真空冶金法回收WC-Co硬质合金废料的研究
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摘要
通过热力学计算,从理论上分析了1 550~2 000℃、压力小于1.73Pa的条件下,采用真空冶金法可以从WC-Co硬质合金废料中分离WC硬质相和钴黏结相。随后,以钴含量为3%~15%的WC-Co硬质合金废料为原料进行了钴含量对钴挥发率、纯度以及对WC粉末质量影响的研究。结果表明,钴挥发率随原料钴含量的增大先增大后减小,钴含量为8%时钴挥发率达最大值86.63%;原料钴含量对金属钴的纯度无明显规律性影响,钴含量为12%时金属钴纯度达最大值99.95%。WC粉末的XRD谱显示,当原料钴含量为3%和15%时出现钴衍射峰,有钴残留,原料钴含量为5%、8%及12%时未出现钴衍射峰,各次试验均未出现W2C相,无明显脱碳;WC粉末的SEM形貌显示,粉末呈近球形,表面光滑,粒径为1~8μm。试验制得了合格WC粉末和金属钴。
Separation of hard phase WC and binder phase Co from WC-Co cemented carbide scraps by vacuum metallurgy under the condition of 1 550~2 000 ℃ and<1.73 Pa was theoretically analyzed based on thermodynamic calculation.WC-Co cemented carbide scraps with cobalt content of 3% ~15% was applied as raw material to analyze relationship between cobalt content and cobalt volatilization rate,cobalt purity rate,and WC powder quality.The results show that cobalt volatilization rate rises first and drops later with increase of cobalt content in raw material,and the maximum cobalt volatilization rate is 86.63%upon cobalt content raw material is 8%.There is no regular relationship between cobalt content and cobalt purity rate,when cobalt content in raw material is 12%,cobalt purity rate is up to 99.95% of the maximum value.As shown by XRD spectrum of WC powder,Co diffraction peak appears upon cobalt content in raw material of 3%and 15%,and cobalt does not volatile completely;while Co diffraction peak does not appear upon cobalt content in raw material of 5%,8% and 12%.W2 C phase does not appear in all experiments,no significant decarburization is presented.SEM microstructure of WC powder shows that powders are nearly spherical with smooth surface and 1~8μm particle size.Qualified WC powder and metal cobalt are produced from experiment.
Separation of hard phase WC and binder phase Co from WC-Co cemented carbide scraps by vacuum metallurgy under the condition of 1 550~2 000 ℃ and<1.73 Pa was theoretically analyzed based on thermodynamic calculation.WC-Co cemented carbide scraps with cobalt content of 3% ~15% was applied as raw material to analyze relationship between cobalt content and cobalt volatilization rate,cobalt purity rate,and WC powder quality.The results show that cobalt volatilization rate rises first and drops later with increase of cobalt content in raw material,and the maximum cobalt volatilization rate is 86.63%upon cobalt content raw material is 8%.There is no regular relationship between cobalt content and cobalt purity rate,when cobalt content in raw material is 12%,cobalt purity rate is up to 99.95% of the maximum value.As shown by XRD spectrum of WC powder,Co diffraction peak appears upon cobalt content in raw material of 3%and 15%,and cobalt does not volatile completely;while Co diffraction peak does not appear upon cobalt content in raw material of 5%,8% and 12%.W2 C phase does not appear in all experiments,no significant decarburization is presented.SEM microstructure of WC powder shows that powders are nearly spherical with smooth surface and 1~8μm particle size.Qualified WC powder and metal cobalt are produced from experiment.
引文
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[3]KIM HWAN-CHEOL,SHON IN-JIN,YOON JIN-KOOK,et al.Consolidation of ultra fine WC and WC-Co hard materials by pulsed current activated sintering and its mechanical properties[J].International Journal of Refractory Metals and Hard Materials,2007,25(1):46-52.
[4]FANG Z ZAK,WANG X,RYU TAEGONG,et al.Synthesis,sintering,and mechanical properties of nanocrystalline cemented tungsten carbide-A review[J].International Journal of Refractory Metals and Hard Materials,2009,27(2):288-299.
[5]WEI C B,SONG X Y,FU J,et al.Simultaneously high fracture toughness and transverse rupture strength in ultrafine cemented carbide[J].Cryst.Eng.Comm.,2013,15(17):3305-3307.
[6]杨斌,陈广军,石安红,等.废旧硬质合金短流程回收技术的研究现状[J].材料导报,2015,29(2):68-74.
[7]LEE JAE-CHUN,KIM EUN-YOUNG,KIM JI-HYE,et al.Recycling of WC-Co hardmetal sludge by a new hydrometallurgical route[J].International Journal of Refractory Metals and Hard Materials,2011,29(3):365-371.
[8]林中坤,林晨光,曹瑞军.国内外硬质合金再生利用的现状与对策[J].硬质合金,2015,31(5):315-321.
[9]陈颢,李剑波,羊建高.硬质合金回收研究进展及发展趋势[J].有色金属科学与工程,2012,3(5):18-22.
[10]杨晓明,杨宏斌,李海涛,等.废料中W、Co元素的二次回收[J].宝鸡文理学院学报(自然科学版),2014,34(3):27-30.
[11]胡宇杰,孙培梅,李洪桂,等.废硬质合金的回收再生方法及研究进展[J].稀有金属与硬质合金,2004,32(3):53-57.
[12]张外平.电溶法处理低钴硬质合金废料的研究[J].硬质合金,2006,23(2):107-109.
[13]张愈祖,蔡传算.含钴硬质合金废料的综合回收[J].矿冶工程,2000,20(2):35-36.
[14]姜文伟,高晋,普崇恩,等.硫酸钠熔炼法处理废硬质合金工艺中钴的回收[J].稀有金属与硬质合金,2000,28(2):22-25.
[15]汤青云,吴永兰,段冬平.硝石熔炼法从废顶锤中回收金属钨和钴[J].湘南学院学报,2004,25(2):51-53.
[16]孙宝琦.关于我国废残硬质合金回收与再生问题的一些看法[J].稀有金属与硬质合金,1998,26(3):12-16.
[17]陈立兰,译.废旧硬质合金的回收-化学法和锌熔法的比较[J].四川有色金属,2000(4):53-56.
[18]戴永年,杨斌.有色金属材料的真空冶金[M].北京:冶金工业出版社,2000:59-60.