电解制备焦磷酸锰（Ⅲ）盐工艺条件及动力学研究

doi:10.11962/1006-4990.2018-0603

摘要/Abstract

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。

关键词: 可溶性三价锰, 焦磷酸, 电解, 动力学

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.

Key words: soluble manganese(Ⅲ), pyrophosphatic acid, electrolysis, kinetics

中图分类号:

TQ137.12

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.

Liu Sihao,Chen Jinfang,Wang Yan. Study on technological condition and kinetic of preparing manganese(Ⅲ) pyrophosphate by electrolysis[J]. Inorganic Chemicals Industry, 2019, 51(9): 24-29.

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温度/℃	三价锰浓度/ （mol·L^-1）	温度/℃	三价锰浓度/ （mol·L^-1）
0	0.033 84	30	0.004 512
10	0.018 05	40	0.001 128
20	0.010 15

扫速/（mV·s^-1）	峰	E_p/V	I_p/A	ΔE_p/V	I_λ/A	I_pa/I_pc	к⁰	ψ
5	氧化	0.738	3.99×10^-2	0.151	5.39×10^-2	2.76	7.42×10^-5	0.032 82
5	还原	0.587	-2.40×10^-2	0.151	5.39×10^-2	2.76	7.42×10^-5	0.032 82
10	氧化	0.790	5.85×10^-2	0.240	6.34×10^-2	2.14	1.29×10^-4	0.040 26
10	还原	0.550	-3.10×10^-2	0.240	6.34×10^-2	2.14	1.29×10^-4	0.040 26
15	氧化	0.814	6.30×10^-2	0.341	6.34×10^-2	1.89	2.73×10^-4	0.069 67
15	还原	0.473	-3.76×10^-2	0.341	6.34×10^-2	1.89	2.73×10^-4	0.069 67
20	氧化	0.846	1.06×10^-1	0.389	1.16×10^-1	1.91	1.79×10^-4	0.039 61
20	还原	0.457	-6.99×10^-2	0.389	1.16×10^-1	1.91	1.79×10^-4	0.039 61
25	氧化	0.868	1.09×10^-1	0.425	1.16×10^-1	1.67	3.67×10^-4	0.072 61
25	还原	0.443	-7.01×10^-2	0.425	1.16×10^-1	1.67	3.67×10^-4	0.072 61

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