和13%。
在具体实施中,调节本申请非金属催化的有机类芬顿反应试剂pH3-9,在紫外光源强度大于0.1mW/cm2条件下辐照10min,即可产生酚类物质,是指苯甲酸经过羟基化过程,产生的加羟基产物和脱羧基后加羟基的酚类物质,如苯酚,2-羟基苯甲酸,3-羟基苯甲酸,4-羟基苯甲酸等。
实施例7
分别配置三个对苯二甲酸/双氧水混合溶液,其中对苯二甲酸的浓度为50μM,双氧水浓度为40μM.分别调节pH=3.0,6.0,11.0,预曝氮气30min至氧气浓度低于2mg/L后,倒入光反应装置的反应管中密封。在低压汞灯(10W,GPH212T5L,贺利氏)辐照下10min(0.1mW/cm2)。
分别利用显色法测定溶液中的双氧水的分解率分别为:30%;99%;100%。本实施例说明在pH>6.0条件下,该有机类芬顿体系均能有效快速的分解双氧水,说明了反应体系的pH范围广的优势。pH=3.0条件下,分解率为30%,促进分解的效果有所减弱,但是依然具有一定的促进效果。
对比实施例1
分别配置浓度为40μM的双氧水,过一硫酸盐和过氧乙酸三种溶液,调节pH=9.0,预曝氮气30min,然后倒入光反应装置的反应管中密封。在低压汞灯辐照下10min。双氧水分解率为5%;过一硫酸盐的分解率为4%;过氧乙酸的分解率为6%。
结合实施例1和实施例2,本对比实施例证明了通过加入苯甲酸类物质可以有效促进过氧化物的分解。
对比实施例2
向含有浓度为50μM的香豆素的水中投加40μM的双氧水得到混合溶液,然后倒入光反应装置的反应管中密封。采用低压汞灯辐照10min。香豆素去除率为10%,同时产生7-羟基香豆素:0.08μM。
结合实施例4,本实施例对比证明了缺氧体系的重要性,排氧操作后(曝氮气),才可以迅速的促进香豆素降解。
对比实施例3
向含有浓度为50μM对苯二甲酸的溶液中,预曝氮气30min,然后倒入光反应装置的反应管中密封。采用低压汞灯辐照5min。采用高效液相色谱仪(Waters 1525,美国)进行检测,并且以标准品来定量,可以获得2-羟基对苯二甲酸0.05μM;对羟基苯甲酸(低于检出限:0.1μM)。结合实施例6,本实施例对比证明了该反应体系可以有效的促进酚类物质的生成。
以上所述实施例仅表达了本发明的实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域技术人员来说,在不脱离本发明构思的前提下,还可以做出若干改进,这些改进都属于本发明的保护范围。
Claims (3)
1.一种非金属催化的有机类芬顿反应试剂,由过氧化物溶液和活化剂组成,其特征在于,所述活化剂为苯甲酸、苯甲酸衍生物中的至少一种;
所述苯甲酸衍生物为官能团取代的苯甲酸或苯甲酸盐化合物中的至少一种;所述官能团取代的苯甲酸为1,3-苯二甲酸、1,4-苯二甲酸、4-羟基苯甲酸、4-甲基苯甲酸、4-氯苯甲酸中的至少一种;所述苯甲酸盐化合物为苯甲酸钠、苯甲酸钾、1,3-苯二甲酸钠中的至少一种;
所述过氧化物为过氧化氢、过氧乙酸、过氧丙酸、过硫酸盐中的至少一种;所述过氧化物与活化剂的摩尔比小于1。
2.如权利要求1所述非金属催化的有机类芬顿反应试剂在降解有机污染物领域中的应用,其特征在于,将所述非金属催化的有机类芬顿反应试剂与含有有机污染物的溶液混合后,调节pH为3-11,缺氧条件下,将溶液置于紫外光源下,即可实现有机污染物的降解;
所述缺氧条件是指溶液中溶解氧的浓度低于2 mg/L,所述紫外光源强度大于0.1 mW/cm2。
3.如权利要求1所述非金属催化的有机类芬顿反应试剂在制备酚类物质或生产羟基自由基中的应用,其特征在于,调节非金属催化的有机类芬顿反应的试剂pH为3-11,缺氧条件下,将试剂置于紫外光源下,即可实现制备酚类物质或生产羟基自由基;
所述酚类物质包括苯酚、2-羟基苯甲酸、3-羟基苯甲酸、4-羟基苯甲酸中的至少一种;
所述缺氧条件是指溶液中溶解氧的浓度低于2 mg/L,所述紫外光源强度大于0.1 mW/cm2。
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