电解亚氯酸钠制备二氧化氯的催化反应动力学研究
收稿日期: 2024-05-30
网络出版日期: 2024-08-28
基金资助
安徽省教育厅重大项目(2024AH040184);石家庄市驻冀高校产学研合作项目(241200074A)
Study on catalytic reaction kinetics for preparation of chlorine dioxide from electrolyzed sodium chlorite
Received date: 2024-05-30
Online published: 2024-08-28
为了开发一种安全、高效、便捷的高纯ClO2制备新方法，系统考察了双室电解池中不同催化剂对电解NaClO2制备ClO2的影响因素及反应动力学规律，并对长期运行下电极的腐蚀情况进行了表征。结果表明，在双室电解池中电解NaClO2可以制得高纯度ClO2。最佳反应条件：NaClO2浓度为0.6 mol/L、NaCl浓度为0.2 mol/L、电流为3 A、反应时间为30 min，此时ClO2收率和纯度分别可达51.2%和95.1%。反应过程为零级反应，k=13.62 mol/（L·min）。MnO2催化效果较好，最佳的物质的量比n（MnO2）/n（NaClO2）=0.10，此时ClO2收率和纯度分别可达66.1%和98.1%；催化反应过程依然为零级反应。MnSO4对制备ClO2有一定催化作用，但浓度过高会堵塞质子膜降低其收率，MnSO4的最佳投加浓度为0.05 mol/L，此时ClO2收率和纯度分别可达56.4%和96.7%。NiSO4、CoSO4会堵塞质子交换膜影响质子迁移效率，从而抑制ClO2生成。XRD、SEM和EDS表征结果表明，长期运行的电极表面会生成TiCl2，但所用的钛基钌铱合金电极并未明显腐蚀，可以长期使用，其结果对开发ClO2新的制备方法提供了理论依据。
吴明松 , 邹志刚 , 王鹤 , 陈瑜 , 郑家星 . 电解亚氯酸钠制备二氧化氯的催化反应动力学研究[J]. 无机盐工业, 2025 , 57(7) : 44 -49 . DOI: 10.19964/j.issn.1006-4990.2024-0308
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
| [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. |
/
| 〈 |
|
〉 |
