活性矿浆脱硫可行性研究及其有效组分分析
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摘要
冶炼低浓度SO_2烟气的经济、达标、无害化治理一直是冶炼行业的难题,目前处理方式主要集中在传统脱硫剂的应用,在以废治废方面的研究鲜有报道。本文提出以硫化镍铜矿选矿过程产生的活性矿浆为低浓度二氧化硫烟气的脱硫剂,建立冶炼烟气脱硫中试验装置,运用扫描电镜、原子吸收法、多种化学元素定量检测法等分析检测手段,研究活性矿浆作为一种廉价脱硫剂的有效组分及脱硫效果。结果表明:活性矿浆脱硫液pH﹥5.5时烟气可达标排放,折算SO_2吸收量为4.15kg/t矿浆,高于理论值3.68kg/t矿浆。活性矿浆中有效脱硫组分以黑云母、绿泥石、白云石、磁铁矿中的活性氧化镁、氧化钙和铁磁性物质为主,其中活性氧化镁与氧化钙参与反应的全过程,在弱酸性介质条件下铁磁性物质参与反应。脱硫后矿浆清液中重金属离子含量均低于排放标准要求,渣属于一般固体废弃物,不会对环境造成污染。
The economy,standard,harmless treatment of the low concentration SO_2 smelting flue gas is always a difficult problem in the smelting industry. The current approach focuses on the application of traditional desulfurizer and the research of treatment with waste is rarely reported. In this paper,the active ore slurry produced from mineral dressing process of Ni-Cu sulfide ores was as desulfurizer to the low concentration of sulfur dioxide flue gas,and the pilot experimental device of flue gas desulfurization was built and the effective components and desulfurization effect of the active ore slurry as a cheap desulfurizer was reported using scanning electron microscopy(SEM),atomic absorption method and various chemical elements quantitative analysis and detection methods. The results indicate that the flue gas can reach to discharge standards when the p H of the active ore slurry is above 5.5,reduced sulfur capacity is 4.15kg/t active ore slurry,which is higher than theoretical value 3.68kg/t. The effective mineral components are mainly biotite,chlorite,dolomite,magnetite,the active magnesium oxide,calcium oxide and ferromagnetic material,in which active magnesium oxide and calcium oxide participate in the whole reaction,and the ferromagnetic material participate in reaction under the condition of weak acid medium. Heavy metal ion content in the slurry supernatant after desulfurization is lower than the discharge standard and the slag is a general solid waste,which cannot cause the environment pollution.
The economy,standard,harmless treatment of the low concentration SO_2 smelting flue gas is always a difficult problem in the smelting industry. The current approach focuses on the application of traditional desulfurizer and the research of treatment with waste is rarely reported. In this paper,the active ore slurry produced from mineral dressing process of Ni-Cu sulfide ores was as desulfurizer to the low concentration of sulfur dioxide flue gas,and the pilot experimental device of flue gas desulfurization was built and the effective components and desulfurization effect of the active ore slurry as a cheap desulfurizer was reported using scanning electron microscopy(SEM),atomic absorption method and various chemical elements quantitative analysis and detection methods. The results indicate that the flue gas can reach to discharge standards when the p H of the active ore slurry is above 5.5,reduced sulfur capacity is 4.15kg/t active ore slurry,which is higher than theoretical value 3.68kg/t. The effective mineral components are mainly biotite,chlorite,dolomite,magnetite,the active magnesium oxide,calcium oxide and ferromagnetic material,in which active magnesium oxide and calcium oxide participate in the whole reaction,and the ferromagnetic material participate in reaction under the condition of weak acid medium. Heavy metal ion content in the slurry supernatant after desulfurization is lower than the discharge standard and the slag is a general solid waste,which cannot cause the environment pollution.
引文
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[20]REN Hao,JI Feifei,SONG Guilan,et al.Collecting property of diphosphonic acid for niobite[J].Reserrch of Environmental Science,2005,12(2):106-110.
[2]LIU Ming,MENG Guixiang,YAN Junjie,et al.Flow characteristics diagnosis and optimization for dust collectors inflow duct in thermal power plants[J].Proceedin of the CSEE,2013,33(11):1-6.
[3]方项林,邵志恒.有色金属冶炼烟气制酸湿法净化工艺研究[J].世界有色金属,2015(9):79-80.FANG Xianglin,SHAO Zhiheng.Research on the process of acid wet purification of the flue gas of nonferrous metals smelting[J].World Nonferrous Metals,2015(9):79-80.
[4]环境保护部,国家质量监督检验检疫总局.镍铜钴工业污染物排放标准:GB25467—2010[S].北京:中国标准出版社,2010.Environmental Protection Department,State Administration for Quality Supervision and Inspection and Quarantine.Emission standard of pollutants for copper,nickel,cobalt industry:GB25467—2010[S].Beijing:China Standards Press,2010.
[5]WANG Fan,WANG Hongmei,ZHANG Fan,et al.SO2/Hg removal from flue gas by dry FGD[J].Mining Science and Technology,2012,22(1):107-110.
[6]彭康,李皓瑜.低浓度二氧化硫冶炼烟气处理工艺[J].化学工业与工程技术,2010,31(6):49-54.PENG Kang,LI Haoyu.Treatment processes of low-SO2metallurgical flue gases[J].Journal of Chemical Industry&Engineering,2010,31(6):49-54.
[7]GUAN Jian,XIAO Yuan,SONG Jimin.A typical flat-panel membrane bioreactor with a composite membrane for sulfur removal[J].Frontiers of Earth Science,2014,8(1):142-149.
[8]KALLINIKOS L E,FARSARI E I,SPARTINOS D N,et al.Simulation of the operation of an industrial wet flue gas desulfurization system[J].Fuel Process Technol.,2010,91(12):1794-1802.
[9]XUE Juanqin,LI Jingxian,LU Xi,et al.Absorption of sulfur dioxide using membrane and enhancement of desorption with ultrasound[J].Transactions of Nonferrous Metals Society of China,2010,20(5):930-934.
[10]XUE Juanqin,LAN Xinzhe,MENG Lingai,et al.Absorption of low concentration sulfur dioxide using liquid-containing microporous membrane[J].Chinese Journal of Process Engineering,2007,7(3):483-489.
[11]郑争志,李钰,王琪.多元胺溶液吸收/解吸SO2的研究[J].合肥工业大学学报:自然科学版,2011,34(1):141-144.ZHENG Zhengzhi,LI Yu,WANG Qi.Absorption and desorption of SO2 by polyamine compounds in aqueous solution[J].Journal of Hefei University of Technology(Natural Science),2011,34(1):141-144.
[12]SHI Lin,GU Guobang.Flue gas desulphurization using sodium sulfide on pilot scale[J].Engineering Sciences,2010,8(2):39-43.
[13]李建隆,梁昌娟,李红海.离子液体脱除SO2技术的研究进展[J].化工进展,2011,30(2):417-424.LI Jianlong,LIANG Changjuan,LI Honghai.Research progress of ionic liquids desulfurization technology[J].Chemical Industry and Engineering Progress,2011,30(2):417-424.
[14]LI Xiaolei,ZHU Chunying,MA Youguang.Removal of SO2 using ammonium bicarbonate aqueous solution as absorbent in a bubble column reactor[J].Frontiers of Chemical Science and Engineering,2013,7(2):185-191.
[15]武春锦,吕武华,梅毅,等.湿法烟气脱硫技术及运行经济性分析[J].化工进展,2015,34(12):4368-4374.WU Chunjin,LV Wuhua,MEI Yi,et al.Application and running economic analysis of wet flue gas desulfurization technology[J].Chemical Industry and Engineering Progress,2015,34(12):4368-4374.
[16]温德清,王正辉,王玉山.金川镍矿浮选尾砂的物质组成及开发应用研究[J].矿物岩石地球化学通报,2001,20(3):198-202.WEN Deqing,WANG Zhenghui,WANG Yushan.Substance component and exploitating studies of dressing tailing in the Jinchuan Nickle Ore Deposit[J].Bulletin of Mineralogy Petrology and Geochemistry,2001,20(3):198-202.
[17]环境保护部,国家质量监督检验检疫总局.危险废物鉴别标准浸出毒性鉴别:GB 5085.3—2007[S].北京:中国标准出版社,2007.Environmental Protection Department,State Administration for Quality Supervision and Inspection and Quarantine.Identification standard for hazardous wastes-Identification for extraction procednre inxicity:GB5085.3—2007[S].Beijing:China Standards Press,2007.
[18]梁树能,甘甫平,闫柏琨,等.绿泥石矿物成分与光谱特征关系研究[J].光谱学与光谱分析,2014,34(7):1763-1768.LIANG Shuneng,GAN Fuping,YAN Bokun,et al.A study on the relationship between the composition and spectral feature parameters in chlorite[J].Spectroscopy and Spectral Analysis,2014,34(7):1763-1768.
[19]傅东.黑云母的理化特性及其开发应用的新途径[J].矿产与地质,2000,14(5):310-310,352.FU Dong.Physical and chemical character of mica and the new way of develop and use[J].Mineral Resources and Geology,2000,14(5):310-310,352.
[20]REN Hao,JI Feifei,SONG Guilan,et al.Collecting property of diphosphonic acid for niobite[J].Reserrch of Environmental Science,2005,12(2):106-110.