从氧化钴矿石中提取钴的试验研究

研究了从氧化钴矿石中回收钴.通过两段浸出,浸出渣中钴质量分数小于0.5%,钴浸出率达99%.通过黄钾铁钒法除铁,氟化钠法除钙、镁,亚硫酸钠法除铜,P204串级萃取法进一步去除杂质Fe、Ca、Mg、Cu、Zn、Mn、Pb、As等,P507萃取分离钴镍,最后通过沉淀得草酸钴产品,产品纯度符合要求.     

Extraction of nickel,cobalt and other metals [Cu,Zn, Fe(III)] with a commercial β-diketone extractant

The extraction of nickel, cobalt, copper and zinc from ammoniacal solutions of ammonium carbonate or ammonium sulphate by solutions of Hostarex DK-16 in kerosene has been investigated as a function of phase contact time, aqueous-phase pH and organicphase reagent concentration. Besides copper, Hostarex DK-16 also partially extracts iron (III) from moderately acidic solutions whereas nickel, cobalt(II), copper and zinc are extracted from neutral or ammoniacal ammonium sulphate and ammonium carbonate solutions. Extraction decreases in the following order of metals: Cu > Co > Ni > Zn. Cobalt(III) is not extracted, but the complex of cobalt(II) with Hostarex DK-16 is slowly oxidized to a cobalt(III) complex which cannot be stripped even when 10 N sulphuric acid is used. Absorption spectra for cobalt complexes with Hostarex DK-16 (purified by preparative thin-layer chromatography) in benzene also suggest oxidation of cobalt(II) to cobalt(III) in the organic phase. Nickel, cobalt(II), zinc and copper can be stripped easily from organic solution with dilute solutions of sulphuric acid. Hostarex DK-16 extracts iron very slowly, nickel moderately rapidly and copper, cobalt(II) and zinc rapidly. Slope analysis and extraction isotherms suggest that the complexes CuR₂, NiR₂ ·HR and CoR₂·HR are present in the organic phase. Nickel can easily be separated from cobalt by extraction with Hosterex DK-16 after oxidation of cobalt in aqueous ammoniacal solution by hydrogen peroxide; however, LIX 64N seems to be a more promising extractant owing to the higher extraction of nickel under analogous conditions and the poorer extraction of zinc in comparison with Hostarex DK-16.     

多金属结核氨浸液中镍钴铜的萃取分离

采用LIX84从氨性溶液中萃取分离镍、钴、铜。首先采用 5级逆流共萃铜、镍 ,钴留在萃余液中 ,含铜、镍的负载有机相经二级洗涤氨 ;用镍电解废液进行 7级逆流选择性反萃镍 ,实现镍与铜的初步分离 ;然后从含铜有机相中反萃铜得到纯净的硫酸铜溶液 ,选择性反萃镍得到含有少量铜的粗镍液 ,该液仍采用LIX84萃取脱铜 ,并回收铜 ,从而将铜、镍彻底分离 ,实现了用一种萃取剂分离氨浸液中的镍、钴、铜。联动连续运转试验结果表明 ,采用本研究确定的萃取工艺流程和萃取设备处理氨浸液 ,萃取分离效果好 ,试验结果稳定、可靠。金属回收率高 ,萃取回收率分别为 ( %) :Ni 99 0 ,Co 99 7,Cu 99 9。     

从废弃炉渣中分离回收钴、镍

用酸（硫酸＋少量硝酸）浸出废弃炉渣,其中的Cu、Ni浸出率达99％以上,Co浸出率为87％。浸出液用铁粉置换法分离铜、黄钠铁矾法除铁、NaF法除钙镁、P204深度除杂、P507分离镍钴,杂质去除率达99．5％以上,Ni、Co回收率均超过94％。     

Separation of iron and manganese from sulphate solutions obtained from indian ocean nodules

Leach liquors obtained by sulphuric acid pressure leaching of Indian Ocean manganese nodules were treated for iron and manganese separation. This separation was carried out by sequential precipitation. Iron was precipitated by pH adjustment using lime slurry. The separation is 99.5%, with about 6.7% loss of copper and 2% loss of cobalt. From the iron-free solution manganese was precipitated as manganese dioxide in the presence of an oxidising agent, potassium perdisulphate. Under optimum conditions manganese precipitation is quantitative. There is a loss of about 27% of the cobalt due to adsorption on the manganese dioxide matrix. Kinetics of precipitation and specific reaction rates have been determined. The loss of cobalt by adsorption has been shown by fitting the data to the classical adsorption equation due to Freundlich.     

Recovery of nickel and cobalt from laterite leach solutions using direct solvent extraction: Part 1 — selection of a synergistic SX system

The separation of nickel and cobalt from impurities such as manganese, magnesium and calcium using solvent extraction with Versatic 10 was largely improved by the addition of a synergistic reagent LIX63 (an α-hydroxyoxime) or 4PC (a pyridine carboxylate ester). With the organic systems containing Versatic 10 alone, the separation factors of nickel and cobalt over manganese were 6 and 15 respectively. When 4PC was added to the system, these increased to 147 and 1870 respectively, and with LIX63, they were even higher at 534 and 7720 respectively. This indicates that the synergistic solvent extraction (SSX) system with Versatic 10 and LIX63 performed very well and better than that with Versatic 10 and 4PC.The SSX system consisting of 0.5 M Versatic 10, 0.45 M LIX63 and 1.0 M TBP in Shellsol D70 performed the best among the systems tested containing LIX63. After a single contact, the extraction of Ni and Co was 99.6% and 96.9%, respectively. Only 6 mg/L Mn, 8 mg/L Mg and 1 mg/L Ca were found in the loaded organic solution. The manganese scrub efficiency was 97.7% at pH 5.3, resulting in a scrubbed organic solution containing only 0.8 mg/L Mn. Over 99% nickel, cobalt and manganese were stripped at pH 2.0, indicating easy stripping of these metals.The SSX system consisting of 0.5 M Versatic 10 and 1.0 M 4PC in Shellsol D70 performed the best among the systems tested containing 4PC. After a single contact, the extraction of Ni and Co was 99.4% and 89.4%, respectively. Some 200 mg/L Mn, 10 mg/L Mg and 48 mg/L Ca were found in the loaded organic solution. The manganese could not be scrubbed at the tested pH range of 5.4-6.0. Very fast Ni and fast Co stripping kinetics were observed, however, the Mn stripping kinetics were very slow. After 2 min of stripping, only 1.22% Mn was stripped.It is concluded that the SSX system containing 0.5 M Versatic 10, 0.45 M LIX63 and 1.0 M TBP performed much better than the SSX system containing 0.5 M Versatic 10 and 1.0 M 4PC in terms of both manganese and calcium behaviour in extraction, scrubbing and stripping.     

从大洋多金属结核氨浸液中萃取分离铜,镍,钴

用ＬＩＸ８４的煤油溶液作萃取剂，从大洋多金属结核的催化还原氨浸溶液中选择性共萃铜和镍，而钴等留在萃余液中，然后选择反萃镍和铜，再生有机相循环使用，铜和镍溶液可用电积回收铜和镍。本工艺只需一种萃取剂便可有效地将铜、镍、钴三者彼此分离，操作简便，可用于处理大洋多金属结核或其它含铜、镍、钴的复杂矿     

Recovery of nickel and cobalt from laterite leach solutions using direct solvent extraction: Part 2: Semi- and fully-continuous tests

In Part 1 of this paper, two synergistic solvent extraction systems consisting of Versatic 10/LIX63/TBP and Versatic 10/4PC were assessed in batch tests for the separation and purification of nickel and cobalt from synthetic laterite leach solution after iron removal. In Part 2, semi- and fully-continuous tests are reported for the Versatic 10/LIX63/TBP system, with conditions optimised for separating nickel and cobalt from manganese, magnesium and calcium.Semi-continuous extraction tests were conducted using the synergistic organic system consisting of 0.50 M Versatic 10, 0.45 M LIX63 and 1.0 M TBP in Shellsol D70. With a pH profile of 5.5/6.1/6.5 for the three stages EX1/EX2/EX3 at 40 °C, the nickel and cobalt extractions were 99.9% with only 5 mg/L nickel and < 1 mg/L cobalt left in the raffinate. With two stages of scrubbing and a pH profile of 5.4/5.0 at 40 °C, about 2 mg/L manganese and less than 1 mg/L magnesium and calcium were left in the scrubbed organic solution. With two stripping stages and an O/A ratio of 10 at 40 °C using 50 g/L H₂SO₄ as strip solution, the stripping efficiencies of nickel and cobalt were over 95%.A fully-continuous pilot plant was operated for 280 h. With an O/A ratio of about 2 and a pH profile of 5.5/5.8/6.0/6.3 for the four stages EX1/EX2/EX3/EX4 at 40 °C, both nickel and cobalt were almost completely extracted. The nickel and cobalt concentration in the raffinate was lower than detection limit of 0.2 mg/L. The manganese, magnesium and calcium concentrations in the loaded organic solution were 34, 8 and 1 mg/L, respectively. Using a pH profile of 5.4/5.0 for SC1/SC2 at an O/A ratio of 10 and 40 °C, the manganese scrubbing efficiency was over 96% and the concentrations of manganese and magnesium in the scrubbed organic solution were < 5 mg/L and that of calcium 1 mg/L. Using three strip stages and a strip solution containing 50 g/L H₂SO₄ and 55 g/L Ni at an O/A ratio of 10 and 40 °C, over 98% Ni and 99% Co were stripped with only 64 mg/L Ni in the stripped organic solution. The nickel concentration in the loaded strip liquor was 86 g/L, giving a ΔNi of 31 g/L. The loaded strip liquor contained less than 1 g/L acid.     

从氨溶液中萃取镍的试验研究

用某镍矿粗制的氢氧化镍中,铁、钙、镁、硅、铜、锌、钴等杂质含量较高,进一步氨浸后,镍、铜、锌、钴等生成金属-氨络合物进入溶液,用氨性萃取剂萃取、硫酸反萃取,可将镍与其他杂质分离,获得满足电积要求的镍溶液.     

Statistical modeling of solvent extraction equilibria: extraction of copper from sulfuric acid and ammoniacal solutions by mixtures of LIX 64N and SME 529

The statistical modeling of the equilibria in the solvent extraction of copper from sulfuric acid and ammoniacal sulfate solutions by mixtures of LIX 64N and SME 529 has been carried out. This study employed an incomplete three-level factorial design involving four variables,viz., the copper and sulfuric acid or ammonia concentrations in the aqueous phase and the concentrations of the two extractants in the organic phase. The equilibrium models showed that the active oximes in LIX 64N and SME 529 are completely compatible as regards the extraction of copper without any synergistic effects between the reagents being observed. The percentage of copper extracted increases with increased extractant concentration in the organic phase, but is affected adversely by increased sulfuric acid and copper sulfate concentrations in the aqueous phase. As expected, the equilibrium extraction of copper is influenced by the diluent, with higher copper extractions being attained with mixtures of LIX 64N and SME 529 in MSB-210 as compared with Escaid 100, a diluent having a higher aromatic content and giving rise to a lower degree of oxime aggregation. The copper loading efficiency of the reagents is high for extractions from ammoniacal solution — 86.6 pct and 89.4 pct copper in the diluents MSB-210 and Escaid 100, respectively, at the center points of the experimental designvs 47.0 pct and 43.3 pct in the case of sulfuric acid solution extractions. Copper loading efficiencies greater than 100 pct are attainable in ammoniacal media, particularly in situations where the aqueous copper concentration is greatly in excess of the combined extradant concentration. This overloading is attributable to the uptake of ammonia by the hydroxyoximes and can be expected to increase with increasing aromatic content of the diluent, as in the case of Escaid 100, as a result of decreased oxime aggregation.     

Electrowinning of Nickel from Aqueous Sulphate Bath in the Presence of Metallic and LIX64N Impurities

The effects of common metallic and LIX64 organic solvent impurities on nickel electrodeposition have been investigated for an economical and viable process development for different raw materials. Variations of bath pH. temperature and current density at different LIX64N concentration were studied to observe the effects on current efficiency, physical appearance of the deposit, deposit contamination, crystallographic orientation intensities and deposit morphology.     

镍精矿加压酸浸新工艺研究

研究了金川镍精矿加压一步全浸镍、钴、铜新工艺,浸出液中和除铜后萃取分离镍钴,镍、钴、铜的浸出率可分别达到99.5%、98%和98%以上。该工艺与硫酸选择性浸出相比具有金属浸出率高、分离彻底、易分别回收等优点。     

Selective separation of copper and nickel by solvent extraction using LIX 984N

Selective separation of copper and nickel from ammoniacal/ammonium carbonate medium was carried out by using LIX 984N diluted with deodourised kerosene. The study of the influence of equilibration time, equilibrium pH, extractant concentration and selective stripping of copper and nickel has been optimized. It was found that both the metal extractions were unaffected by the changes in pH. Nickel extraction equilibrium was reached at a longer contact time than that for copper and nickel extraction depends greatly on the extractant concentration in the organic phase. Co-extraction, ammonia scrubbing and selective stripping of copper and nickel were performed for a solution containing 3 g dm^− 3 each of copper and nickel and 60 g dm^− 3 ammonium carbonate. The extraction and the percentage of stripping for nickel and copper were almost quantitative.     

Manganese metallurgy review. Part III: Manganese control in zinc and copper electrolytes

Manganese is often associated with zinc and copper minerals, and can build up in the processing circuits. Part III of the review outlines the current practice and new developments to get a better understanding of manganese behaviour and control in electrowinning of zinc and copper, and identifies suitable methods and processes to control manganese.In zinc electrowinning, the presence of small amounts of manganese (1–5 g/L) can minimise the corrosion rate of the anodes and reduce the contamination of the cathodic zinc with lead, but excess manganese results in significant decreases in the current efficiency. The neutralized zinc feed solution that contains little acid is considered to be the best place to implement manganese control. Various methods and processes for manganese control in zinc electrowinning have been developed. Oxidative precipitation and solvent extraction are the most important methods. For the neutralized zinc solution at pH 5, oxidative precipitation using a strong oxidant such as Caro's acid and SO₂/O₂ can selectively precipitate manganese as insoluble MnO₂ or Mn(OOH), leaving other impurities, e.g., Mg, Cl⁻, F⁻, etc. in the circuit. Solvent extraction of zinc using D2EHPA (di-2-ethylhexyl phosphoric acid) can selectively recover zinc from the solution and leave other impurities including manganese in the raffinate.In copper solvent and electrowinning circuits, the problem of manganese is mainly associated with the decrease in the current efficiency and degradation of the solvent caused by the higher valent manganese species generated on the anode. The prevention or minimisation of Mn(II) oxidation during the electrowinning is critical. This can be achieved by adding ferrous ions or sulfur dioxide to control the cell potential.     

复杂铜钴矿浸出溶液处理试验

以复杂铜钴矿浸出溶液为原料,采用M5774萃取铜,硫酸反萃,铜的萃取率和反萃率均大于99%,萃余液用SO_2/空气混合气氧化中和除铁、锰,除铁后液铁和铝均小于0.005g/L,锰没有完全除掉,采用活性氧化镁沉淀镍和钴,在较优条件下,镍、钴沉淀率分别为97.73%和94.33%,用活性氧化钙沉淀锰和镁。     

Production of electrolytic manganese dioxide from purified solutions after the leaching of manganese-bearing slurry

The production of electrolytic manganese dioxide from purified solutions after the leaching of manganese-bearing slurry is investigated. The influence of the anodic current density on the electrolysis of manganese-bearing solutions is determined. The preliminary purification of manganese-bearing solutions before electrolysis is discussed. Purification of the solution at pH 6.5–7.0 ensures the maximum deposition of all the impurities that interfere with electrolysis: copper, zinc, nickel, cobalt, aluminum, phosphorus, arsenic, antimony, iron (III), and iron (II). After impurity deposition, the pulp is filtered; the hydrate deposits are washed; and the filtered liquid is sent for electrolysis to obtain electrolytic manganese dioxide. The samples of electrolytic manganese dioxide are studied by means of X-ray fluorescent analysis, X-ray phase analysis, and scanning electron microscopy. The results show that the electrolytic manganese dioxide obtained in the laboratory with anodic current density I_a = 150–200 A/m² meets all the requirements on a highly active product: the content of the basic component (MnO₂) in the experiments is 95.0–96.5 wt %.     

Purification of Cobalt Chloride Solutions from Impurities by Mixtures of Extractants

The purification of cobalt chloride solutions from iron, copper and nickel by mixtures of extractants have been conducted. The composition of solutions obtained after dissolution of cobalt concentrate was in g/1: 150-180 Co, 12-18 Ni, 1-2 Cu, 5-8 Fe, and 10-15 HCl. Monocarboxylic acids with straight or branched chains were used as one of the components of extraction mixture and as the solvent. For purification of solutions from iron, 0.2-0.3 M solutions of tertiary amines in monocarboxylic acids were used. A mixture of monocarboxylic acids and aliphatic non-chelating aldoximes (heptaloxime) was used for purification of solutions from copper. Aldoximes concentration in the mixture was 0.2-0.25 M. For nickel extraction 1.5-2.0 M solution of heptaloxime in monocarboxylic acids was used. Stripping was conducted by hydrochloric acid solution 5-15 g/ 1.

The purification of cobalt solutions from impurities by these extractants was effective. Thus, the separation coefficients are for iron/cobalt - 5 x 104, for copper/cobalt ～ 5 x 10', and for nickel/cobalt -100. The extraction scheme has been tested on industrial scale. The results have supported the high efficiency of this purification. Thus, metallic cobalt obtained from the purified solutions by electrolysis had the composition in %: 99.98 Co; 0.003 Ni; 0.001 Cu; 0.003 Fe.     

从废旧三元锂离子电池中回收有价金属的新工艺研究

废旧三元锂离子电池经过放电、焙烧、破碎、筛分等预处理方法分离出电池活性物质、集流体与钢壳,再采用H2SO4-Na2SO3对废电池粉料（活性物质）进行浸出,浸出液调节pH至4.5,过滤以除去铁和铝,滤液再调pH至11左右,将锂和镍钴锰分离,得到的锂液经过浓缩后加入Na2CO3得到工业级的LiCO3,在镍钴锰富集物中加入氨水将锰和镍钴分离,最后使用P507分离镍和钴,在相比O/A=1,平衡pH=4.5,有机相组成为25% P507 75%溶剂油,经二级逆流萃取后钴的萃取率为99.3%。使用200 g/L硫酸为反萃剂,相比为5时,钴的回收率达99.21%。反萃液使用草酸铵沉钴,萃余液中的镍采用氢氧化钠沉淀,整个工艺流程中钴的回收率为91.82%,镍的回收率为91.12%。     

重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。     

重量法测定镧镍合金中稀土总量

准确测定镧镍合金中稀土总量,对于有效控制镧镍合金的生产技术和产品质量具有重要意义。因镧镍合金中镍含量在50%(质量分数,下同)以上,其他共存元素中钴约10%、锰约5%,故很难通过单一分离方式彻底分离共存元素。实验依次采用氟化分离、氨水分离、草酸沉淀方式分离共存元素,进而对镧镍合金中稀土总量的测定进行探讨。试样经盐酸和硝酸溶解,采用氢氟酸、氨水、草酸沉淀稀土,逐一分离去除干扰元素,在pH值为1.8~2.0条件下,稀土元素沉淀为草酸稀土,950℃灼烧草酸稀土生成稀土氧化物(不含氧化钍),再以镧对氧化镧换算成金属稀土总量。盐酸-硝酸能够完全平稳溶解试样,且测定结果(30.42%)与参考值(30.43%)相符;采用氟化分离、氨水分离、草酸沉淀的分离方式很好地去除了镍、钴、锰、铝、铜、铁等非稀土杂质;按照实验方法测定镧镍合金样品中稀土总量,结果的相对标准偏差(RSD,n=11)均小于0.50%;加标回收率为 99%~101%。按照实验方法选取两家实验室对镧镍合金中稀土总量进行测定数据比对,结果基本一致并与参考值相符。