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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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000003203 everyday effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 2
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- 239000012028 Fenton's reagent Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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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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 |
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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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