无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ
研究与开发

电解制备焦磷酸锰(Ⅲ)盐工艺条件及动力学研究

  • 刘思浩 ,
  • 陈金芳 ,
  • 王岩
展开
  • 武汉工程大学化工与制药学院,绿色化工过程教育部重点实验室,湖北武汉 430073
刘思浩(1995— ),男,硕士研究生,研究方向为电化学;E-mail: 745571160@qq.com。

收稿日期: 2019-03-21

  网络出版日期: 2020-06-10

基金资助

国家自然科学基金项目(20876118)

Study on technological condition and kinetic of preparing manganese(Ⅲ) pyrophosphate by electrolysis

  • Sihao Liu ,
  • Jinfang Chen ,
  • Yan Wang
Expand
  • Key Laboratory for Green Chemical Process of Ministry of Education,Wuhan Institute of Technology,Wuhan 430073,China

Received date: 2019-03-21

  Online published: 2020-06-10

摘要

首次采取二极室在焦磷酸介质中电解制备可溶性三价锰盐。分别研究了电流密度、焦磷酸浓度、电解温度等因素对电极反应制备可溶性三价锰盐浓度和电流效率的影响。通过单因素条件实验进行了工艺参数的优化,对工艺的影响因素进行了具体的解释分析,并对焦磷酸介质下锰(Ⅲ)/锰(Ⅱ)在石墨电极上的动力学参数进行了计算。最佳工艺条件:电解时间为5 h左右,电流密度为10.87 mA/cm2,电解温度为0 ℃,电解液为0.3 mol/L磷酸二氢锰+3 mol/L焦磷酸。在最佳工艺条件下电解制备可溶性三价锰的浓度最高,而且电流效率也较高。通过电化学测试的参数进行动力学计算,锰(Ⅲ)/锰(Ⅱ)在0.3 mol/L磷酸二氢锰+3 mol/L焦磷酸电解液中为准可逆过程,过程的条件电极电位为1.315 V vs.NHE,二价锰离子在这个体系中的扩散系数为8.347×10-6 cm2/s。

本文引用格式

刘思浩 , 陈金芳 , 王岩 . 电解制备焦磷酸锰(Ⅲ)盐工艺条件及动力学研究[J]. 无机盐工业, 2019 , 51(9) : 24 -29 . DOI: 10.11962/1006-4990.2018-0603

Abstract

Two-compartment cell was firstly used to electrolyze soluble trivalent manganese in the pyrophosphatic acid.The factors of current density,concentration of pyrophosphatic acid and electrolytic temperature etc.to the concentration of soluble trivalent manganese and current efficiency were investigated respectively.The process parameters were optimized by single factor conditional experiment.The influencing factors of the process were explained and analyzed.The kinetic parameters of manganese(Ⅲ)/manganese(Ⅱ) on the graphite electrode under the pyrophosphatic acid medium were also calculated.The optimal technological conditions were as follows: the electrolytic time was about 5 h,the current density was 10.87 mA/cm2,the electrolytic temperature was 0 ℃,the electrolyte was 0.3 mol/L MnH4P2O8+3 mol/L pyrophosphatic acid.Under the optimal conditions,the concentration of electrolyze soluble trivalent manganese and the current efficiency were the best.The kinetic calculation was carried out by electrochemical test parameters.manganese(Ⅲ)/manganese(Ⅱ) was quasi-reversible in 0.3 mol/L MnH4P2O8+3 mol/L pyrophosphatic acid electrolyte.The conditional electrode potential of the process was 1.315 V vs.NHE,the diffusion coefficient of divalent manganese ions in the system was 8.347×10-6 cm2/s.

参考文献

[1] Li B, Zhang Z, Zheng X , et al. Flow injection chemiluminescence determination of isoniazid using on-line electrogenerated manganese(Ⅲ) as oxidant[J]. Microchemical Journal, 1999,63(3):374-380.
[2] Otamonga J P, Abdel-Mageed A, Agater I B , et al. A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species[J]. Luminescence:The Journal of Biological and Chemical Luminescence, 2015,30(5):507-511.
[3] 邹远林, 张丹维, 刘颖 , 等. 醋酸锰作用下二烯丙基叔胺与[60]富勒烯的自由基环加成反应[J]. 有机化学, 2004,24(12):1614-1618.
[4] Aslan H, ?ktemer A, Dal H , et al. Synjournal of ferrocene substituted dihydrofuran derivatives via manganese(Ⅲ) acetate mediated radical addition-cyclization reactions[J]. Tetrahedron, 2017,73(51):7223-7232.
[5] Chuang C P, Chen Y J . ChemInform abstract:Manganese(Ⅲ) acetate mediated oxidative radical cyclizations of α-substituted N-[2-(phenylethynyl)phenyl] acetamides[J]. ChemInform, 2016,47(31):1911-1918.
[6] 雷英杰, 毕野, 欧阳杰 , 等. 醋酸锰(Ⅲ)催化2-(4-氨基苯基)苯并噻唑衍生物的合成研究[J]. 化学研究与应用, 2012,24(10):1596-1599.
[7] 许伟 . 三价锰和Bu3SnH/AIBN引发的自由基反应研究[D]. 苏州:苏州大学, 2010.
[8] Burnea F K B, Shi H, Ko K C , et al. Reduction potential tuning of first row transition metal MⅢ/MⅡ(M=Cr,Mn,Fe,Co,Ni) hexaden tate complexes for viable aqueous redox flow battery catholytes:A DFT study[J]. Electrochimica Acta, 2017,246:156-164.
[9] 米常焕 . Mn(Ⅲ)/Mn(Ⅱ)作为液流电池正极的可行性及锂离子电池锡基负极材料的研究[D]. 乌鲁木齐:新疆大学, 2002.
[10] 靳明辉 . 液流电池Mn(Ⅲ)/Mn(Ⅱ)正极电对的特性及电极反应机理研究[D]. 重庆:重庆大学, 2009.
[11] 米常焕, 夏熙, 张校刚 . 氧化还原液流电池单电极Mn3+/Mn2+的电化学行为[J]. 电源技术, 2003,27(1):2-4,7.
[12] 米常焕, 夏熙, 张校刚 . 酸性介质中Mn(Ⅲ)/Mn(Ⅱ)在铂电极上的氧化还原特性[J]. 应用化学, 2003,20(2):183-185.
[13] 张晓波, 刘红光, 叶学海 , 等. 焙烧温度对锰酸锂结构及电化学性能影响研究[J]. 无机盐工业, 2012,44(7):31-32,46.
[14] Barek J, Berka A, Steyermark A . The use of trivalent manganese compounds in titrimetry[J]. C R C Critical Reviews in Analytical Chemistry, 1980,9(1):55-95.
[15] Pastor T J, Pastor F T . The role of manganese(Ⅳ) compounds as oxi dants-a review[J]. Talanta, 2000,52(6):959-970.
[16] 王金凤 . 玻璃基质氧化锰化学发光传感器研究[D]. 西安:陕西师范大学, 2010.
[17] Selim R G, Lingane J J . Coulometric titration with higher oxidation states of manganese:Electrolytic generation and stability of manganese(Ⅲ) in sulfuric acid media[J].Analytica Chimica Acta, 1959(21):536-540.
[18] Barnett N W, Hindson B J, Jones P , et al. Chemically induced phosphorescence from manganese(Ⅱ) during the oxidation of various compounds by manganese(Ⅲ),(Ⅳ)break and(Ⅶ) in acidic aque ous solutions[J]. Analytica Chimica Acta, 2002,451(2):181-188.
[19] 王金凤, 王春艳, 霍宇飞 , 等. 可用于化学发光检测的Mn(Ⅲ)溶液的制备[J]. 河南化工, 2010,27(7):32-33.
[20] Mahadevaiah, Galil M S A, Kumar M S Y , et al. Exploitation of simple redox reaction between manganese(Ⅲ) and o-tolidine for a highly sensitive spectrophotometric determination of ascorbic acid[J]. Analytical Chemistry An Indian Journal, 2007,6(2):70-74.
[21] Kemp T J, Waters W A . The oxidation of malonic acid by manganic sulphate[J].Journal of the Chemical Society, 1964(0):1489-1493.
[22] Yang E L, Shi J J, Liang H C . On-line electrochemical production of ferrate (Ⅵ) for odor control[J]. Electrochimica Acta, 2012,63:369-374.
[23] 王歌, 赵晓昱, 张瑾 , 等. 不同晶型二氧化锰的可控制备条件研究[J]. 无机盐工业, 2017,49(8):14-18.
文章导航

/