铝电解废阴极浸提及燃烧特性的实验研究
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摘要
铝电解废阴极(简称SPL)是铝电解工业中产生的废物。据估算我国现在每年废弃约12万吨的废阴极。铝电解废阴极是有毒的危害固体废弃物,会对环境造成严重的污染,危害人身健康,必须要仔细处理。因此,寻找替代填埋的方法已经被认为是全世界铝电解工作者目前面临的不可避免的挑战。
本文对废阴极进行了浸提实验研究,利用XRD衍射仪对废阴极的物相进行了分析,分别采用水、碱、酸等不同的介质对废阴极进行了浸提:并研究了废阴极在高温炉中燃烧时气态氟的排放特性,采用高温水解-氟离子选择电极法对试样及燃烧后残渣中氟进行了测定;另外,通过添加铁铝系氧化物及碱金属等不同的添加剂对废阴极燃烧时析出氟进行了固氟研究。结果表明:在不同的浸提介质中,废阴极中氟化物浸提率按高低顺序为:酸浸介质＞碱浸介质＞水浸介质(超声波)＞水浸介质(振荡器);2mol/LHCI酸浸浸提率约为79.51%,EDS能谱分析表明2mol/LHCI酸浸后残渣中氟化物含量约为3.01%,而采用碱、酸联合浸提后残渣中氟化物含量几乎为零;废阴极中氟析出率随燃烧温度的升高而逐渐增加,到1200℃时几乎全部析出;1200℃时氟析出率随停留时间的增加而增加,30 min后氟的析出率为98.26%;铁铝系氧化物添加剂中添加Al_2O_3后固氟效果最好,达到37.07%,碱金属添加剂中添加NaCl后固氟效果最好,达到41.79%。
本文通过对废阴极的浸提及燃烧特性实验研究,为废阴极的回收利用提供了一定的理论依据。
Spent Potlining(SPL) is the byproduct waste of aluminum electrolytsis industry. Its annual production is about 0.12 million tons in China now. Spent potlining is a hazardous solid waste product, and cause serious environmental pollution, and endanger human health. therefore, SPL must be managed carefully. Finding alternatives to landfill disposal has been widely recognized as one of the inevitable challenges facing the global aluminum researchers today.
We carried out leaching experiment of fluorides in SPL, and characterized crystal composition of the samples using X-ray diffraction (XRD), and studied the conditions of SPL's leaching by H_2O、NaOH、HCl; We also researched fluorine emission characteristics when combusting in the high temperature tube furnaces, and determined the fluorine quantity in SPL samples and remained samples by the high temperature hydrolyzation-fluorine ion selective electrode; At the same time, we researched effect of fluorine retention using compound additive with Fe and Al and alkali metal during high-temperature tube furnace. The results showed that the quantity of fluorides can be leached by the different medium, and the sequence of leaching ability of different medium is as follows: acid leaching fluoride>alkaline leaching fluoride>water leaching fluoride; acid leaching is 79.51 %, in addition, fluorine element content in SPL after acid and alkali associated with acid leaching is 3.01 % and zero respectively using ESD; The fluorine emission tends to increase with increasing combustion temperature, and fluoride is almost entirely separated out in 1200℃; The fluorine emission increases with increasing retention period, and the fluorine emission rate reached 98.26 % at 1200℃in 30 minutes; fluorine retention rate is increased by 37.07 % additived with Al_2O_3 which was best in compound additive with Fe and Al, and is increased by 41.79 % additived with NaCl which was best in compound additive with alkali metal.
Through the research of leaching and Combustion characteristics on SPL, it could provide theoretical basis for recovering of SPL.
本文对废阴极进行了浸提实验研究,利用XRD衍射仪对废阴极的物相进行了分析,分别采用水、碱、酸等不同的介质对废阴极进行了浸提:并研究了废阴极在高温炉中燃烧时气态氟的排放特性,采用高温水解-氟离子选择电极法对试样及燃烧后残渣中氟进行了测定;另外,通过添加铁铝系氧化物及碱金属等不同的添加剂对废阴极燃烧时析出氟进行了固氟研究。结果表明:在不同的浸提介质中,废阴极中氟化物浸提率按高低顺序为:酸浸介质＞碱浸介质＞水浸介质(超声波)＞水浸介质(振荡器);2mol/LHCI酸浸浸提率约为79.51%,EDS能谱分析表明2mol/LHCI酸浸后残渣中氟化物含量约为3.01%,而采用碱、酸联合浸提后残渣中氟化物含量几乎为零;废阴极中氟析出率随燃烧温度的升高而逐渐增加,到1200℃时几乎全部析出;1200℃时氟析出率随停留时间的增加而增加,30 min后氟的析出率为98.26%;铁铝系氧化物添加剂中添加Al_2O_3后固氟效果最好,达到37.07%,碱金属添加剂中添加NaCl后固氟效果最好,达到41.79%。
本文通过对废阴极的浸提及燃烧特性实验研究,为废阴极的回收利用提供了一定的理论依据。
Spent Potlining(SPL) is the byproduct waste of aluminum electrolytsis industry. Its annual production is about 0.12 million tons in China now. Spent potlining is a hazardous solid waste product, and cause serious environmental pollution, and endanger human health. therefore, SPL must be managed carefully. Finding alternatives to landfill disposal has been widely recognized as one of the inevitable challenges facing the global aluminum researchers today.
We carried out leaching experiment of fluorides in SPL, and characterized crystal composition of the samples using X-ray diffraction (XRD), and studied the conditions of SPL's leaching by H_2O、NaOH、HCl; We also researched fluorine emission characteristics when combusting in the high temperature tube furnaces, and determined the fluorine quantity in SPL samples and remained samples by the high temperature hydrolyzation-fluorine ion selective electrode; At the same time, we researched effect of fluorine retention using compound additive with Fe and Al and alkali metal during high-temperature tube furnace. The results showed that the quantity of fluorides can be leached by the different medium, and the sequence of leaching ability of different medium is as follows: acid leaching fluoride>alkaline leaching fluoride>water leaching fluoride; acid leaching is 79.51 %, in addition, fluorine element content in SPL after acid and alkali associated with acid leaching is 3.01 % and zero respectively using ESD; The fluorine emission tends to increase with increasing combustion temperature, and fluoride is almost entirely separated out in 1200℃; The fluorine emission increases with increasing retention period, and the fluorine emission rate reached 98.26 % at 1200℃in 30 minutes; fluorine retention rate is increased by 37.07 % additived with Al_2O_3 which was best in compound additive with Fe and Al, and is increased by 41.79 % additived with NaCl which was best in compound additive with alkali metal.
Through the research of leaching and Combustion characteristics on SPL, it could provide theoretical basis for recovering of SPL.
引文
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[9]邱竹贤,魏庆斌,张明杰.铝电解中阳极效应的研究[J].东北大学学报,1982(1):1-10.
[10]邱竹贤,张明杰,何鸣鸿,等.低温铝电解的研究[J].轻金属,1984(3):35-36.
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[12]工业环境保护国家工程研究中心.我国工业固体废弃物排放和处理现状发展趋势和对策,2001年全国环保产业工作会议,http://www.bjjnbb.com.cn.
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[14]王振成主编.固体废物处理及利用[M].西安交通大学出版社,1987:6-10.
[15]王运江,刘永刚,张亚苏,等.废阴极碳块为原料生产碳素保护环的方法[P].中国专利.00114512,2000.11.22..
[16]李旺兴,陈喜平,刘凤琴,等.一种铝电解槽废阴极炭块无害化的处理方法[P].中国专利.200510124019.2005.11.28.
[17]赵隆昌,王辉.铝电解槽废内衬的综合回收方法[P].中国.01106228,2001.02.28.
[18]谷源欣.铝电解废阴极碳块工业规模回收利用[J].轻金属,1993(9):22-25.
[19]邱竹贤,翟秀静,卢惠民,等.铝工业废旧碳阴极材料的综合利用[J].轻金属,1999(11):42-44.
[20]卢惠民,邱竹贤.浮选法综合利用铝电解槽废阴极炭块的工艺研究[J].金属矿山,1997(6):32-34.
[21]侯新.铝电解炭渣回收利用技术[J].兰州工业高等专科学校学报.2002,9(4):39-43.
[22]Wangxing,Chen Xiping.Running results of the SPL detoxifying pilot plant in Chalco[J].135th TMS Annual Meeting,2006(3):12-16.
[23]Snodgrass,John 13.Cambridge,et al.Method for the recovery of fluorides from spent aluminum potlining and the production of an environmentally safe waste residue[P].United States Patent:4444740,1984.04.24.
[24]Bell.Process for the utilization of waste materials from electrolytic aluminum reduction systems[P].United States Patent:4113832,1978.9.12.
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[26]Kruger.Process for producing hydrogen fluoride from fluorine containing materials by continuous pyrohydrolysis[P].United States Patent:4294816,1981.10.13.
[27]Orth.Recovery of sodium fluoride and other chemicals from spent carbon liners[P].United States Patent:4,113,831.1978.12.9.
[28]O.J.Siljan,T.Grande,C.Schoning.Refractories for Aluminium Electrolysis Cells-PART Ⅳ:Comparison of Laboratory Investigations and Autopsies of Pot Linings[J].Aluminium,2001,77(10):809-814.
[29]陈喜平,李旺兴,周子民,等.铝电解废槽内衬的危害性研究[J].轻金属,2005(12):33-36.
[30]陈庆林,刘玉兰.氟的土壤地球化学与地方性氟中毒[J].环境科学,1981,2(6):5-9.
[31]邱竹贤.铝电解原理与应用[M].中国矿业大学出版社,1998,7:446-474.
[32]Wangxing,Chen Xiping.Running results of the SPL detoxifying pilot plant in Chalco[J].135th TMS Annual Meeting,2006(3):12-16.
[33]李方义,李清.铝电解槽废阴极内衬的回收利用[J].矿产保护与利用,2001(4):51-54.
[34]A.Agrawal,K.K.Sahu,B.D.Pandey.Solid waste management in non-ferrous industries in India[J]Resources Conservation and recycling,2003(11):103-105.
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[36]Wansfield,K.Swayn,G.Harpley.J.SPL treatment and fluoride recycling project[J].TMS Annual Meeting,EPD Congress,2002(2):315-327.
[37]齐庆杰,刘建忠,王继仁,等.煤中氟化物浸提试验研究[J].辽宁工程技术大学学报,2003,22(5):577-579.
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