Process and kinetics of hydrochloric acid leaching of high-carbon ferrochromium

doi:10.16085/j.issn.1000-6613.2023-0350

Abstract

Abstract:

The valence state of chromium in the production process of traditional chromium salt industry needs to go through the transformation of trivalent to hexavalent and then to trivalent. The high toxicity of hexavalent chromium has led to chromium becoming a key heavy metal for national prevention and control. The sustainable development of chromium salt industry urgently requires the development of new technologies to avoid hexavalent chromium generation, and acid leaching of chromium-containing raw materials is a feasible way. In this paper, we proposed a new process for the preparation of trivalent chromium salts by acid leaching using high-carbon ferrochrome alloy as raw material and hydrochloric acid as leaching agent. The leached chromium chloride and ferrous chloride could be prepared as trivalent chromium salt products, which can be used as electrolyte for ferrochrome liquid flow battery. In this paper, the effect of reaction temperature, hydrochloric acid concentration, stirring rate and reaction time on the leaching rate of chromium and iron was systematically studied based on the analysis of elemental content, physical phase composition and morphology of high-carbon ferrochrome. The results showed that the chromium leaching rate was 92% and the iron leaching rate was 95% at a reaction temperature of 100℃, a hydrochloric acid concentration of 9mol/L, a stirring rate of 250r/min and a reaction time of 6h. The kinetics of the leaching of high-carbon ferrochrome in hydrochloric acid was further investigated. The leaching process of high-carbon ferric chromium was consistent with the unreacted contraction nucleation model, and the chromium leaching process was controlled by the chemical reaction with apparent activation energy E_a=65.95kJ/mol. The iron leaching process was controlled by the chemical reaction with apparent activation energy E_a=63.85kJ/mol.

Key words: leaching, high-carbon ferrochrome, hydrochloric acid, kinetics, chromium chloride

摘要：

传统铬盐行业生产过程中铬的价态需经过三价到六价再到三价的转化。六价铬的高毒性导致铬成为国家重点防控的重金属。铬盐行业的可持续发展亟需开发避免六价铬产生的新技术，含铬原料的酸浸为可行的途径。本文提出以高碳铬铁合金为原料，盐酸为浸出剂的酸性浸出制备三价铬盐新工艺。浸出后的氯化铬和氯化亚铁可制备出三价铬盐产品，其可作为铁铬液流电池的电解液。本文在对高碳铬铁元素含量、物相组成及形貌等分析的基础上，系统研究了反应温度、盐酸浓度、搅拌速率和反应时间对铬和铁浸出率的影响规律。结果表明，在反应温度100℃、盐酸浓度9mol/L、搅拌速率250r/min、反应时间6h的条件下，铬浸出率为92%，铁浸出率为95%。进一步研究了高碳铬铁在盐酸中浸出的动力学。高碳铬铁的浸出过程符合未反应收缩核模型，铬浸出过程受化学反应控制，表观活化能E_a=65.95kJ/mol；铁浸出过程受化学反应控制，表观活化能E_a=63.85kJ/mol。

关键词: 浸出, 高碳铬铁, 盐酸, 动力学, 氯化铬

CLC Number:

TF803.21

WANG Peng, ZHANG Yang, FAN Bingqiang, HE Dengbo, SHEN Changshuai, ZHANG Hedong, ZHENG Shili, ZOU Xing. Process and kinetics of hydrochloric acid leaching of high-carbon ferrochromium[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 510-517.

汪鹏, 张洋, 范兵强, 何登波, 申长帅, 张贺东, 郑诗礼, 邹兴. 高碳铬铁盐酸浸出过程工艺及动力学[J]. 化工进展, 2023, 42(S1): 510-517.

Figures/Tables 13

References 27

1	丁翼. 中国铬盐生产状况与展望[J]. 化工进展, 2004, 23(4): 345-348.
	DING Yi. Status and prospects of chromium salt production in China[J]. Chemical Progress, 2004, 23(4): 345-348.
2	李兆业. 我国铬盐现状与展望[J]. 铬盐工业, 2004(2): 40-50.
	LI Zhaoye. Current situation and prospect of chromium salt in China[J]. Chromium Salt Industry, 2004(2): 40-50.
3	王永光, 杨正吕, 张美娜, 等. Cr(Ⅲ)媒染剂在獭兔毛染色中的应用研究[J]. 皮革科学与工程, 2019, 29(1): 51-56.
	WANG Yongguang, YANG Zhenglu, ZHANG Meina, et al. Study on the application of Cr(Ⅲ) mordant in the dyeing of otter hair[J]. Leather Science and Engineering, 2019, 29(01): 51-56.
4	董喜恩, 胡宁播, 罗根祥, 等. 六水合三氯化铬催化蔗糖脱水合成5-羟甲基糠醛[J]. 精细石油化工进展, 2010, 11(4): 28-30.
	DONG Xi'en, HU Ningbo, LUO Genxiang, et al. Synthesis of 5-hydroxymethylfurfural by dehydration of sucrose catalyzed by chromium trichloride hexahydrate[J]. Advances in Fine Petrochemicals, 2010, 11(4): 28-30.
5	郑剑, 屠振密, 李宁, 等. 三价铬电镀装饰铬工艺及特性研究[J]. 材料保护, 2008(1): 24-27+85.
	ZHENG Jian, TU Zhenmi, LI Ning, et al. Study on the process and characteristics of decorative chromium plating with trivalent chromium[J]. Materials Protection, 2008(1): 24-27+85.
6	杨林, 王含, 李晓蒙, 等. 铁-铬液流电池250kW/1.5MW·h示范电站建设案例分析[J]. 储能科学与技术, 2020, 9(3): 751-756.
	YANG Lin, WANG Han, LI Xiaomeng, et al. Case study of the construction of a 250kW/1.5MW·h demonstration power plant with iron-chromium liquid flow battery[J]. Energy Storage Science and Technology, 2020, 9(3): 751-756.
7	RUAN W, MAO J, YANG S, et al. Designing Cr complexes for a neutral Fe-Cr redox flow battery[J]. Chemical Communications, 2020, 56(21): 3171-3174.
8	WANG S, XU Z, WU X, et al. Excellent stability and electrochemical performance of the electrolyte with indium ion for iron-chromium flow battery[J]. Electrochimica Acta, 2021, 368: 137524.
9	ZENG Y K, ZHAO T S, ZHOU X L, et al. A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries[J]. Journal of Power Sources, 2017, 352: 77-82.
10	纪柱. 开发实施中的中国铬酸钠新工艺(Ⅰ)[J]. 无机盐工业, 2010, 42(1): 1-4, 30.
	JI Zhu. Development and implementation of a new process for sodium chromate in China(Ⅰ)[J]. Inorganic Salt Industry, 2010, 42(1): 1-4, 30.
11	张大威, 李霞, 纪柱. 铬铁矿无钙焙烧工艺参数控制研究[J]. 无机盐工业, 2012, 44(6): 37-39.
	ZHANG Dawei, LI Xia, JI Zhu. Study on the control of calcium-free roasting process parameters of chromite[J]. Inorganic Salt Industry, 2012, 44(6): 37-39.
12	纪柱. 铬铁矿无钙焙烧的反应机理[J]. 无机盐工业, 1997(1): 18-21.
	JI Zhu. The reaction mechanism of calcium-free roasting of chromite[J]. Inorganic Salt Industry, 1997(1): 18-21.
13	张懿. 绿色过程工程[J]. 过程工程学报, 2001, 1(1): 10-15.
	ZHANG Yi. Green process engineering[J]. Journal of Process Engineering, 2001, 1(1): 10-15.
14	ZHANG Y, LI Z H, QI T, et al. Green chemistry of chromate cleaner production[J]. Chinese Journal of Chemistry, 1999, 17(3): 258-266.
15	XU H B, ZHANG S L, ZHANG Y, et al. Oxidative leaching of a Vietnamese chromite ore in highly concentrated potassium hydroxide aqueous solution at 300℃ and atmospheric pressure[J]. Minerals Engineering, 2005, 18(5): 527-535.
16	VARDAR E, ERIC R H, LETOWSKI F K. Acid leaching of chromite[J]. Minerals Engineering, 1994, 7(5/6): 605-617.
17	冷启超. 铬铁矿硫酸浸出过程及废渣循环利用研究[D]. 沈阳: 东北大学, 2017.
	LENG QC. Study on sulfuric acid leaching process and waste slag recycling of chromite ore[D]. Shenyang: Northeastern University, 2017.
18	GEVECI A, TOPKAYA Y, AYHAN E. Sulfuric acid leaching of Turkish chromite concentrate[J]. Minerals Engineering, 2002, 15(11): 885-888.
19	ZHAO Q, LIU C, SHI P, et al. Sulfuric acid leaching of South African chromite. Part 1: Study on leaching behavior[J]. International Journal of Mineral Processing, 2014, 130: 95-101.
20	JIANG M, ZHAO Q, LIU C, et al. Sulfuric acid leaching of South African chromite. Part 2: Optimization of leaching conditions[J]. International Journal of Mineral Processing, 2014, 130: 102-107.
21	ZHAO Q, LIU C, SHI P, et al. Sulfuric acid leaching kinetics of South African chromite[J]. International Journal of Minerals, Metallurgy, and Materials, 2015, 22: 233-240.
22	田仪娟. 铬铁矿盐酸浸出过程及机理研究[D]. 重庆: 重庆理工大学, 2022.
	TIAN Yijuan. Study on the process and mechanism of chromite hydrochloric acid leaching[D]. Chongqing: Chongqing University of Technology, 2022.
23	王飞. 以高碳铬铁合金粉为原料制备三氧化二铬[D]. 长沙: 中南大学, 2009.
	WANG Fei. Preparation of chromium trioxide from high-carbon ferrochrome alloy powder[D]. Changsha: Central South University, 2009.
24	王亲猛. 碳素铬铁中元素有效分离及综合利用研究[D]. 长沙: 中南大学, 2011.
	WANG Qinmeng. Research on effective separation and comprehensive utilization of elements in ferrochrome carbon[D]. Changsha: Central South University, 2011.
25	刘继军, 林红梅, 胡国荣, 等. 利用铬铁合金生产铬盐的新工艺研究[J]. 无机盐工业, 2021, 53(6): 156-159.
	LIU Jijun, LIN Hongmei, HU Guorong, et al. Study on a new process of producing chromium salt using ferrochrome alloy[J]. Inorganic Salt Industry, 2021, 53(6): 156-159.
26	冯金婷, 秦庆伟, 陈荣升, 等. 低品位铅冰铜硫酸氧化浸出动力学[J]. 有色金属(冶炼部分), 2022(11): 17-23.
	FENG Jinting, QIN Qingwei, CHEN Rongsheng, et al. Kinetics of sulfuric acid oxidative leaching of low-grade lead and copper[J]. Nonferrous Metals(Smelting), 2022(11): 17-23.
27	钱龙. 高砷硫化铜精矿硫酸浸出实验研究[D]. 昆明: 昆明理工大学, 2020.
	QIAN Long. Experimental study on sulfuric acid leaching of high-arsenic copper sulfide concentrate[D]. Kunming: Kunming University of Technology, 2020.

T/K	T^-1/(10^-3K^-1)	k	lnk	R²
343	2.92	0.00866	-4.75	0.946
353	2.83	0.02139	-3.84	0.967
363	2.75	0.03309	-3.41	0.961
373	2.68	0.05884	-2.83	0.998

T/K	T^-1/(10^-3K^-1)	k	lnk	R²
343	2.92	0.00866	-4.75	0.946
353	2.83	0.02139	-3.84	0.967
363	2.75	0.03309	-3.41	0.961
373	2.68	0.05884	-2.83	0.998

T/K	T^-1/(10^-3K^-1)	k	lnk	R²
343	2.92	0.009620	-4.64	0.846
353	2.83	0.023200	-3.76	0.944
363	2.75	0.035030	-3.35	0.915
373	2.68	0.061700	-2.79	0.983

T/K	T^-1/(10^-3K^-1)	k	lnk	R²
343	2.92	0.009620	-4.64	0.846
353	2.83	0.023200	-3.76	0.944
363	2.75	0.035030	-3.35	0.915
373	2.68	0.061700	-2.79	0.983

[1]	GU Yongzheng, ZHANG Yongsheng. Dynamic behavior and kinetic model of Hg⁰ adsorption by HBr-modified fly ash [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 498-509.
[2]	MA Yi, CAO Shiwei, WANG Jiajun, LIN Liqun, XING Yan, CAO Tengliang, LU Feng, ZHAO Zhenlun, ZHANG Zhijun. Research progress in recovery of spent cathode materials for lithium-ion batteries using deep eutectic solvents [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 219-232.
[3]	LI Weihua, YU Qianwen, YIN Junquan, WU Yinkai, SUN Yingjie, WANG Yan, WANG Huawei, YANG Yufei, LONG Yuyang, HUANG Qifei, GE Yanchen, HE Yiyang, ZHAO Lingyan. Leaching behavior of heavy metals from broken ton bags filled with fly ash in acid rain environment [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4917-4928.
[4]	LU Yang, ZHOU Jinsong, ZHOU Qixin, WANG Tang, LIU Zhuang, LI Bohao, ZHOU Lingtao. Leaching mechanism of Hg-absorption products on CeO₂/TiO₂ sorbentsin syngas [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3875-3883.
[5]	WANG Junjie, PAN Yanqiu, NIU Yabin, YU Lu. Molecular level catalytic reforming model construction and application [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3404-3412.
[6]	LI Weihua, WU Yinkai, SUN Yingjie, YIN Junquan, XIN Mingxue, ZHAO Youjie. Progress on evaluation methods for toxic leaching of heavy metals from MSW incineration fly ash [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2666-2677.
[7]	CHANG Zhankun, ZHANG Chi, SU Bingqin, ZHANG Congzheng, WANG Jian, QUAN Xiaohui. Effect of H₂S gaseous substrate on sludge bioleaching treatment efficiency [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2733-2743.
[8]	GE Weitong, LIAO Yalong, LI Mingyuan, JI Guangxiong, XI Jiajun. Preparation and dechlorination kinetics of Pd-Fe/MWCNTs bimetallic catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1885-1894.
[9]	CHEN Shaoqin, HU Ling, LEI Tianya, WANG Rong, SHU Jiancheng, CHEN Mengjun. Mechanical activation for zinc enhanced leaching from zinc calcine [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1649-1658.
[10]	LI Yun, CUI Nan, XIONG Xingxing, HUANG Zhiyuan, WANG Dongliang, XU Dan, LI Jun, LI Zebing. Influence of rare earth element Er(Ⅲ) on performance of short-cut nitrification and its inhibition kinetics [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1659-1668.
[11]	SONG Ye, CHEN Yuzhuo, SONG Yuncai, FENG Jie. Catalyst design and reactor analysis for in-situ purification of organic solid waste syngas [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1383-1396.
[12]	WANG Wei, ZHANG Dongxu, LI Zunzhao, WANG Xiaolin, HUANG Qiyu. Research progress on the growth behavior of hydrates in water-in-oil emulsion systems [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1155-1166.
[13]	DUAN Yihang, GAO Ningbo, QUAN Cui. Effect of hydrothermal treatment on pyrolysis characteristics and kinetics of oily sludge [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 603-613.
[14]	KANG Yu, GOU Zenian. Kinetics studies of carbon gas hydrate separation in the presence of amino acids and DTAC [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5067-5075.
[15]	LI Jingjing, ZHAO Yao, XU Fengchi, LI Kangjian. Heavy metal leaching characteristics of porous asphalt mixture containing MSWI-BAA under different stormwater runoff flow rates [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5520-5530.