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非贵金属催化电解无害化去除硝酸盐氮的反应机制

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叶舒帆, 张杨, 宋跃群, 林海转, 胡筱敏. 非贵金属催化电解无害化去除硝酸盐氮的反应机制[J]. 环境化学, 2013, 32(5): 755-761. doi: 10.7524/j.issn.0254-6108.2013.05.006
引用本文: 叶舒帆, 张杨, 宋跃群, 林海转, 胡筱敏. 非贵金属催化电解无害化去除硝酸盐氮的反应机制[J]. 环境化学, 2013, 32(5): 755-761. doi: 10.7524/j.issn.0254-6108.2013.05.006
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YE Shufan, ZHANG Yang, SONG Yuequn, LIN Haizhuan, HU Xiaomin. Study on reaction mechanism of NO3--N harmless removal by non-precious metals catalytic electrolysis[J]. Environmental Chemistry, 2013, 32(5): 755-761. doi: 10.7524/j.issn.0254-6108.2013.05.006
Citation: YE Shufan, ZHANG Yang, SONG Yuequn, LIN Haizhuan, HU Xiaomin. Study on reaction mechanism of NO3--N harmless removal by non-precious metals catalytic electrolysis[J]. Environmental Chemistry, 2013, 32(5): 755-761. doi: 10.7524/j.issn.0254-6108.2013.05.006
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非贵金属催化电解无害化去除硝酸盐氮的反应机制

  • 1.

    温州市环境保护设计科学研究院, 温州, 325027;

  • 2.

    温州医学院信息与工程学院, 温州, 325035;

  • 3.

    东北大学, 沈阳, 110004

  • 基金项目:

    浙江省省级环境保护专项资金项目(温财行[2012]827-5)

    温州医学院人才启动项目(QTJ11008)资助.

Study on reaction mechanism of NO3--N harmless removal by non-precious metals catalytic electrolysis

  • 1.

    Wenzhou Environmental Protection Design & Research Institute, Wenzhou, 325027, China;

  • 2.

    College of Information & Engineering, Wenzhou Medical College, Wenzhou, 325035, China;

  • 3.

    Northeastern University, Shenyang, 110004, China

  • Fund Project:

  • 摘要: 以Ti/Co-Fe-Cu为阴极,Ti/IrO2-RuO2为阳极组成无隔膜电解体系,对非贵金属催化电解无害化去除NO3--N的反应机制进行了实验研究和理论分析.结果表明,NO3--N阴极催化还原过程中,反应物、产物需要通过对流、扩散作用,克服电场力,迁移至目标位置;在非贵金属的催化作用下,NO3--N受还原剂攻击,逐步还原为NH4+-N;还原中间产物NO-N和NH-N直接生成N2-N的过程受抑制,产物NH4+-N难以被再度直接氧化.添加Cl-作为支持电解质,实验电解体系发生阳极析氯、Cl2水解、NH4+-N氯氧化等过程,可将NH4+-N氧化为N2-N,且出水中NO3--N、NO2--N、氯胺类浓度很低.NO3--N无害化去除的反应机制是NO3--N在催化作用下,经传质、吸脱附、电子交换过程,还原为NH4+-N,NH4+-N经由Cl-→Cl2→HOCl →Cl-电解氯氧化循环,最终生成N2-N.
    Abstract: In this study, experimental research and theoretical analysis on reaction mechanism of NO3--N harmless removal catalyzed by non-precious metal in the no-diaphragm electrolysis system which constituted of Ti/Co-Fe-Cu cathode & Ti/IrO2-RuO2 anode have been carried out. The results showed that reactants and products overcame electric field force and moved to target position through convection and diffusion effect in the process of cathode catalytic reduction. When catalyzed by non-precious metal, NO3--N was attacked by the reductant and then reduced to NH4+-N gradually; The direct generation of N2-N from intermediate products NO-N and NH-N was suppressed, and NH4+-N was difficult to be directly oxidized. Cl- was added as supporting electrolyte, and NH4+-N was oxidized to N2-N in experimental electrolysis system through chlorine evolution on anode, Cl2 hydrolysis and NH4+-N chlorine-oxidation, etc. Besides, the concentrations of NO3--N, NO2--N and chloramines in experimental effluent were pretty low. It's speculated that the reaction mechanism of NO3--N harmless removal in this study is as following: NO3--N was catalytic reduced to NH4+-N through mass transfer, adsorption, desorption and electronic exchange, and then NH4+-N was oxidized to N2-N by the electrolysis chlorine oxidation circulation of Cl-→Cl2→HOCl→Cl-.
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  • [1] 杨琰, 蔡鹤生, 刘存富, 等. NO3-中15N和18O 同位素新技术在岩溶地区地下水氮污染研究中的应用——以河南林州食管癌高发区研究为例[J]. 中国岩溶, 2004, 23(3): 206-212
    [2] Sandor J, Kiss I, Farkas O, et al. Association between gastric cancer mortality and nitrate content of drinking water: Ecological study on small area inequalities[J]. European Journal of Epidemiology, 2001, 17: 443-447
    [3] Barada P D, Sanjeev C. Electrochemical denitrification of simlutated ground water[J]. Water Res, 2005, 39: 4065-4072
    [4] Vorlop K D, Tacke T. Erste schritte auf dem weg zur edelmetall katalysierten nitrund nitritent fernung aus trinkwasser[J]. Chem Ing Tech, 1989, 61: 836-845
    [5] 高建峰, 徐春燕, 王久芬, 等. 无机膜复合催化反应器脱除水中硝酸盐氮[J]. 环境化学, 2008, 27(5): 596-599
    [6] Gauthard F, Epron F, Barbier J. Palladium and platinum-based catalysts in the catalytic reduction of nitrate in water: Effect of copper, silver, or gold addition[J]. J Catal, 2003, 220(1): 182-191
    [7] 周丽, 邓慧萍, 桑松表. 多孔钛板负载Pd-Cu催化还原水中硝酸盐氮的研究[J]. 环境化学, 2008, 27(2): 172-176
    [8] 周丽, 邓慧萍, 刘振中, 等. 多孔钛板负载Pd-Sn电催化去除硝酸盐氮的研究[J]. 供水技术, 2007, 1(5): 32-36
    [9] Jacinto S, Hannelore V. Catalytic hydrogenation of nitrates in water over a bimetallic catalyst [J]. Appl Catal B: Environ, 2005, 57(4):247-256
    [10] Wang Y, Qu J H, Liu H J. Effect of liquid property on adsorption and catalytic reduction of nitrate over hydrotalcite-supported Pd-Cu catalyst [J]. J Mol Catal A: Chem, 2007, 272(1/2): 31-37
    [11] Barrabes N, Just J, Dafinov A, et al. Catalytic reduction of nitrate on Pt-Cu and Pd-Cu on active carbon using continuous reactor the effect of copper nanoparticles[J]. Appl Catal B: Environ, 2006, 62(1/2): 77-85
    [12] Garron A, Epron F. Use of formic as reducing agent for application in catalytic reduction of nitrate in water [J]. Water Res, 2005, 39(13): 3073-3081
    [13] Chaplin B, Roundy E, Guy K, et al. Effects of natural water ions and humic acid on catalytic nitrate reduction kinetics using an alumina supported Pd-Cu catalyst[J].Environ Sci Tech, 2006, 40 (9): 3075-3081
    [14] 张燕, 陈英旭, 刘宏远. Pd-Cu/γ-Al2O3催化还原硝酸盐的研究[J]. 催化学报, 2003, 24(4): 270-274
    [15] 叶舒帆, 胡筱敏, 张杨, 等. 一种新型电化学法处理硝态氮废水的初步研究[J]. 环境科学, 2010, 30(8): 1827-1833
    [16] 叶舒帆, 胡筱敏, 董俊, 等. 钛基修饰电极催化电解去除水中硝酸盐氮的研究[J]. 中国环境科学, 2011, 31(1): 44-49
    [17] 胡筱敏, 叶舒帆, 和英滇, 等. 电解催化还原-氯氧化无害化去除水中硝酸盐氮[J]. 环境科学研究, 2011, 24(5): 533-539
    [18] 叶舒帆, 胡筱敏, 和英滇, 等. 非贵金属催化还原水中的硝酸盐氮[J]. 环境化学, 2011, 30(10): 1711-1717
    [19] Lidia S, Santosh N K, Rao N N, et al. Influence of anode material on electrochemical oxidation for the treatment of tannery wastewater[J]. Water Res, 2005, 39: 1601-1613
    [20] 褚衍洋, 杨波, 李玲玲, 等. 氨氮在两种电解质体系下的电化学氧化[J]. 高校化学工程学报, 2010, 24(1): 71-75
    [21] 陈金銮. 氨氮的电氧化技术及其应用研究. 北京: 清华大学, 2008: 33
    [22] Prusse U, Hahnlein M, Daum J, et al. Improving the catalytic nitrate reduction[J]. Catal Today, 2000, 55(1/2): 79-90
    [23] 高建峰. 水中硝酸盐氮复合催化还原无害化的原理和技术研究. 天津: 南开大学, 2004: 33
    [24] Warna J, Turunen I, Salmi T, et al. Kinetics of nitrate reduction in monolith reactor [J]. Chem Eng Sci, 1994, 49(28B): 5763-5773
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  • 收稿日期:  2012-08-27

非贵金属催化电解无害化去除硝酸盐氮的反应机制

  • 1.  温州市环境保护设计科学研究院, 温州, 325027;
  • 2.  温州医学院信息与工程学院, 温州, 325035;
  • 3.  东北大学, 沈阳, 110004
  • 收稿日期:  2012-08-27
基金项目:

浙江省省级环境保护专项资金项目(温财行[2012]827-5)

温州医学院人才启动项目(QTJ11008)资助.

摘要: 以Ti/Co-Fe-Cu为阴极,Ti/IrO2-RuO2为阳极组成无隔膜电解体系,对非贵金属催化电解无害化去除NO3--N的反应机制进行了实验研究和理论分析.结果表明,NO3--N阴极催化还原过程中,反应物、产物需要通过对流、扩散作用,克服电场力,迁移至目标位置;在非贵金属的催化作用下,NO3--N受还原剂攻击,逐步还原为NH4+-N;还原中间产物NO-N和NH-N直接生成N2-N的过程受抑制,产物NH4+-N难以被再度直接氧化.添加Cl-作为支持电解质,实验电解体系发生阳极析氯、Cl2水解、NH4+-N氯氧化等过程,可将NH4+-N氧化为N2-N,且出水中NO3--N、NO2--N、氯胺类浓度很低.NO3--N无害化去除的反应机制是NO3--N在催化作用下,经传质、吸脱附、电子交换过程,还原为NH4+-N,NH4+-N经由Cl-→Cl2→HOCl →Cl-电解氯氧化循环,最终生成N2-N.

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