从钴废料回收钴产品
摘要
本文研究了从钴锂膜废料和硬质合金处理渣中回收生产氧化钴、氧化亚钴、超细钴粉等钴产品。
依据钴锂膜废料的组成特点，采用碱溶除铝、酸浸出、喷淋沉铁铝之后，溶液直接草酸铵沉钴，再煅烧制取钴氧化物产品工艺处理钴锂膜废料。通过实验室条件试验，确定最佳条件：液固比4:1、温度80℃、时间1h、n(NaOH)／3n(渣中Al)=1.10，在此最佳条件下，85％以上的铝进入溶液，钴浸出率＞99.5％，钴直收率为91.5％，总回收率95.4％，钴氧化物符合国标Y类产品要求，钴粉符合硬质合金生产标准
以钴锂膜废料处理过程中生产的COCl_2溶液制取的Co(OH)_2为原料，用乙二醇为溶剂和还原剂，制得了分散性很好，球形超细钴粉。NaOH浓度的增加，能够大大提高反应速度。单位体积乙二醇中的Co(OH)_2加入量及添加剂的用量，均对钴粉的的粒度与形貌产生一定的影响。在Co(OH)_2 150g/L、NaOH用量40g/L及30g表面活性剂/L乙二醇，194℃回流2h的条件下，制得的钴粉的粒度分析表明粒度分布较窄，平均粒径为0.88μm，比表面积为2.705m~2/g。
In this article the productions, such as cobalt oxide, cobaltous oxide and ultrafine cobalt powder, were recovered from the scraps of cobalt and lithium film and residues of treating hard alloys.
According to the constituent characteristics of the scraps of cobalt and lithium film, the flow sheet includes these steps, such as removing aluminum by alkali solution, leaching cobalt by hydrochloric acid, removing aluminous, cupric and ferric, depositing cobalt with ammonium oxalate and calcining the cobalt oxalate. After laboratory experiments studying, the optimum conditions of every process were determined. In the processing of removing the aluminum by alkali solution, when the
optimum conditions were ratio of liquid and solid 4:1, temperature 80℃,
reacting time 1 hour, nNaOH/3nAl(in residues) 1-1. more than 85% Al enter into the solution. In order to reducing the consumption of hydrochloric acid using in leaching and of alkali using in neutralizing, two steps of leaching were used. At the first step the optimum conditions were hydrochloric
acid 2.4~2.5mol/L , temperature 80℃, reacting time 2 hours. Through
increasing the terminal hydrochloric acid concentration of the second decomposition step, the cobalt content in the residues is lower than 1.0% and leaching ratio is more than 99.5%. In the process of removing Fe, Al
by spray-pour method, temperature was more than 80℃ and terminal pH
value was controlled ranging from 5.5 to 6.0. The content of Fe, Al in the purified solution was lower than 0.008g/L and 0.014g/L respectively. The cobalt content in the purified residues was lower than 1.0% averagely and the direct and sum recovery is 91.5% and 95.4% respectively. The quality of cobalt oxide accords with the requirement of grade Y of national standards.
The flow sheet includes roasting, leaching, depositing Fe and Cu by spray-pour method, directly depositing cobalt by ammonium oxalate and calcining. The product of grade T1 was recycled from the residues of treating hard alloys. According to the characteristic of residues that cobalt exists in Co9S8 form, sodium nitrate is used as oxidant. The optimum
conditions of roasting are W(NaNO3)/W(residues) 0.8 times, temperature 750℃, time 2.5 hours. The spray-pour method is used during the process
of purification, which avoids forming the iron hydroxide colloid. The terminal pH value was controlled ranging from 5.5 to 6.0, some impurities, such as Fe3+ and Cu2+, can be removed thoroughly. The average cobalt content in the purified residues is about 1.0% and the direct and sum recovery is 90.15% and 92.78% respectively. The recovery of tantalum is 85% and the tantalum content in residues is more than 15%.
Ultrafine, monodispersed, spherical cobalt powder has been fabricated by reducing cobalt hydroxide with glycol. The basic material of cobalt hydroxide was produced by depositing cobalt chloride solution which is recycled from the scraps of cobalt and lithium film. It was investigated that the increasing of NaOH concentration speeds the reaction rate greatly. The concentration of cobalt hydroxide and surfactant bring about effects on the morphology and particle size.
依据钴锂膜废料的组成特点，采用碱溶除铝、酸浸出、喷淋沉铁铝之后，溶液直接草酸铵沉钴，再煅烧制取钴氧化物产品工艺处理钴锂膜废料。通过实验室条件试验，确定最佳条件：液固比4:1、温度80℃、时间1h、n(NaOH)／3n(渣中Al)=1.10，在此最佳条件下，85％以上的铝进入溶液，钴浸出率＞99.5％，钴直收率为91.5％，总回收率95.4％，钴氧化物符合国标Y类产品要求，钴粉符合硬质合金生产标准
以钴锂膜废料处理过程中生产的COCl_2溶液制取的Co(OH)_2为原料，用乙二醇为溶剂和还原剂，制得了分散性很好，球形超细钴粉。NaOH浓度的增加，能够大大提高反应速度。单位体积乙二醇中的Co(OH)_2加入量及添加剂的用量，均对钴粉的的粒度与形貌产生一定的影响。在Co(OH)_2 150g/L、NaOH用量40g/L及30g表面活性剂/L乙二醇，194℃回流2h的条件下，制得的钴粉的粒度分析表明粒度分布较窄，平均粒径为0.88μm，比表面积为2.705m~2/g。
In this article the productions, such as cobalt oxide, cobaltous oxide and ultrafine cobalt powder, were recovered from the scraps of cobalt and lithium film and residues of treating hard alloys.
According to the constituent characteristics of the scraps of cobalt and lithium film, the flow sheet includes these steps, such as removing aluminum by alkali solution, leaching cobalt by hydrochloric acid, removing aluminous, cupric and ferric, depositing cobalt with ammonium oxalate and calcining the cobalt oxalate. After laboratory experiments studying, the optimum conditions of every process were determined. In the processing of removing the aluminum by alkali solution, when the
optimum conditions were ratio of liquid and solid 4:1, temperature 80℃,
reacting time 1 hour, nNaOH/3nAl(in residues) 1-1. more than 85% Al enter into the solution. In order to reducing the consumption of hydrochloric acid using in leaching and of alkali using in neutralizing, two steps of leaching were used. At the first step the optimum conditions were hydrochloric
acid 2.4~2.5mol/L , temperature 80℃, reacting time 2 hours. Through
increasing the terminal hydrochloric acid concentration of the second decomposition step, the cobalt content in the residues is lower than 1.0% and leaching ratio is more than 99.5%. In the process of removing Fe, Al
by spray-pour method, temperature was more than 80℃ and terminal pH
value was controlled ranging from 5.5 to 6.0. The content of Fe, Al in the purified solution was lower than 0.008g/L and 0.014g/L respectively. The cobalt content in the purified residues was lower than 1.0% averagely and the direct and sum recovery is 91.5% and 95.4% respectively. The quality of cobalt oxide accords with the requirement of grade Y of national standards.
The flow sheet includes roasting, leaching, depositing Fe and Cu by spray-pour method, directly depositing cobalt by ammonium oxalate and calcining. The product of grade T1 was recycled from the residues of treating hard alloys. According to the characteristic of residues that cobalt exists in Co9S8 form, sodium nitrate is used as oxidant. The optimum
conditions of roasting are W(NaNO3)/W(residues) 0.8 times, temperature 750℃, time 2.5 hours. The spray-pour method is used during the process
of purification, which avoids forming the iron hydroxide colloid. The terminal pH value was controlled ranging from 5.5 to 6.0, some impurities, such as Fe3+ and Cu2+, can be removed thoroughly. The average cobalt content in the purified residues is about 1.0% and the direct and sum recovery is 90.15% and 92.78% respectively. The recovery of tantalum is 85% and the tantalum content in residues is more than 15%.
Ultrafine, monodispersed, spherical cobalt powder has been fabricated by reducing cobalt hydroxide with glycol. The basic material of cobalt hydroxide was produced by depositing cobalt chloride solution which is recycled from the scraps of cobalt and lithium film. It was investigated that the increasing of NaOH concentration speeds the reaction rate greatly. The concentration of cobalt hydroxide and surfactant bring about effects on the morphology and particle size.
引文
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[05]Kameswari S. Preparation and characterization of fine cobalt metal and oxide Powders. PMAI News letters, 19784(4):16～21
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[10]Hanf N W, Schmidt C G. Roasting d leaching of witwatersrand pyrite concentrates. Journal of The South African Institute of Mining and Metallurgy, 1979, 79(13): 365～371
[11]Anand S, Das R P, Jena P K. Sulphuric acid pressure leaching of Cu-Ni-Co matte obtained from copper converter slag-optimisation through factorial design. Hydrometallurgy, 1991, 26(3): 379～388
[12]Pandey B D, Bagehi D, Kumar V, et al. Pressure sulpuric acid leaching of a sulphide concentrate to recover copper, nickel and cobalt. Transactions of the Institution of Mining and Metallurgy, Section C: Mineral Processing and Extractive Metallurgy, 2002, 111(May/Aug.): 106～109
[13]Vu C, Han K N, Lawson F. Leaching behavior of cobaltous and cobalto-cobaltic oxidein ammonia and acid solutions. Hydrometallurgy, 1980, 6(1-2): 75～87
[14]Jana R K, Akerkar D D. Studies of the metal-ammonia-carbon dioxide-water system in extraction metallurgy of polymetallic sea nodules. Hydrometallurgy, 1989, 22(3): 363～378
[15]Lawrence R W, Poulin R, Kalin M, et al. The potential biotechnology in the mining industry.Mineral processing and extractive Metallurgy review,1998,19(1): 5
[16]汪夏燕，李朋恺，易雯．废触媒回收钴生产氧化钴工艺的研究．无机盐工业，
1998，30(5)：33～34
[17]林河成．从钴催化剂废料中回收氧化钴的研究．世界有色金属，1998，(9)：19～22
[18]苏念英，崔嘉麟．废金刚石刀具中钴的回收利用．广西化工，1997，26(3)：56～58
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[20]柴立元，钟海云．电解法回收废旧硬质合金．稀有金属与硬质合金，1996，(9)：38～42
[21]赵庭凯，唐谟堂．湿法炼锌净化钴渣新处理工艺．中南工业大学学报(自然科学版)，2001，32(4)：371～75
[22]Yan Huang, Chunshan Zhou. Hydrometallurgical process for recovery of cobalt from zinc plant residue. Hydrometallurgy, 2002, 63(3): 225～234
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