铬铁矿无钙焙烧渣的SO2还原解毒

doi:10.11949/j.issn.0438-1157.20170863

摘要/Abstract

摘要：

系统地对铬铁矿无钙焙烧渣进行了表征，并研究了SO₂还原解毒铬渣，提出了机械活化与SO₂还原相结合的解毒工艺。结果表明，该铬渣主要物相组成是（Fe，Mg）（Cr，Fe）₂O₄和MgAlFeO₄，铬渣中Cr₂O₃含量为12.23%，铬渣粒径越小，含有的总Cr（Ⅵ）、水溶性Cr（Ⅵ）、难溶性Cr（Ⅵ）量越小。SO₂还原解毒铬渣工艺过程中搅拌能有效强化外扩散过程，液固比增大有利于铬渣中Cr（Ⅵ）的浸出，铬渣中Cr（Ⅵ）的浸出随温度升高先增加后急剧降低，反应体系中压力变化对铬渣还原解毒效果影响不大。优化的SO₂还原解毒铬渣条件为：压力0.1 MPa、温度60℃、搅拌速度500 r·min^-1、反应时间60 min，此时铬渣中Cr（Ⅵ）的去除率达90%；机械活化90 min的铬渣进行SO₂还原解毒60 min后，渣中的Cr（Ⅵ）去除率达到98.1%，含量降至25 mg·kg^-1以下，达到国家排放标准。

关键词: 无钙焙烧铬渣, 还原解毒, 浸取, 机械活化

Abstract:

Chromium ore processing residue (COPR) from roasting chromite without calcium is characterized systematically.The detoxification of COPR by SO₂ reduction is investigated. The detoxification process combining mechanical activation with SO₂ reduction is proposed. The results show that the main phases of the COPR are (Fe, Mg) (Cr,Fe) ₂O₄ and MgAlFeO₄. The content of Cr₂O₃ in the CPR is 12.23%. The smaller the particle size of COPR, the lower the content of the total Cr(Ⅵ), water-soluble Cr(Ⅵ) and insoluble Cr(Ⅵ). In the detoxification process of COPR by SO₂ reduction, stirring can promote the process of external diffusion effectively and increasing liquid solid ratio is beneficial to the leaching of Cr(Ⅵ) in the COPR. With the increase of temperature, the leaching of Cr(Ⅵ) in COPR increases first, then decreases sharply. The pressure of reaction system has little influence on the detoxification of the COPR. Under the optimized experimental conditions:the pressure 0.1 MPa, the temperature 60℃, the stirring speed 500 r·min^-1, and the reaction time 60 min, the removal rate of Cr(Ⅵ) in COPR was 90%, while the removal rate of Cr(Ⅵ) in COPR was 98.1%, and Cr(Ⅵ) content falls below 25 mg·kg^-1, meeting the national discharge standard after 90 min of mechanical activation to the COPR.

Key words: chromite processing residue, reductive detoxification, leaching, mechanical activation

中图分类号:

TQ136.1

吴俊, 全学军, 李纲, 鹿存房, 罗华政. 铬铁矿无钙焙烧渣的SO₂还原解毒[J]. 化工学报, 2018, 69(4): 1678-1686.

WU Jun, QUAN Xuejun, LI Gang, LU Cunfang, LUO Huazheng. Detoxification of chromium ore processing residue from roasting chromite without calcium by SO₂ reduction[J]. CIESC Journal, 2018, 69(4): 1678-1686.

参考文献 37

[1]	LEGRAND L, EL FIGUIGUI A, MERCIER F, et al. Reduction of aqueous chromate by Fe(Ⅱ)/Fe(Ⅲ) carbonate green rust:kinetic and mechanistic studies[J]. Environmental Science & Technology, 2004, 38(17):4587-4595.
[2]	BO B L, FALLMAN A M, LARSSON L B. Environmental impact of ferrochrome slag in road construction[J]. Waste Management, 2001, 21(3):255-264.
[3]	SUN Y, YANG X, LI D, et al. Simplified calculation for mixing amount of chromium residue used as dolomite in sintering and ironmaking process[J]. Inorganic Chemicals Industry, 2009, 41(5):48-50.
[4]	MENG F, ZHANG M, XIAO Y, et al. Research on application of chromium residue as cement mineralizer[J]. Inorganic Chemicals Industry, 2007, 39(10):49-51.
[5]	WANG Y, YANG Z, CHAI L, et al. Diffusion of hexavalent chromium in chromium-containing slag as affected by microbial detoxification[J]. Journal of Hazardous Materials, 2009, 169(1/2/3):1173-1178.
[6]	LIAO C Z, TANG Y, LEE P H, et al. Detoxification and immobilization of chromite ore processing residue in spinel-based glass-ceramic[J]. Journal of Hazardous Materials, 2016, 321:449-455.
[7]	WHITTLESTON R A, STEWART D I, MORTINMER R J, et al. Chromate reduction in Fe(Ⅱ)-containing soil affected by hyperalkaline leachate from chromite ore processing residue[J]. Journal of Hazardous Materials, 2011, 194(5):15-23.
[8]	DHAL B, DAS N N, THATOI H N, et al. Characterizing toxic Cr(Ⅵ) contamination in chromite mine overburden dump and its bacterial remediation[J]. Journal of Hazardous Materials, 2013, 260(6):141-149.
[9]	QUAN X, TAN H, ZHAO Y, et al. Detoxification of chromium slag by chromate resistant bacteria[J]. Journal of Hazardous Materials, 2006, 137(2):836-841.
[10]	纪柱. 铬渣治理工程实用技术[M]. 北京:化学工业出版社, 2011:33-47. JI Z. Practical Technology of COPR Treatment Project[M]. Beijing:Chemical Industry Press, 2011:33-47.
[11]	WU J, LI C, YANG F. The disposition of chromite ore processing residue (COPR) incorporating industrial symbiosis[J]. Journal of Cleaner Production, 2015, 95:156-162.
[12]	MOON D H, WAZNE M, KOUTSOSPYROS A, et al. Evaluation of the treatment of chromite ore processing residue by ferrous sulfate and asphalt[J]. Journal of Hazardous Materials, 2009, 166(1):27-32.
[13]	SAMUEL J, PAUL M L, PULIMI M, et al. Hexavalent chromium bioremoval through adaptation and consortia development from Sukinda chromite mine isolates[J]. Ind. Eng. Chem. Res., 2012, 51(9):3740-3749.
[14]	DHAL B, THATOI H, DAS N, et al. Reduction of hexavalent chromium by Bacillus sp. isolated from chromite mine soils and characterization of reduced product[J]. Journal of Chemical Technology & Biotechnology, 2010, 85(11):1471-1479.
[15]	PANDEY B, KINRADE S D, CATALAN L J. Effects of carbonation on the leachability and compressive strength of cement-solidified and geopolymer-solidified synthetic metal wastes[J]. Journal of Environmental Management, 2012, 101(2):59-67.
[16]	HUANG D, DRUMMOND C H Ⅲ, WANG J, et al. Incorporation of chromium(Ⅲ) and chromium(Ⅵ) oxides in a simulated basaltic, industrial waste glass-ceramic[J]. Journal of the American Ceramic Society, 2005, 87(11):2047-2052.
[17]	陈振林, 黄志强. 二氧化碳常温浸提法回收铬渣中铬的研究[J]. 无机盐工业, 2006, 38(8):42-44. CHEN Z L, HUANG Z Q. Study on the recovery of Cr(Ⅵ) from chrome residue by extracting with carbon dioxide at normal temperature[J].Inorganic Chemicals Industry, 2006, 38(8):42-44.
[18]	赵备备, 王少娜, 郑诗礼, 等. 铬盐无钙焙烧渣加压硫酸浸出[J]. 过程工程学报, 2014, 14(6):915-922. ZHAO B B, WANG S N, ZHENG S L, et al. Pressure leaching of chromium-containing slag from non-calcium roasting with sulfuric acid[J].The Chinese Journal of Process Engineering, 2014, 14(6):915-922.
[19]	杨得军. 铬盐无钙焙烧工艺中钒、铬的分离富集研究[D]. 昆明:昆明理工大学, 2013. YANG D J. Study on the separation and enrichment of vanadium and chromium chromate free calcium roasting process[D]. Kunming:Kunming University of Science and Technology, 2013.
[20]	SUN T, CHEN J, LEI X, et al. Detoxification and immobilization of chromite ore processing residue with metakaolin-based geopolymer[J]. Journal of Environmental Chemical Engineering, 2014, 2(1):304-309.
[21]	LIU S, CHEN L, GAO Y. Hexavalent chromium leaching influenced factors in the weathering chrome slag[J]. Advanced Materials Research, 2014, 952:783-787.
[22]	YU K P, ZHANG H L, CHEN B, et al. Investigation of reaction mechanism on the lime-free roasting of chromium-containing slag[J]. Metallurgical and Materials Transactions B, 2015, 46(6):2553-2563.
[23]	YU K P, CHEN B, ZHANG H L, et al. Influence of silica on the lime-free roasting of chromium-containing slag[J]. Metallurgical and Materials Transactions B, 2016, 47(1):1-9.
[24]	CHEN G, WANG J J, WANG X H, et al. An investigation on the kinetics of chromium dissolution from Philippine chromite ore at high oxygen pressure in KOH sub-molten salt solution[J]. Hydrometallurgy, 2013, 139(3):46-53.
[25]	LEE K T, KOON O W. Modified shrinking unreacted-core model for the reaction between sulfur dioxide and coal fly ash/CaO/CaSO4, sorbent[J]. Chemical Engineering Journal, 2009, 146(1):57-62.
[26]	夏清, 陈常贵. 化工原理[M].天津:天津大学出版社, 2005:80-84. XIA Q, CHEN C G. Unit Operations of Chemical Engineering[M]. Tianjin:Tianjin University Press, 2005:80-84.
[27]	MOHAN D, PITTMAN C U JR. Activated carbons and low cost adsorbents for remediation of tri-and hexavalent chromium from water[J]. Journal of Hazardous Materials, 2006, 137(2):762-811.
[28]	呼世斌, 黄蔷蕾.无机及分析化学[M].北京:高等教育出版社, 2009:229-232, 502. HU S B, HUANG Q L. Inorganic and Analytical Chemistry[M]. Beijing:Higher Education Press, 2009:229-232, 502.
[29]	SAHA B, ORVIG C. Biosorbents for hexavalent chromium elimination from industrial and municipal effluents[J]. Coordination Chemistry Reviews, 2010, 254(23/24):2959-2972.
[30]	周鲁.物理化学教程[M]. 北京:科学出版社, 2006:210-239. ZHOU L. Physical Chemistry[M]. Beijing:China Science Publishing & Media Ltd., 2006:210-239.
[31]	程治良, 全学军, 代黎, 等.水力喷射空气旋流器用于含Cr(Ⅵ)废水处理[J].化工学报, 2014, 65(4):1403-1410. CHENG Z L, QUAN X J, DAI L, et al. Treatment of Cr(Ⅵ)-containing wastewater in a water-sparged aerocyclone[J].CIESC Journal, 2014, 65(4):1403-1410.
[32]	MIRETZKY P, FERNANDEZ C A. Cr(Ⅵ) and Cr(Ⅲ) removal from aqueous solution by raw and modified lignocellulosic materials:a review[J]. Journal of Hazardous Materials, 2010, 180(1/2/3):1-19.
[33]	史焱, 詹先成, 吕太平, 等. 抗氧剂亚硫酸钠、亚硫酸氢钠及焦亚硫酸钠氧化反应速率常数的测定[J]. 化学学报, 2006, 64(6):496-500. SHI Y, ZHAN X C, LÜ T P, et al. Determination of oxidation rate constants of antioxidants sodium sulfite, sodium bisulfite and sodium pyrosulfite[J]. Acta Chimica Sinica, 2006, 64(6):496-500.
[34]	王艳玲.无机化学[M].北京:石油工业出版社, 2008:98-107. WANG Y L. Inorganic Chemistry[M]. Beijing:Petroleum Industry Press, 2008:98-107.
[35]	吴爱祥, 刘超, 尹升华, 等. 类砂岩型矿石的浸出特性[J].中国有色金属学报, 2014, 24(7):1856-1863. WU A X, LIU C, YIN S H, et al. Leaching properties of quasi-sandstone type ore[J]. The Chinese Journal of Nonferrous Metals, 2014, 24(7):1856-1863.
[36]	KALINKIN A M, KALINKINA E V, ZALKIND O A, et al. Chemical interaction of calcium oxide and calcium hydroxide with CO2 during mechanical activation[J]. Inorganic Materials, 2005, 41(10):1073-1079.
[37]	ZHANG Y, ZHENG S L, DU H, et al. Effect of mechanical activation on alkali leaching of chromite ore[J]. Transactions of Nonferrous Metals Society of China, 2010, 20(5):888-891.

铬铁矿无钙焙烧渣的SO₂还原解毒

Detoxification of chromium ore processing residue from roasting chromite without calcium by SO₂ reduction

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	郑涛, 刘海燕, 张睿, 孟祥海, 岳源源, 刘植昌. 基于分子筛绿色合成的天然硅铝矿物介尺度活化研究进展[J]. 化工学报, 2022, 73(6): 2334-2351.
[2]	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.
[3]	王曰杰, 李玲玲, 何春宏. 炼油废催化剂生物淋滤脱金属研究进展[J]. 化工学报, 2021, 72(2): 901-912.
[4]	吴玉花,丁欣,李小露,高红凤,冯炜,白红存,郭庆杰. 离子液体-微波辅助从黄连提取小檗碱的实验与分子模拟[J]. 化工学报, 2020, 71(7): 3123-3131.
[5]	方俊华,唐琦,李杨,李遥瑶,吕秋颖,范准,周健,许劲. 污泥水热碳化中磷的形态变化及金属浸出行为[J]. 化工学报, 2020, 71(7): 3288-3295.
[6]	马密霞, 秦宁, 闵清, 胡文祥. 微波超声波联用萃取白藜芦醇及其苷的HPLC测定[J]. 化工学报, 2019, 70(S1): 124-129.
[7]	李兵, 杨义, 刘作华, 陶长元, 谷德银, 许传林, 王运东. 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.
[8]	苏银皎, 刘轩, 李丽锋, 李晓航, 姜平, 滕阳, 张锴. 三类煤阶煤中汞的赋存形态分布特征[J]. 化工学报, 2019, 70(4): 1559-1566.
[9]	叶鹏, 全学军, 秦险峰, 封承飞, 李纲, 鹿存房, 齐学强, 蒋丽. 铬铁矿无钙焙烧渣盐酸浸出[J]. 化工学报, 2019, 70(11): 4428-4436.
[10]	李昌辉, 孟玲, 桂霞, 云志. 一种提取与分离冬凌草甲素的方法[J]. 化工学报, 2018, 69(S2): 240-245.
[11]	袁洪友, 武书彬, 阴秀丽, 黄艳琴, 刘华财, 王贵金, 詹昊, 吴创之. 草浆黑液热解和燃烧碱回收过程硅元素的分布[J]. 化工学报, 2018, 69(5): 2191-2198.
[12]	贺理珀, 孙淑英, 于建国. 退役锂离子电池中有价金属回收研究进展[J]. 化工学报, 2018, 69(1): 327-340.
[13]	王倩, 郭莉, 陈绍华, 薛余化, 杜冬云. 辉光放电等离子体辅助碱浸铜冶炼烟灰中铜砷分离[J]. 化工学报, 2017, 68(5): 1932-1939.
[14]	徐亚红, 徐中慧, 蒋灶, 肖博. 镁热剂/铝热剂体系SHS法固化处理无钙焙烧铬渣[J]. 化工学报, 2017, 68(11): 4309-4315.
[15]	丁琳琳, 王延吉, 吴兆亮, 邓菲, 李瑞, 刘伟. 基于甘草配伍黄芩同时泡沫分离甘草酸和黄芩苷[J]. 化工学报, 2017, 68(1): 170-177.