电解亚氯酸钠制备二氧化氯的催化反应动力学研究

doi:10.19964/j.issn.1006-4990.2024-0308

Abstract

Abstract:

In order to develop a safe，efficient and convenient method for the preparation of high-purity ClO₂，the factors influencing the preparation of ClO₂ from electrolysis of NaClO₂ by examining the influence of different catalysts in a double-compartment electrolytic cell were systematically investigated and the law of reaction kinetics，and the corrosion of the electrodes under long-term operation was characterized.The results showed that high-purity ClO₂ could be prepared by electrolyzing NaClO₂ in a double chamber electrolytic cell.The optimal reaction conditions were NaClO₂ concentration of 0.6 mol/L，NaCl concentration of 0.2 mol/L，current of 3 A，and reaction time of 30 min，at which the ClO₂ yield and purity could reach 51.2% and 95.1%，respectively.The reaction process was a zero-stage reaction，k=13.62 mol/（L·min）.MnO₂ showed better performace，the best substance ratio n（MnO₂）/n（NaClO₂）=0.10，the yield and purity of ClO₂ could reach 66.1% and 98.1%，respectively.The catalytic reaction process was still a zero-stage reaction.MnSO₄ had certain catalytic effect on the preparation of ClO₂，the concentration was too high and block the proton membrane to reduce its yield，the optimal concentration of MnSO₄ was 0.05 mol/L，the yield and purity of ClO₂ could be up to 56.4% and 96.7%，respectively.NiSO₄，CoSO₄ blocked the proton exchange membrane to affect the efficiency of proton migration，which inhibited the generation of ClO₂.The characterization results of XRD，SEM and EDS showed that TiCl₂ was generated on the surface of the electrode for a long period of time，but the titanium-based ruthenium-iridium alloy electrode used did not corrode significantly，and it could be used for a long period of time，and the results provided a theoretical basis for the development of a new method of preparation of ClO₂.

Key words: disinfection, chlorine dioxide, sodium chlorite, electrolysis, reaction kinetics

CLC Number:

TQ124.43

WU Mingsong, ZOU Zhigang, WANG He, CHEN Yu, ZHENG Jiaxing. Study on catalytic reaction kinetics for preparation of chlorine dioxide from electrolyzed sodium chlorite[J]. Inorganic Chemicals Industry, 2025, 57(7): 44-49.

Figures/Tables 7

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References 20

[1]	陈虹，王群，方欣，等.二氧化氯的抗菌效果及其在食品保鲜中的研究进展［J］.保鲜与加工，2024，24（1）：90-96.
	CHEN Hong， WANG Qun， FANG Xin，et al.Antibacterial effect of chlorine dioxide and its research progress in food preservation［J］.Storage and Process，2024，24（1）：90-96.
[2]	郭锦棠，宋巧巧，高田田，等.固态二氧化氯消毒剂的制备与性能研究［J］.天津大学学报（自然科学与工程技术版），2022，55（9）：903-908.
	GUO Jintang， SONG Qiaoqiao， GAO Tiantian，et al.Preparation and performance analysis of a solid chlorine dioxide disinfectant［J］.Journal of Tianjin University（Science and Technology），2022，55（9）：903-908.
[3]	刘张义，郝丽梅，衣颖，等.气体二氧化氯快速制备技术及其在消毒中的应用研究［J］.中国消毒学杂志，2021，38（6）：410-413.
	LIU Zhangyi， HAO Limei， YI Ying，et al.Study on rapid preparation of gas chlorine dioxide and its application in disinfection［J］.Chinese Journal of Disinfection，2021，38（6）：410-413.
[4]	刘远鹏，张学武，甘云润.一种电解法制备高纯二氧化氯设备的研究［J］.中国新技术新产品，2017（4）：7-8.
	LIU Yuanpeng， ZHANG Xuewu， GAN Yunrun.Research on equipment for preparing high-purity chlorine dioxide by electrolysis［J］.China New Technologies and Products，2017（4）：7-8.
[5]	刘艳霞，韩瑞雄，赵红，等.电解法制高纯二氧化氯工艺在水处理中的应用［J］.无机盐工业，2011，43（12）：57-59.
	LIU Yanxia， HAN Ruixiong， ZHAO Hong，et al.Application of preparation process of high pure chlorine dioxide by electrolysis method in water treatment［J］.Inorganic Chemicals Industry，2011，43（12）：57-59.
[6]	韩瑞雄.电解法制备高纯二氧化氯的技术研究［D］.北京：北京化工大学，2010.
	HAN Ruixiong.Research on electrolytic preparation of extremely pure chlorine dioxide［D］.Beijing：Beijing University of Chemical Technology，2010.
[7]	TIAN Mei， LI Yingying， SUN Haochen，et al.Preparation of chlorine dioxide by electrocatalytic reduction of sodium chlorate［J］.Advanced Materials Research，2013，781-784：342-345.
[8]	邓新华，黄志明，乔海东.中联电解法二氧化氯发生装置的研究与应用［C］//全国化工标准物质委员会二氧化氯专业委员会.二氧化氯与水处理技术研讨会论文集.北京：化学工业出版社，2010：57-63.
[9]	翁述贤，薄采颖，贾普友，等.二氧化氯的制备及应用进展［J］.纤维素科学与技术，2022，30（3）：62-71.
	WENG Shuxian， BO Caiying， JIA Puyou，et al.Progress of preparation and application of chlorine dioxide［J］.Journal of Cellulose Science and Technology，2022，30（3）：62-71.
[10]	WU C T， CHANG Chenyu， LI Yiying，et al.An efficiency analysis for the production of chlorine dioxide by the electrolysis of brine in seawater desalination plants［J］.Water Quality Research Journal，2019，54（2）：127-133.
[11]	王洋.电氧化法制备二氧化氯溶液的研究［D］.长春：吉林大学，2012.
	WANG Yang.Investigations on electro-oxidation preparation of chlorine dioxide solution［D］.Changchun：Jilin University，2012.
[12]	范丹丹，田颖，韩立达，等.催化电解亚氯酸钠制备高纯二氧化氯［J］.功能材料，2017，48（9）：9150-9156.
	FAN Dandan， TIAN Ying， HAN Lida，et al.Catalytic electrolysis of sodium chlorite to prepare highly pure chlorine dioxide［J］.Journal of Functional Materials，2017，48（9）：9150-9156.
[13]	吴少宇，蔡郡倬，冉一伽，等.电化学活化NaClO₂去除再生灌溉水中磺胺地索辛［J］.四川轻化工大学学报（自然科学版），2023，36（5）：16-25.
	WU Shaoyu， CAI Junzhuo， RAN Yijia，et al.Electrochemical activation of NaClO₂ for removal of sulfadimethoxine antibiotics from reclaimed irrigation water［J］.Journal of Sichuan University of Science & Engineering（Natural Science Edition），2023，36（5）：16-25.
[14]	BERGMANN H， KOPARAL S.The formation of chlorine dioxide in the electrochemical treatment of drinking water for disinfection［J］.Electrochimica Acta，2005，50（25/26）：5218-5228.
[15]	韩瑞雄，周俊波.电解法制备高纯ClO₂技术［J］.化学工程，2010，38（7）：54-57，70.
	HAN Ruixiong， ZHOU Junbo.Electrolytic preparation technology of extremely pure ClO₂ ［J］.Chemical Engineering（China），2010，38（7）：54-57，70.
[16]	刘宇鹤，吴明松，王欣舒，等.二氧化氯稳定性相关基本性质及影响因素综述［J］.无机盐工业，2021，53（3）：18-23.
	LIU Yuhe， WU Mingsong， WANG Xinshu，et al.Review of basic properties and influence factors related to stability of chlorine dioxide［J］.Inorganic Chemicals Industry，2021，53（3）：18-23.
[17]	赵宏伟.二氧化锰合成及催化氧化甲醛应用研究［D］.成都：电子科技大学，2023.
	ZHAO Hongwei.Manganese dioxide synthesis and application research on catalytic oxidation of formaldehyde［D］.Chengdu：University of Electronic Science and Technology of China，2023.
[18]	王傲雪，郭琳，郑金玉，等.固体氧化物电解池材料发展现状与展望［J］.洁净煤技术，2023，29（3）：62-77.
	WANG Aoxue， GUO Lin， ZHENG Jinyu，et al.Research status and development prospect of solid oxide electrolyzer cells materials［J］.Clean Coal Technology，2023，29（3）：62-77.
[19]	YANG Shasha， RAO Dewei， YE Jingjing，et al.Mechanism of transition metal cluster catalysts for hydrogen evolution reaction［J］.International Journal of Hydrogen Energy，2021，46（5）：3484-3492.
[20]	CHANDRASEKARA PILLAI K， KWON T O， PARK B B，et al.Using RuO₂ anode for chlorine dioxide production in an un-divided electrochemical cell［J］.Water Science and Technology，2010，61（8）：2151-2160.

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Study on catalytic reaction kinetics for preparation of chlorine dioxide from electrolyzed sodium chlorite

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