富钴结壳浸出液中钴镍的N235萃取分离

对大洋富钴结壳硫酸活化浸出液经萃取分离铜、锌、锰后得到的镍钴富集溶液，用N235萃取分离镍钴。钴镍氯化物溶液用N235萃取分离的最佳的萃取工艺条件为室温，相比（O／A）=2～3：1。混合时间0．5min。经四级逆流萃取、洗涤与反萃。钴萃取率达99．99％，反萃率达99．81％，反萃液钴镍比达10^6。萃取分离后得到的氯化钴和氯化镍溶液纯度高，既可满足电解沉积金属的要求，又适于生产高纯化工产品。     

某地石材加工废料选矿提纯试验研究

以某地石材加工废料为原料,通过工艺矿物学研究石材加工废料性质,针对其性质采用了“脱泥-中磁选-强磁选-磁选提纯”的工艺流程,得到K2O与Na2O总含量大于12%、TFe含量为0.11%、白度为68.35%的优质长石,可实现对工业石材加工废料的回收和综合利用。     

形貌控制合成介孔纤维状钴酸镍粉末

以可溶性氯化镍、氯化钴和草酸为原料, 利用氨为配位剂, 通过配位共沉淀-热分解法制备了多孔纤维状钴酸镍(NiCo₂O₄)粉末。采用XRD、SEM、TEM、IR以及BET对前驱体和NiCo₂O₄粉末的物相、成分与形貌进行了表征, 系统考察了配位共沉淀条件对前驱体粉末形貌、粒度和成分的影响。采用DTA/TG研究了钴酸镍前驱体粉末的热分解历程。结果表明：Ni²⁺-Co²⁺-NH₃-NH₄⁺-C₂O₄^2--H₂O反应体系中, 在溶液pH=8.0、温度50 ℃、金属离子浓度0.5 mol/L的条件下可得到纤维状钴酸镍前驱体粉末; 氨与镍钴离子配合生成含氨草酸镍钴复盐是纤维状形貌形成的机理。在空气气氛中300 ℃热分解该前驱体粉末即可得到比表面积97 m²/g、平均孔径11 nm、轴径比30~50的纤维状多孔NiCo₂O₄粉末。     

Cyanex272在镍钴分离中的应用

研究黑镍除钴渣酸溶后溶液用Cyanex272萃取钴,实现钴、镍的深度分离,并介绍其工业生产应用.试验结果表明混合时间3rnin,Co的萃取率可达98%以上;经2级萃取溶液中的Co2+由4.5降至0.01g/L以下;负载有机相经三级洗涤[Co]/[Ni]达到529.20;通过三级萃取,三级洗涤,钴的萃取率达99.90%以上,镍钴分离系数βCo/Ni为2.50×105;两级反萃使有机相含Co2+降至0.020g/L以下;采用去离子水二级洗涤,Cl-几乎100%被洗掉,不会进入硫酸镍溶液中循环积累.工业实践中黑镍除钴渣酸溶后溶液经P204萃取除铜、铁-Cyanex272萃取分离镍钴-氯化钴溶液草酸沉淀-草酸钴煅烧,产出的精制氧化钴粉达到国家Y1级标准,产出的硫酸镍溶液完全满足生产1#电镍的要求.     

加铝熔炼—酸浸回收镍基高温合金废料

采用加铝熔炼—酸浸技术回收镍基高温合金废料,首先采用加铝熔炼技术制备加铝合金,然后利用机械破碎方式破碎加铝合金制备加铝合金粉,最后用盐酸浸出合金粉回收合金废料中的钴镍等金属。结果表明,加铝熔炼过程中铝加入质量分数为30%,熔炼温度为1 600℃时所得加铝合金质脆、易破碎,破碎后所得合金粉粒度小且粒度分布窄,破碎合金粉粒度D90为20μm左右。对此合金粉采用盐酸浸出的效果比采用硫酸的好,最佳盐酸浸出工艺条件为:盐酸浓度5mol/L、温度85℃、液固比10mL/g、浸出时间60min,在此条件下合金中的镍钴铝铬等元素进入浸出液,而钛、钼等稀有元素主要富集在渣中,合金中各金属的浸出率在80%～90%。     

加铝熔炼—酸浸技术回收镍基高温合金废料

采用加铝熔炼—酸浸技术回收镍基高温合金废料,首先采用加铝熔炼技术制备加铝合金,然后利用机械破碎方式破碎加铝合金制备加铝合金粉,最后用盐酸浸出合金粉回收合金废料中的钴镍等金属。结果表明,加铝熔炼过程中铝加入质量分数为30%,熔炼温度为1 600 ℃时所得加铝合金质脆、易破碎,破碎后所得合金粉粒度小且粒度分布窄,破碎合金粉粒度D90为20 μm左右,对此合金粉采用盐酸浸出的效果比采用硫酸的好,最佳盐酸浸出工艺条件为：盐酸浓度5 mol/L、温度85 ℃、液固比10 mL/g、浸出时间60 min,在此条件下合金中的镍钴铝铬等元素进入浸出液,而钛、钼等稀有元素主要富集在渣中,合金中各金属的浸出率在80%~90%。     

废旧三元锂电池回收中间产物铝渣的资源化研究

采用氢氧化钠碱浸-碳分工艺处理废旧电池回收中间产物——铝渣, 实现了废渣中的镍钴锰与铝分离并分步回收。结果表明, 在反应温度200 ℃、氢氧化钠浓度6 mol/L、苛性比为5、碱浸5 h条件下, 碱浸液中铝浸出率可达97.70%, 镍钴锰浸出率小于0.23%; 碱浸渣经浸出-除杂-萃取后, 得到Ni、Co、Mn含量均大于100 g/L, Fe、Al含量均小于0.001 g/L的纯净硫酸镍、硫酸钴、硫酸锰溶液, 从而实现废旧三元锂电池中铝与镍钴锰的资源化高效回收利用。     

采用离心萃取器萃取净化氯化浸出镍溶液

本研究了氯化浸出含镍物料所得的含钴铁量的高的镍溶液的净化和钴铁回收工艺，采用Ｎ２３５－异辛醇－煤油萃取体系在离心萃取器中分离镍与钴，铜，铁，锌，用离子交换除铅，用活性碳除有机物，得到可用于生产１号标准电镍的氯化镍溶液以及含Ｃｏ大于１００ｇ／Ｌ，Ｃｏ／Ｎｉ大于４０００的氯化钴溶液和含Ｆｅ大于２５ｇ／Ｌ，Ｆｅ／Ｎｉ大于１０００的氯化铁溶液，镍，钴回收率分别大于９９％和９７％。     

金刚线切割废料制备铝硅合金的研究

在晶体硅片生产过程中会产生大量的切割废料,不仅造成资源浪费,而且带来环境污染,有效回收该废料已成为亟待解决的问题。以晶体硅金刚线切割废料为硅源制备铝硅合金,引入冰晶石作为熔剂来促进硅的溶解。研究了冰晶石分子比对合金硅含量、切割废料利用率以及铝损失率的影响,得到较优的冰晶石分子比为1.6,此时得到的合金硅含量为11.74%,切割废料利用率为64.75%,铝损失率为4.78%。合金产物的XRD分析及金相表征结果表明制得的铝硅合金组织较为均匀。此外,对熔炼过程的机理也进行了系统的研究,结果表明,熔炼过程可分为两步:第一步,切割废料表面的SiO_2被熔解,使得颗粒内部的硅暴露出来;第二步,熔盐中的Si与Al液在界面处接触,生成Al-Si进入铝液。     

WC-Co硬质合金废料的回收利用

研究WC Co硬质合金废料回收利用的真空加锌熔散 真空脱锌 盐酸浸出工艺流程。在锌 /合金比为 2 ,熔散温度85 0℃ ,恒温 10～ 12h、真空度 0～ 1 3 3kPa的情况下 ,可将废WC Co合金片熔散。蒸锌温度 85 0℃、时间 2～ 3h、真空度 0～ 1 3 3kPa时 ,得到含Zn <1%且疏松易碎的炉料。浸液净化后浓缩结晶产出氯化钴 ,浸渣WC可返回硬质合金厂作原料 ,Co回收率达 97%。该工艺流程短 ,可操作性强 ,具推广应用价值     

The recovery of nickel from high-pressure acid leach solutions using mixed hydroxide product – LIX®84-INS technology

This route for the recovery of nickel from HPAL laterite solutions was successfully demonstrated by the Centaur Mining Cawse Nickel Operation and has been selected by BHPBilliton for their Ravensthorpe Nickel–Yabulu Refinery circuit. The mixed hydroxide route is also well suited to treatment of solutions by other leach processes such as Activox^®.The technology can use an acid strip coupled to nickel electrowinning or an ammonia strip and basic nickel carbonate production. The solvent extraction technology involved in these two circuits is reviewed and compared. The ancillary operations of pregnant leach solution clarification, reagent remediation, reductive stripping of cobalt, zinc and copper transfers are discussed. The treatment of ammoniacal leach solutions containing higher copper concentrations than those normally seen in laterite processing is also addressed.Possible routes for recovery of cobalt and nickel from the solvent extraction circuit are also discussed.     

大洋多金属结核催化还原氨浸提取镍钴铜

本研究以亚铜离子为催化剂、一氧化碳为还原剂，在常温常压下，于氨一碳酸铵水溶液中直接还原大洋多金属结核（又称锰结核），同时选择浸出镍、钴、铜等有价金属，锰与铁、硅等杂质一起留在浸出渣中，视市场需求决定锰的回收与否及产品方案，具有较强的市场应变能力。文章叙述了结核的还原反应动力学及还原氨浸的试验结果。该工艺对不同类型（低铁型和高铁型）的结核同样适应，在优化的工艺条件下，有价金属浸出率分别达（％）：Ｎｉ９７～９９、Ｃｏ９０～９５、Ｃｕ９０～９５，特别是钴的浸出率较传统的还原焙烧－氨浸有显著提高。     

废电池合金制备氯化镍溶液的工艺研究

对用废旧电池熔铸的含镍废合金制备氯化镍溶液的工艺进行了研究.采用的工艺流程为:盐酸体系膜电解→化学沉淀法除杂→萃取除杂.通过该工艺流程获得的三级萃余液中镍含量大于30 g/L、铁为痕量、钴为0.51 g/L、铜含量小于0.0183 mg/L,该溶液可直接用于电镍生产.     

从红土镍矿中提取镍钴铁的新工艺研究

针对云南省元江红土镍矿的矿物组成特点,在比较国内外红土镍矿处理工艺的基础上,提出了还原—磨矿—选别—氧化浸出工艺处理该矿,并进行了全流程试验。首先进行了还原—磨矿—选别试验研究,主要考察了还原温度、还原时间、添加剂配比和还原剂配比对指标的影响;其次进行了综合试验。试验结果表明,还原—磨矿—选别可以抛弃红土镍矿中80%以上的脉石,同时实现镍钴铁富集,氧压浸出工艺可实现镍钴与铁的分离,并获得铁红产品。通过试验,获得的技术指标为:从原矿至氢氧化镍(钴)段,镍直收率大于75%、钴直收率大于70%和铁直收率大于80%;氢氧化镍产品镍的品位大于31%,氢氧化钴产品钴的品位大于0.70%,铁红产品铁含量大于62%,铁红达到铁精矿要求,可以作为铁精矿出售。该工艺实现了镍钴铁综合回收,资源利用率高,环境友好,为综合回收红土镍矿中镍钴铁提供一条新的工艺技术路线。     

新疆阜康冶炼厂无污染工艺及环境治理

本文作为联合国发展中国家１９９６年６月２４～２９日北京无污染工艺专家研讨会论文，介绍了阜康冶炼厂无污染新工艺和环境治理的有关情况，并从理论上阐述了无污染工艺和污水治理的技术原理。阜康冶炼厂环境保护和治理比较好，其主要原因在于铜镍高冰镍硫酸选择性湿法精炼新工艺。该工艺除流程简单、金属回收率高、能耗低、化学药剂消耗少等优点外，显著特点是无环境污染。镍在精炼过程中不产生有害气体和粉尘，没有废渣。生产中跑冒滴漏和冲洗地面所排出的少量含镍污水，经污水处理站氢氧化钠沉淀和离子交换，可达到工业废水重金属镍离子小于１ｍｇ／Ｌ的国家排放标准。同时，选择性浸出新工艺可获得比较纯净的镍钴浸出液，经净化除钴和不溶阳极电积可生产出达到国家标准的１＃电镍。因此，该工艺的采用符合国际社会洁净工艺的发展趋势，它不仅给企业带来良好效益，而且有利于环境保护。     

Recovery of nickel and cobalt from leach solutions of nickel laterites using a synergistic system consisting of Versatic 10 and Acorga CLX 50

A direct solvent extraction (DSX) process to recover nickel and cobalt from laterite leach solutions is potentially more cost effective compared to the traditional precipitation and re-leaching method. A synergistic solvent extraction (SSX) system consisting of Versatic 10 and Acorga CLX 50 in ShellSol 2046 was studied for DSX nickel and cobalt recovery from a synthetic solution using semi-continuous tests. The effect of pH on the metal distribution profile and metal separation were investigated. It was found that the SSX system can effectively recover nickel and cobalt and separate them from manganese, calcium and magnesium. Over 99% of Ni and Co was extracted using four stages of semi-continuous extraction from the synthetic laterite solution at pH 6.3 and an A/O flowrate ratio of 1:1. More than 80% of the manganese was rejected to the raffinate. The co-extraction of calcium was less than 5% and the co-extraction of magnesium was negligible under these conditions. The co-extracted manganese and calcium were readily scrubbed in three stages semi-continuous scrubbing. The loaded strip liquor with a high concentration of nickel (71.3 g/L Ni) was obtained after two-stage continuous stripping. The final strip solution pH of 3 would be suitable for nickel electrowinning. A conceptual DSX process flowsheet using the SSX system to recover nickel and cobalt from laterite leach solutions after iron removal has been proposed.     

电池用钴基合金废料中有价金属的综合回收

根据某钴基合金废料的组成特点,依据沉淀反应的基本原理,采用“酸溶－ＮａＯＨ沉铝－ＮａＯＨ沉钴－Ｎａ２ＣＯ３深锂”工艺流程处理该废料。试验表明,最佳沉铝条件为：温度８０℃、ｐＨ值４．５;最佳沉钴温度３０℃、ｐＨ＝８;Ａｌ、Ｃｏ及Ｌｉ的回收率分别达到了９１．６％、９１．５％和９５．６％。     

Selective reductive leaching of oxidised cobalt containing residue

Nickel was selectively leached from an industrial nickel-cobalt Mixed Hydroxide Precipitate (MHP) under mildly acidic, strongly oxidizing conditions. The resulting cobalt rich residues contained 14-21 wt.% Ni, 3-7 wt.% Co and 3-9 wt.% Mn. The selective extraction of nickel and cobalt from these residues was studied using weak acid and weak acid-reductive leaching. Without the reducing agent, nickel preferentially leached. The controlled addition of a reducing agent increased the extent of nickel leaching and solubilised a portion of the cobalt while manganese remained stable in the solid phase. The extent of copper, iron and aluminium leaching was controlled by pH adjustment.     

Nickel laterite processing and electrowinning practice

Nickel as cathodes, rounds, powders, and salts, is recognized as a useful substance in heavy industry. Today, only a few producers recover this important metal, which is employed worldwide in diverse commercial and residential applications. Nickel and associated metal values are traditionally recovered from ores by mineral processing, smelting and refining processes. Associated host minerals contain non-ferrous metals such as copper, cobalt, precious metals such as gold and silver, and the platinum group of metals. The future trend is expected to involve the processing of laterites, which account for about 70% of the world's nickel resources, by means of efficient pressure acid leaching and SX-EW facilities. Large quantities of laterites are found in Australia, Cuba, Indonesia, New Caledonia, and the Philippines. Laterites are easily mined by open pit methods whereas sulphidic ores generally involve more expensive underground mining. Cobalt, zinc, and copper are extracted from these sources as by-products. Modern automated plants for processing laterites feature state-of-the-art technology and environmental compliance. Production plants range in nameplate annual capacity from 10 to 50 thousand metric tonnes of nickel contained in the final product(s).On a worldwide basis the writers are aware of 12 nickel electrowinning refineries which produce class I nickel products. The paper describes the established industrial processes for nickel recovery by means of being electrowon from either an aqueous sulphate medium or chloride medium after initial leaching and solution purification techniques. Laterites are the main source of feedstock for production of ferronickel as described herein. The paper includes information regarding nickel-bearing deep sea nodules and secondary scrap processing to recover nickel values. For completeness, other extraction processes involving pellets from the carbonyl process, nickel powders, and briquettes are noted in the compendium of nickel processing practice which includes pyrometallurgical principles. The purpose of the review for nickel operating practice is to provide a complete extractive processing summary rather than the reader reviewing many authors.     

Kinetics of selective chlorination of pre-reduced limonitic nickel laterite using hydrogen chloride

The selective chlorination process of pre-reduced limonitic nickel laterite using hydrogen chloride was investigated in this work. In HCl-O₂-H₂O-N₂ atmosphere, the effects of variations in temperature, the partial pressures of hydrogen chloride, oxygen and water vapor, and total gas flow rate were all studied. It was found that the chlorination of nickel and cobalt could be described by two stages; and it was controlled by gas diffusion through product layer. Four apparent activation energies, including 20.43 kJ/mol and 12.89 kJ/mol for the first and second stage of nickel chlorination, 14.95 kJ/mol and 13.02 kJ/mol for the first and second stage of cobalt chlorination respectively, were obtained in the temperature range of 420-460 °C. And the apparent reaction order of hydrogen chloride was also obtained. During the selective chlorination, the oxidation of pre-reduced ore could take place with the selected conditions; chlorinated iron was mostly rejected as hematite and thus nickel and cobalt were selectively chlorinated by hydrogen chloride.