CN105776415A - 一种有效降解污水中氧化多壁碳纳米管的方法 - Google Patents
一种有效降解污水中氧化多壁碳纳米管的方法 Download PDFInfo
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Abstract
本发明公开了一种有效降解污水中氧化多壁碳纳米管的方法，该方法通过紫外光‑芬顿法对污水中氧化多壁碳纳米管进行降解。本发明通过紫外光结合芬顿法可产生更多的·OH，显著提高降解有机物分解速率，破坏O‑MWNTs的碳骨架，有机碳被氧化成CO2气体。
Description
技术领域
本发明属于碳基材料降解技术领域，具体涉及一种有效降解污水中氧化多壁碳纳米管的方法。
背景技术
自从90年代初Iijima等发现具有纳米尺寸的多壁碳纳米管（MWNTs）以来，多壁碳纳米管受到众多国内外学者的广泛关注。多壁碳纳米管具有独特的中空管状结构，具有大的比表面积和高的化学稳定等优点，使其在很多领域具有广阔的应用前景，例如：场发射体、储氢材料、为电子元件、催化剂载体等。
由于多壁碳纳米管的广泛应用，在其合成、制造和使用过程中都会产生释放，导致环境风险增大。且工业生产中多采用强酸对多壁碳纳米管进行氧化，排出的污水中由于含有多壁碳纳米管而对生物存在毒性作用。Allen等一些研究者采用生物酶法降解碳纳米管，但是这种方法降解周期长，成本高，并且生物酶在强酸环境中难以存活，不适用工业污水中碳纳米管氧化物的降解。Zhang等研究者采用细菌降解多壁碳纳米管，但是这个方法需要额外的碳源，降解后的MWNTs需要进一步研究其对环境的影响，并没表明其最终产物是无害的。所以，寻找一种能有效且经济的降解氧化多壁碳纳米管（O-MWNTs）是非常必要的。
发明内容
本发明的目的是为了解决现有技术中存在的缺陷，提供一种能有效降解工业污水中氧化多壁碳纳米管的方法。
为了达到上述目的，本发明提供了一种有效降解污水中氧化多壁碳纳米管的方法，该方法通过紫外光-芬顿法对污水中氧化多壁碳纳米管进行降解。
具体步骤如下：
(1)取200mL工业污水，其中氧化多壁碳纳米管的浓度为0.4~0.5mg/mL，搅拌均匀后，超声30 ~ 60分钟；
(2)采用浓度为1 mol/ L 的NaOH溶液调节pH值为2 ~ 4，优选pH值为3；
(3)然后加入1 mL浓度为5 ppm 的FeCl3 水溶液，搅拌均匀，再加入2-4 mL（优选加入量为2 mL）H2O2溶液，搅拌均匀；所述H2O2溶液浓度为1 g/L；
(4)将步骤（3）制备的溶液放在紫外光λ= 185 nm波长条件下照射，每天添加1-2 mL（优选加入量为1 mL）的所述H2O2溶液，照射时间为24小时至7天，优选照射时间为7天。
本发明相比现有技术具有以下优点：本发明通过紫外光结合芬顿法可产生更多的·OH，显著提高降解有机物分解速率，破坏O-MWNTs的碳骨架，使其降解成CO2。使用短波长 (λ= 185 nm) 使其降解更彻底，从而消除其对环境的毒性危害。另外，芬顿试剂对环境不会产生污染，避免了花费额外人力物力进行后续的处理，同时使用的芬顿试剂价格便宜，降解周期短。
附图说明
图1为本发明实施例中污水的降解过程图；
图2为本发明实施例中污水在降解过程中的紫外光谱图；
图3为本发明实施例中污水在降解6天后与O-MWNTs的红外光谱对比图。
图1中，1、2、3、4、5分别为污水在降解1、4、8、24和168小时的样品；
图3中，A为O-MWNTs，B为降解6天后的污水样品。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
取工业污水200 mL，其中氧化多壁碳纳米管浓度为0.4 mg/mL，超声30 min；用NaOH 水溶液（浓度为1 mol/ L） 调节溶液的pH= 3；然后加入1 mL FeCl3 水溶液（浓度为5ppm），搅拌均匀，再加入 2 mL H2O2溶液（浓度为1 g/L），将溶液放在紫外光λ= 185 nm波长条件下照射，每天添加1 mL的H2O2溶液（浓度为1 g/L），降解7天。
从图1中，从样品1至5可以发现O-MWNTs溶液由悬浊液变成水溶液，其粒径尺寸变小。降解8小时后，样品3溶液开始变浅，由深褐色变成浅棕色，说明O-MNTs的C=C键与羟基自由基开始了加成反应，C-C被打开，碳骨架逐渐消失。7天后，O-MWNTs几乎完全降解，样品5溶液变澄清。
同时，分别在降解0、1、2、4、6、8、12、24、72、144和168小时，取出降解的污水，进行紫外光谱测试。从图2可知，在紫外波长198 nm处，污水的吸光度为0.53。随着降解时间的增加，样品吸光度先增加后减小，到7天后几乎为0。说明O-MWNTs在7天后可达到完全降解。
对降解6天的污水和O-MWNTs进行红外光谱对比，从图3可看出，O-MWNTs样品A在3131 cm-1附近有一个较宽较强的吸收峰应属OH的伸缩动峰；在1700 cm-1处有一个较弱的吸收峰为O-MWNTs的羰基上的C=O伸缩振动吸收峰；在1400 cm-1处有一个较强的吸收峰应属C-H弯曲振动峰。说明O-MWNTs含有羟基、羧基等官能团可使其溶于水中。降解6天后的样品B在3430 cm-1附近有一个较强的吸收峰应属OH的伸缩动峰；在1636 cm-1附近的峰应为C=O和OH之间氢键的振动吸收；1140 cm-1附近的峰应为C-O-C伸缩振动吸收；在2360 cm-1附近有一个较强的峰应为CO2的吸收峰。说明O-MWNTs在光芬顿降解过程中降解产物主要以C-O-C形式存在，并且在降解6天后，有大量的CO2产生。从而证明了O-MWNTs是可以被羟基自由基氧化成CO2和H2O。
Claims (3)
1.一种有效降解污水中氧化多壁碳纳米管的方法，其特征在于：通过紫外光-芬顿法对污水中氧化多壁碳纳米管进行降解。
2.根据权利要求1所述的方法，其特征在于：包括以下步骤：
(1)取200mL工业污水，其中氧化多壁碳纳米管的浓度为0.4~0.5mg/mL，搅拌均匀后，超声30 ~ 60分钟；
(2) 采用浓度为1 mol/ L 的NaOH溶液调节pH值为2 ~ 4；
(3) 然后加入1 mL浓度为5 ppm 的FeCl3 水溶液，搅拌均匀，再加入2-4 mLH2O2溶液，搅拌均匀；所述H2O2溶液浓度为1 g/L；
(4) 将步骤（3）制备的溶液放在紫外光λ= 185 nm波长条件下照射，每天添加1-2 mL的所述H2O2溶液，照射时间为24小时至7天。
3.根据权利要求2所述的方法，其特征在于：所述步骤（2）中加入H2O2溶液2 mL；所述步骤（4）中H2O2溶液每天添加量为1 mL；所述照射时间为7天。
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| CN107737432A (zh) * | 2017-09-22 | 2018-02-27 | 深圳市中科摩方科技有限公司 | 一种碳纳米材料的高效降解转化方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2500323A1 (en) * | 2011-03-14 | 2012-09-19 | E' Cosi' S.R.L. | Method for the degradation of industrial wastewater and apparatus for performing the method |
| CN103819034A (zh) * | 2014-02-24 | 2014-05-28 | 华北电力大学 | 超声波联合光-Fenton氧化修复有机污染地下水的系统及方法 |
| KR20150039942A (ko) * | 2013-10-04 | 2015-04-14 | 국립대학법인 울산과학기술대학교 산학협력단 | 카본나노튜브/퍼설페이트 시스템을 이용한 수중 오염물질 처리방법 및 장치 |
| CN105253950A (zh) * | 2015-11-13 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | 紫外光协同电Fenton体系降解有机废水的方法及设备 |
| CN105347430A (zh) * | 2015-11-05 | 2016-02-24 | 南京信息工程大学 | 一种有效降解污水中氧化石墨烯的方法 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2500323A1 (en) * | 2011-03-14 | 2012-09-19 | E' Cosi' S.R.L. | Method for the degradation of industrial wastewater and apparatus for performing the method |
| KR20150039942A (ko) * | 2013-10-04 | 2015-04-14 | 국립대학법인 울산과학기술대학교 산학협력단 | 카본나노튜브/퍼설페이트 시스템을 이용한 수중 오염물질 처리방법 및 장치 |
| CN103819034A (zh) * | 2014-02-24 | 2014-05-28 | 华北电力大学 | 超声波联合光-Fenton氧化修复有机污染地下水的系统及方法 |
| CN105347430A (zh) * | 2015-11-05 | 2016-02-24 | 南京信息工程大学 | 一种有效降解污水中氧化石墨烯的方法 |
| CN105253950A (zh) * | 2015-11-13 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | 紫外光协同电Fenton体系降解有机废水的方法及设备 |
Non-Patent Citations (1)
| Title |
|---|
| 林彩凤等: "高浓度酚醛废水的处理", 《厦门大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107737432A (zh) * | 2017-09-22 | 2018-02-27 | 深圳市中科摩方科技有限公司 | 一种碳纳米材料的高效降解转化方法 |
| CN107737432B (zh) * | 2017-09-22 | 2020-05-08 | 深圳市中科摩方科技有限公司 | 一种碳纳米材料的高效降解转化方法 |
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