工业硫酸镍生产技术进展

doi:10.16085/j.issn.1000-6613.2015.08.028

摘要/Abstract

摘要： 含镍原料主要有产品、原矿、冶炼副产、废料等4类。含镍原料不同,生产工业硫酸镍的工艺技术也有很大的差别。根据制备工业硫酸镍的研究进展和生产现状,本文将上述4类原料进一步细分为10种,产品分为金属镍、羰基镍,原矿分为硫化镍矿、红土镍矿,冶炼副产分为粗制硫酸镍、退镀废液/电镀污泥和酸洗污泥,含镍废料分为废催化剂、电池废料和废合金。本文以含镍原料为出发点,对各种含镍原料制备工业硫酸镍的生产技术进行了综述,特别详细地介绍了各生产技术中浸出和精炼工艺的进展,同时结合现有技术工艺提出了理论可行的技术路线;根据对各种原料生产企业的实地考察,总结了工业硫酸镍现有工业化的生产情况;最后展望了工业硫酸镍制备的发展方向。

关键词: 工业硫酸镍, 含镍原料, 生产技术

Abstract: Raw materials containing nickel are classified in four categories, including nickel products, ores, byproducts and waste materials. The preparation technologies of nickel sulfate for industrial use varies with different raw materials. According to the research progresses and production status of nickel sulfate, the four categories of nickel-containing raw materials were further classified into ten sub-categories in this paper. Nickel products were categorized into metallic nickel and nickel carbonyl, nickel ores were categorized into nickel sulphide ores and nickel laterite ores, byproducts were categorized into nickel sulfate, deplating wastewater/electroplating sludge, and pickling sludge, and waste materials were categorized into spent nickel-based catalyst, spent batteries and nickel alloy scrap. This paper reviewed the strengths of raw materials containing nickel, progresses in the industrial preparation technologies of nickel sulfate respectively, presented leaching and refining techniques in detail particularly, and proposed feasible processes in theory. In addition, industrialization production status was summarized based on the comprehensive survey of existing plants. Finally, the perspective of preparation technologies of nickel sulfate with each material was also put forward.

Key words: nickel sulfate for industrial use, raw materials containing nickel, production technologies

中图分类号:

王亚秦, 付海阔. 工业硫酸镍生产技术进展[J]. 化工进展, 2015, 34(08): 3085-3092,3104.

WANG Yaqin, FU Haikuo. Progresses in the preparation technologies of nickel sulfate for industrial use[J]. Chemical Industry and Engineering Progree, 2015, 34(08): 3085-3092,3104.

参考文献

[1] Luo H J, Song B N, Liu Y H, et al. Electroless Ni-P plating on Mg-Li alloy by two-step method[J]. Trans. Nonferrous Met. Soc. China, 2011, 21(10): 2225-2230.
[2] Yang M J, Nan J M, Hou X L, et al. Preparation and electrochemical performances of nickel metal hydride batteries with high specific volume capacity[J]. Chin. J. Chem. Eng., 2008, 16(6): 944-948.
[3] 张煜, 邱运仁. 纳米氧化镍的制备及性能表征[J]. 化工进展, 2010, 29(5): 918-921.
[4] Kresse G, Hafner J. First-principles study of the adsorption of atomie H on Ni(111), (100) and (110)[J]. Surf. Sci., 2000, 459(l-2): 287-302.
[5] Kammler T, Lee J, Kuppers J. A kinetie study of the interaction of gaseous H(D) atoms with D(H) adsorbedon Ni(100) surfaces[J]. J. Chem. Phys., 1997, 106(17): 7362-737.
[6] 李国庭, 胡庆福, 李保林, 等. 低温空气氧化溶解法制取硫酸镍[J]. 煤炭与化工, 1998(4): 4-5.
[7] Fierro C, Benet G E, Zallen A, et al. Process for converting nickel to nickel sulfate: US, 007364717 B2[P]. 2008-04-29.
[8] 王军. 稀硫酸-过氧化氢体系对镍金属溶解性的探讨[J]. 金川科技, 2007(4): 13-15.
[9] 李东波. 金属镍直接制备精制硫酸镍研究[D]. 昆明: 昆明理工大学, 2011.
[10] 李大平. 电解法制备硫酸镍工艺研究[J]. 河南化工, 1999 (8): 10-12.
[11] Rademan J A M, Lorenzen L, van Deventer J S J. The leaching characteristics of Ni-Cu matte in the acid-oxygen pressure leach process at Impala Platinum[J]. Hydrometallurgy, 1999, 52(3): 231-252.
[12] Fugleberg S, Hultholm S, Holohan T. Method for leaching nickel-copper matte employing substantially neutral leaching solutions: US, 5628817[P]. 1995-11-13.
[13] 徐广平, 安本, 周敖东, 等. 水淬高冰镍硫酸选择性浸出制取电池级高纯硫酸镍工艺: 中国, CN1243838C[P]. 2003-11-13.
[14] 付海阔, 王亚秦, 莫裕杏, 等. 红土镍矿酸浸沉镍后液中镁资源化的研究进展[J]. 矿产综合利用, 2013(6): 4-8.
[15] Fittock J E. Nickel and cobalt refining by QNI Pty Ltd, Yabulu, Queensland[R]. Melbourne: Australian institute of mining and metallurgy, 2009.
[16] Chen S L, Guo X Y, Shi W T, et al. Extraction of valuable metals from low-grade nickeliferous laterite ore by reduction roasting-ammonia leaching method[J]. J. Cent. South Univ. Technol., 2010, 17(4): 765-769.
[17] 张仪, 张新普, 杨德学, 等. 一种硫酸和氨联合浸出红土镍矿生产硫酸镍的方法: 中国, 102417980B[P]. 2011-11-18.
[18] Xue J Q, Lu X, Du Y W, et al. Ultrasonic-assisted oxidation leaching of nickel sulfide concentrate[J]. Chin. J. Chem. Eng., 2010, 18(6): 948-953.
[19] Crundwell F K, Moats M S, Ramachandran V, et al. Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metals[M]. Germany: Elsevier Ltd., 2011: 95-107.
[20] Donegan S. Direct solvent extraction of nickel at Bulong operations[J]. Miner. Eng., 2006, 19(12): 1234-1245.
[21] 莫兴德, 肖连生, 张贵清, 等. HBL110从红土镍矿加压浸出液中萃取镍的研究[J]. 有色金属: 冶炼部分, 2014(6): 30-33.
[22] Mendes F D, Martins A H. Selective nickel and cobalt uptake from pressure sulfuric acid leach solutions using column resin sorption[J]. Int. J. Miner. Process., 2005, 77(1): 53-63.
[23] Wang X W, Chen Q Y, Yin Z L, et al. Homogeneous precipitation of As, Sb and Bi impurities in copper electrolyte during electrorefining[J]. Hydrometallurgy, 2011, 105(3-4): 355-358.
[24] 欧阳淮, 贾荣. 电池工业用精制硫酸镍的生产[J]. 有色金属: 冶炼部分, 2004(4): 23-25.
[25] Agrawal A, Manoj M K, Kumari S, et al. Extractive separation of copper and nickel from copper bleed stream by solvent extraction route[J]. Miner. Eng., 2008, 21(15): 1126-1130.
[26] 吴展, 陈志友, 侯琼英, 等. 一种粗硫酸镍精制并回收有价金属的方法: 中国, 103224259A[P]. 2013-05-15.
[27] 刘振海, 王鹏, 姜洪泉, 等. 铜镍电镀退镀废液资源化处理工艺[J]. 环境科学, 2002, 23(2): 113-116.
[28] 郑云朋. 硝酸退镀液中铜镍分离回收与资源化工艺研究[D]. 杭州: 浙江工业大学, 2009.
[29] Agrawal A, Sahu K K. An overview of the recovery of acid from spent acidic solutions from steel and electroplating industries[J]. J. Hazard. Mater., 2009, 171(1-3): 61-75.
[30] Li C C, Xie F C, Ma Y, et al. Multiple heavy metals extraction and recovery from hazardous electroplating sludge waste via ultrasonically enhanced two-stage acid leaching[J]. J. Hazard. Mater. 2010, 178 (1-3): 823-833.
[31] 郭学益, 石文堂, 李栋, 等. 采用旋流电积技术从电镀污泥中回收铜和镍[J]. 中国有色金属学报, 2010, 20(12): 2425-2430.
[32] 罗爱平, 吴芳. 一种综合处理含镍废料生产硫酸镍的方法: 中国, 1022212698B[P]. 2011-05-19.
[33] 祝万鹏, 杨志华. 溶剂萃取法回收电镀污泥中的有价金属[J]. 给水排水, 1995, 21(12): 16-18.
[34] 张广柱. 氨法回收电镀污泥中镍的工艺研究[D]. 南宁: 广西大学, 2009.
[35] Amaral F A D, Santos V S, Bernardes A M. Metals recovery from galvanic sludge by sulfate roasting and thiosulfate leaching[J]. Miner. Eng., 2014, 60: 1-7.
[36] Rossini G, Bernardes A M. Galvanic sludge metals recovery by pyrometallurgical and hydrometallurgical treatment[J]. J. Hazard. Mater., 2006, 131(1-3): 210-216.
[37] Fournier D, Lemieux R, Couillard D. Essential interactions between thiobacillus ferrooxidans and heterotrophic microorganisms during a wastewater sludge bioleaching process[J]. Environ. Pollut., 1998, 101(2): 303-309.
[38] Rastegar S O, Mousavi S M, Shojaosadati S A. Cr and Ni recovery during bioleaching of dewatered metal-plating sludge using acidithiobacillus ferrooxidans[J]. Bioresour. Technol., 2014(167): 61-68.
[39] Li L F, Caenen P, Jiang M F. Electrolytic pickling of the oxide layer on hot-rolled 304 stainless steel in sodium sulphate[J]. Corros. Sci., 2008, 50(10): 2824-2830.
[40] Zhang H W, Hong X. An overview for the utilization of wastes from stainless steel industries[J]. Resou., Conserv. Recy., 2011, 55(8): 745-754.
[41] Ognyanova A, Ozturk A T, de Michelis I, et al. Metal extraction from spent sulfuric acid catalyst through alkaline and acidic leaching[J]. Hydrometallurgy, 2009, 100(1-2): 20-28.
[42] 刘富强, 朱兆华, 邓华利. 废镍催化剂中有价金属回收试验研究[J]. 三峡环境与生态, 2008, 1(2): 21-23.
[43] 王玉强. 双氧水氢化废镍催化剂回收利用的研究[J]. 当代化工, 2006, 35(2): 90-92.
[44] Mishra D, Kim D J, Ralph D E, et al. Bioleaching of spent hydro-processing catalyst using acidophilic bacteria and its kinetics aspect[J]. J. Hazard. Mater., 2008, 152(3): 1082-1091.
[45] Amiria F, Mousavi S M, Yaghmaei S, et al. Bioleaching kinetics of a spent refinery catalyst using Aspergillus niger at optimal conditions[J]. Biochem. Eng., 2012(67): 208-217.
[46] Bharadwaj A, Ting Y P. Bioleaching of spent hydrotreating catalyst by acidophilic thermophile Acidianus brierleyi: Leaching mechanism and effect of decoking[J]. Bioresour. Technol., 2013(130): 673-680.
[47] 彭容秋. 再生有色金属冶金[M]. 沈阳: 东北大学出版社, 1994: 129-148.
[48] 徐承坤, 翟玉春, 田彦文. 镉镍废电池湿法回收工艺[J]. 电源技术, 2001, 25(1): 32-34.
[49] 孔祥华, 王晓峰. 旧镉镍电池湿法回收处理电池[J]. 电池, 2001, 31(2): 97-99.
[50] Velgosová O, Kaduková J, Marcinčáková R, et al. Influence of H₂SO₄and ferric iron on Cd bioleaching from spent Ni-Cd batteries[J]. Waste Manage., 2013, 33(2): 456-461.
[51] Bouvier A, Foelzer A, Kleinsorgen K, et al. Process for recovery of metals from used nickel-metal hydride accumulators: EP, 19950940265[P]. 1995-12-01.
[52] Zhang P W, Yokoyam T, Wakui Y, et al. Recovery of metal values from spent nickel–metal hydride rechargeable batteries[J]. J. Power Sources, 1999, 77(2): 116-122.
[53] 杨志远. 废旧镍氢电池中镍钴回收工艺的研究[D]. 沈阳: 东北大学, 2008.
[54] 夏煜, 黄美松, 杨小中, 等. 用废Ni-MH电池正极材料制备电子级硫酸镍的研究[J]. 矿冶工程, 2005, 25(4): 46-53.
[55] 余海军, 谢英豪, 张铜柱. 车用动力电池回收技术进展[J]. 中国有色金属学报, 2014, 24(2): 446-460.
[56] 柳松, 古国榜. 镍基高温合金废料的回收[J]. 无机盐工业, 1999, 31(2): 38-39.
[57] Shen Y F, Xue W Y, Niu W Y. Recovery of Co(Ⅱ) and Ni(Ⅱ) from hydrochloric acid solution of alloy scrap[J]. Trans. Nonferrous Met. Soc. China, 2008, 18(5): 1262-1268.
[58] 刘熙光, 李德华, 陈良健, 等. 用废镍铁片生产高纯度硫酸镍[J]. 湿法冶金, 2000, 19(4): 42-43.
[51] Bouvier A, Foelzer A, Kleinsorgen K, et al. Process for recovery of metals from used nickel-metal hydride accumulators: EP, 19950940265[P]. 1995-12-01.
[52] Zhang P W, Yokoyam T, Wakui Y, et al. Recovery of metal values from spent nickel–metal hydride rechargeable batteries[J]. J. Power Sources, 1999, 77(2): 116-122.
[53] 杨志远. 废旧镍氢电池中镍钴回收工艺的研究[D]. 沈阳: 东北大学, 2008.
[54] 夏煜, 黄美松, 杨小中, 等. 用废Ni-MH电池正极材料制备电子级硫酸镍的研究[J]. 矿冶工程, 2005, 25(4): 46-53.
[55] 余海军, 谢英豪, 张铜柱. 车用动力电池回收技术进展[J]. 中国有色金属学报, 2014, 24(2): 446-460.
[56] 柳松, 古国榜. 镍基高温合金废料的回收[J]. 无机盐工业, 1999, 31(2): 38-39.
[57] Shen Y F, Xue W Y, Niu W Y. Recovery of Co(Ⅱ) and Ni(Ⅱ) from hydrochloric acid solution of alloy scrap[J]. Trans. Nonferrous Met. Soc. China, 2008, 18(5): 1262-1268.
[58] 刘熙光, 李德华, 陈良健, 等. 用废镍铁片生产高纯度硫酸镍[J]. 湿法冶金, 2000, 19(4): 42-43.