刚柔组合桨强化软锰矿浸出过程的反应动力学特性

doi:10.11949/0438-1157.20201304

化工学报 ›› 2021, Vol. 72 ›› Issue (5): 2586-2595.DOI: 10.11949/0438-1157.20201304

• 催化、动力学与反应器 • 上一篇下一篇

刚柔组合桨强化软锰矿浸出过程的反应动力学特性

谢昭明^1,²(),陈庚^1,²,刘仁龙^1,²,刘作华^1,²,岑少斗^1,²,陶长元^1,²,郭胜惠³

^1.重庆大学化学化工学院，重庆 400044
^2.煤矿灾害动力学与控制国家重点实验室，重庆大学，重庆 400044
^3.昆明理工大学冶金与能源工程学院，云南昆明 650093

收稿日期:2020-09-11 修回日期:2020-10-29 出版日期:2021-05-05 发布日期:2021-05-05
通讯作者: 谢昭明
作者简介:谢昭明（1973—），男，博士，副教授，xiezm@cqu.edu.cn
基金资助:
国家自然科学基金-云南省联合基金项目(U1802255);煤矿灾害动力学与控制国家重点实验室自主研究课题重点项目(2011DA105287-zd201902)

Reaction kinetics characteristics of pyrolusite leaching process enhanced by rigid-flexible combined impeller

XIE Zhaoming^1,²(),CHEN Geng^1,²,LIU Renlong^1,²,LIU Zuohua^1,²,CEN Shaodou^1,²,TAO Changyuan^1,²,GUO Shenghui³

^1.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
^2.State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, China
^3.Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China

Received:2020-09-11 Revised:2020-10-29 Online:2021-05-05 Published:2021-05-05
Contact: XIE Zhaoming

摘要/Abstract

摘要：

在软锰矿湿法浸出过程中，采用传统搅拌桨反应器，容易出现流体“打旋”现象，导致传质效果差，进而降低反应效率。因而，本研究将刚柔组合桨应用于软锰矿的还原浸出过程，强化浸出过程的传质行为，提高锰矿浸出率。结果表明，在黄铁矿与软锰矿质量比为0.20，硫酸浓度为1.5 mol/L，液固比为10，温度为363 K下，软锰矿中锰的浸出率达到90.12%，与传统桨叶相比，锰浸出率提高5.5%。同时，研究发现浸出过程遵循核收缩模型且受表面化学反应控制，黄铁矿与软锰矿质量比、初始硫酸浓度、液固比的反应级数分别为1.2679、0.4182、1.1959，反应动力学方程为1- （1-X）^1/3=0.96×10³（ $m F e S 2 / m M n O 2$ ）^1.2679[H₂SO₄]^0.4182（L/S）^1.1959exp（-41.75 ×10³/RT）t，浸出反应的表观活化能为41.75 kJ/mol。刚柔组合桨体系下的软锰矿浸出反应表观活化能相比传统搅拌体系下的软锰矿浸出反应表观活化能的文献报道值降低4.515~20.54 kJ/mol。

关键词: 软锰矿, 湿法冶金, 还原, 浸取, 刚柔组合桨, 动力学

Abstract:

In the process of wet leaching of pyrolusite, the traditional stirring blade reactor is prone to fluid “swirling”, which leads to poor mass transfer effects and lower reaction efficiency. In this paper, rigid-flexible combined impeller was applied to reduction leaching process of pyrolusite to enhance manganese ore leaching efficiency. The results show that under the condition of pyrite-to-pyrolusite mass ratio is 0.20, the sulfuric acid concentration is 1.5 mol/L, the liquid-to-solid mass ratio is 10, and the temperature is 363 K, the leaching rate of manganese in pyrolusite reaches 90.12%, which is 5.5% higher than that of traditional impeller. Simultaneously, it is also found that the leaching process follows the shrinking core model and is controlled by the surface chemical reaction. The reaction orders of pyrite-to-pyrolusite mass ratio, sulfuric acid concentration and liquid-to-solid ratio are 1.2679, 0.4182 and 1.1959, respectively, and kinetic equation is 1- (1-X)^1/3=0.96×10³( $m F e S 2 / m M n O 2$ )^1.2679×[H₂SO₄]^0.4182(L/S)^1.1959exp(-41.75×10³/RT)t, the apparent activation energy of the leaching process is 41.75 kJ /mol. The apparent activation energy of pyrolusite leaching reaction in rigid-flexible combined impeller system is 4.515—20.54 kJ/mol lower than that in regular agitation system.

Key words: pyrolusite, hydrometallurgy, reduction, leaching, rigid-flexible combined impeller, kinetics

中图分类号:

TQ 027.6

谢昭明, 陈庚, 刘仁龙, 刘作华, 岑少斗, 陶长元, 郭胜惠. 刚柔组合桨强化软锰矿浸出过程的反应动力学特性[J]. 化工学报, 2021, 72(5): 2586-2595.

XIE Zhaoming, CHEN Geng, LIU Renlong, LIU Zuohua, CEN Shaodou, TAO Changyuan, GUO Shenghui. Reaction kinetics characteristics of pyrolusite leaching process enhanced by rigid-flexible combined impeller[J]. CIESC Journal, 2021, 72(5): 2586-2595.

图/表 21

图1 软锰矿的 XRD 物相分析

Fig.1 XRD analysis of pyrolusite

图2 黄铁矿的 XRD 物相分析

Fig.2 XRD analysis of pyrite

表1 软锰矿的主要化学成分分析(质量分数)

Table 1 Main chemical composition of pyrolusite by XRF analysis

O	Mn	Fe	Si	Ca	Al	其他
33.11%	31.63%	26.02%	3.69%	0.52%	3.05%	1.98%

表2 黄铁矿的主要化学成分分析(质量分数)

Table 2 Main chemical composition of pyrite by XRF analysis

Fe	S	Si	Zn	Al	Ca	其他
50.29%	38.06%	2.04%	5.47%	1.13%	1.67%	1.34%

图3 反应装置1—搅拌电机；2—刚柔组合桨；3—反应槽；4—热电偶；5—恒温水浴锅

Fig.3 Reaction device

图4 实验采用的刚柔组合搅拌桨1—搅拌轴；2—桨叶；3—塑料带(长度约为桨间距的1.2倍)

Fig.4 The experimental impeller

图5 温度对锰浸出率的影响

Fig 5 Effect of temperature on manganese leaching efficiency

表3 不同速控步骤拟合结果R2值对比

Table 3 Contrast of R2 of different kinetic equation

温度/K	液膜扩散控制		产物脱落扩散控制		化学反应控制
温度/K	k₁/min^-1	R²	k_m/min^-1	R²	k_r/min^-1	R²
343	0.00196	0.9846	0.000209	0.9421	0.00088	0.9921
348	0.00218	0.9671	0.000302	0.9920	0.00107	0.9872
353	0.00259	0.9771	0.000476	0.9773	0.00139	0.9966
358	0.00285	0.9356	0.000677	0.9954	0.00169	0.9921
363	0.00282	0.9648	0.000779	0.9824	0.00192	0.9973

图6 不同温度下的线性拟合曲线

Fig.6 Linear fitting curves at different temperatures

图7 反应速率常数与温度的关系

Fig.7 Natural logarithm of reaction rate constant versus leaching temperature

图8 黄铁矿与软锰矿质量比对锰浸出率的影响

Fig.8 Effect of mass ratio of pyrite and pyrolusite on manganese leaching efficiency

图9 lnk与ln(mFeS2/mMnO2)的关系

Fig.9 Plot of k as a function of mass ratio of pyrite and pyrolusite

图10 初始硫酸浓度对锰浸出率的影响

Fig.10 Effect of H2SO4 concentration on manganese leaching efficiency

图11 lnk与ln[H2SO4]的关系

Fig.11 Plot of k as a function of H2SO4 concentration

图12 液固比对锰浸出率的影响

Fig.12 Effect of liquid-solid ratio on leaching efficiency

图13 lnk与ln(L/S)的关系

Fig.13 Plot of k as a function of liquid to solid ratio

图14 实验值与动力学方程检验值

Fig.14 Experimental value and kinetic equation test value

图15 不同搅拌桨强化软锰矿浸出反应的对比

Fig.15 Comparison of leaching reaction of pyrolusite enhanced by various agitaed impeller

图16 不同搅拌方式浸出锰渣的XRD谱图

Fig.16 XRD patterns of manganese slag enhanced leaching by different impeller

图17 不同搅拌桨强化浸出锰渣微观形貌

Fig.17 Micromorphology of manganese slag enhanced leaching by different impeller

图18 不同搅拌桨强化软锰矿浸出示意图

Fig.18 Mechanism diagram of pyrolusite leaching enhanced by different impeller

参考文献 32

1	刘江. 中国资源利用战略研究[M]. 北京: 中国农业出版社, 2002.
	Liu J. Research on China's Resource Utilization Strategy[M]. Beijing: China Agriculture Press, 2002.
2	Teng F, Luo S H, Kang X, et al. Preparation of manganese dioxide from low-grade pyrolusite and its electrochemical performance for supercapacitors[J]. Ceramics International, 2019, 45(17): 21457-21466.
3	Chen G, Ling Y Q, Li Q N, et al. Investigation on microwave carbothermal reduction behavior of low-grade pyrolusite[J]. Journal of Materials Research and Technology, 2020, 9(4): 7862-7869.
4	Li C X, Zhong H, Wang S, et al. Manganese extraction by reduction-acid leaching from low-grade manganese oxide ores using CaS as reductant[J]. Transactions of Nonferrous Metals Society of China, 2015, 25(5): 1677-1684.
5	Lasheen T A, El Hazek M N, Helal A S. Kinetics of reductive leaching of manganese oxide ore with molasses in nitric acid solution[J]. Hydrometallurgy, 2009, 98(3/4): 314-317.
6	Nayl A A, Ismail I M, Aly H F. Recovery of pure MnSO₄∙H₂O by reductive leaching of manganese from pyrolusite ore by sulfuric acid and hydrogen peroxide[J]. International Journal of Mineral Processing, 2011, 100(3/4): 116-123.
7	Furlani G, Pagnanelli F, Toro L. Reductive acid leaching of manganese dioxide with glucose: identification of oxidation derivatives of glucose[J]. Hydrometallurgy, 2006, 81(3/4): 234-240.
8	Su H F, Wen Y X, Wang F, et al. Reductive leaching of manganese from low-grade manganese ore in H₂SO₄ using cane molasses as reductant[J]. Hydrometallurgy, 2008, 93(3/4): 136-139.
9	Tian X K, Wen X X, Yang C, et al. Reductive leaching of manganese from low-grade manganese dioxide ores using corncob as reductant in sulfuric acid solution[J]. Hydrometallurgy, 2010, 100(3/4): 157-160.
10	Naik P K, Sukla L B, Das S C. Aqueous SO₂ leaching studies on Nishikhal manganese ore through factorial experiment[J]. Hydrometallurgy, 2000, 54(2/3): 217-228.
11	Ekmekyapar A, Asin C, Demirkiran N, et al. Reductive leaching of pyrolusite ore by using sawdust for production of manganese sulfate[J]. Russian Journal of Non-Ferrous Metals, 2012, 53(3): 211-217.
12	Sahoo R N, Naik P K, Das S C. Leaching of manganese from low-grade manganese ore using oxalic acid as reductant in sulphuric acid solution[J]. Hydrometallurgy, 2001, 62(3): 157-163.
13	谢红艳, 王吉坤, 杨世诚, 等. 从软锰矿中湿法浸出锰的研究进展[J]. 中国锰业, 2011, 29(1): 5-12.
	Xie H Y, Wang J K, Yang S C, et al. Review on research of wet way leaching of manganese from pyrolusite[J]. China's Manganese Industry, 2011, 29(1): 5-12.
14	冯雅丽, 张旭, 李浩然, 等. FeS₂-MnO₂-H₂SO₄浸出软锰矿反应[J]. 东北大学学报(自然科学版), 2014, 35(2): 241-244.
	Feng Y L, Zhang X, Li H R, et al. Pyrolusite leaching reactions In FeS₂-MnO₂-H₂SO₄ system[J]. Journal of Northeastern University (Natural Science), 2014, 35(2): 241-244.
15	袁明亮, 梅贤功, 陈荩, 等. 两矿法浸出软锰矿的工艺与理论[J]. 中南工业大学学报, 1997, 28(4): 329-332.
	Yuan M L, Mei X G, Chen J, et al. Technique and theory of two ore method to leach manganese dioxide ore[J]. Journal of Central South University of Technology (Natural Science), 1997, 28(4): 329-332.
16	Qin W S. Leaching of pyrolusite-pyrite in sulfuric acid media[J]. Mining and Metallurgical Engineering, 1993, 13(4): 52-56.
17	魏有仪, 罗健. 天然饱水条件下黄铁矿氧化过程的热力学探讨[J]. 矿物岩石, 1998, 18(S1): 119-123.
	Wei Y Y, Luo J. Thermodynamics analysis of oxidized course of pyrite under natural abundant water[J]. Journal of Mineralogy and Petrology, 1998, 18(S1): 119-123.
18	Long H, Dixon D G. Pressure oxidation of pyrite in sulfuric acid media: a kinetic study[J]. Hydrometallurgy, 2004, 73(3/4): 335-349.
19	孙铭, 冯雅丽, 李浩然, 等. 用黄铁矿-硫酸还原浸出软锰矿工艺及动力学研究[J]. 湿法冶金, 2016, 35(5): 377-382.
	Sun M, Feng Y L, Li H R, et al. Leaching process and dynamics of pyrolusite using pyrite and sulfuric acid[J]. Hydrometallurgy of China, 2016, 35(5): 377-382.
20	刘立泉, 戴晖, 张昭. 二氧化硫浸出软锰矿的动力学研究[J]. 湿法冶金, 1999, 18(1): 34-39.
	Liu L Q, Dai H, Zhang Z. Kinetics study of leaching manganese ore with sulfur dioxide [J]. Hydrometallurgy of China, 1999, 18(1): 34-39.
21	Zhang X R, Liu Z H, Wu X B, et al. Electric field enhancement in leaching of manganese from low-grade manganese dioxide ore: kinetics and mechanism study[J]. Journal of Electroanalytical Chemistry, 2017, 788: 165-174.
22	陶长元, 孙大贵, 刘作华, 等. 微波辅助高价锰还原浸出动力学研究[J]. 中国锰业, 2010, 28(1): 21-24.
	Tao C Y, Sun D G, Liu Z H, et al. A study on kinetics of high valent manganese oxide reducing leaching under microwave irradiation[J]. China's Manganese Industry, 2010, 28(1): 21-24.
23	Wu F F, Zhong H, Wang S, et al. Kinetics of reductive leaching of manganese oxide ore using cellulose as reductant[J]. Journal of Central South University, 2014, 21(5): 1763-1770.
24	Su H F, Liu H K, Wang F, et al. Kinetics of reductive leaching of low-grade pyrolusite with molasses alcohol wastewater in H₂SO₄[J]. Chinese Journal of Chemical Engineering, 2010, 18(5): 730-735.
25	刘作华, 郑雄攀, 朱俊, 等. 一种刚柔组合的搅拌桨: 103721606A[P]. 2014-04-16.
	Liu Z H, Zheng X P, Zhu J, et al. A rigid-flexible combined impeller: 103721606A [P]. 2014-04-16.
26	刘作华, 孙瑞祥, 王运东, 等. 刚-柔组合搅拌桨强化流体混沌混合[J]. 化工学报, 2014, 65(9): 3340-3349.
	Liu Z H, Sun R X, Wang Y D, et al. Chaotic mixing intensified by rigid-flexible coupling impeller[J]. CIESC Journal, 2014, 65(9): 3340-3349.
27	李兵, 杨义, 刘作华, 等. 湿法磷酸固-液体系混沌混合与浸出强化行为[J]. 化工学报, 2019, 70(5): 1742-1749.
	Li B, Yang Y, Liu Z H, et al. Solid-liquid chaotic mixing and leaching enhancement performance in phosphoric acid leaching process[J]. CIESC Journal, 2019, 70(5): 1742-1749.
28	谷德银, 刘作华, 邱发成, 等. 穿流-刚柔组合桨强化固液两相的悬浮行为[J]. 化工学报, 2017, 68(12): 4556-4564.
	Gu D Y, Liu Z H, Qiu F C, et al. Solid-liquid suspension behavior intensified by punched rigid-flexible impeller[J]. CIESC Journal, 2017, 68(12): 4556-4564.
29	邱发成, 刘作华, 刘仁龙, 等. 偏心射流-刚柔组合桨搅拌器内混沌混合行为研究[J]. 化工学报, 2018, 69(2): 618-624.
	Qiu F C, Liu Z H, Liu R L, et al. Chaotic mixing performance in rigid-flexible impeller stirred tank with eccentric air jet[J]. CIESC Journal, 2018, 69(2): 618-624.
30	陈家镛. 湿法冶金手册[M]. 北京: 冶金工业出版社, 2005: 1383.
	Chen J Y. Handbook of Hydrometallurgy[M]. Beijing: Metallurgical Industry Press, 2005: 1383.
31	Deng R R, Xie Z M, Liu Z H, et al. Leaching kinetics of vanadium catalyzed by electric field coupling with sodium persulfate[J]. Journal of Electroanalytical Chemistry, 2019, 854: 113542.
32	Wu D D, Wen S M, Deng J S. Leaching kinetics of cerussite using a new complexation reaction reagent[J]. New Journal of Chemistry, 2015, 39(3): 1922-1929.

[1]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[2]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[3]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[4]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[5]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[6]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[7]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[8]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[9]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[10]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[11]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[12]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[13]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[14]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[15]	何宣志, 何永清, 闻桂叶, 焦凤. 磁液液滴颈部自相似破裂行为[J]. 化工学报, 2023, 74(7): 2889-2897.

刚柔组合桨强化软锰矿浸出过程的反应动力学特性

Reaction kinetics characteristics of pyrolusite leaching process enhanced by rigid-flexible combined impeller

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 21

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价