红土镍矿酸浸废水中铁镁分离与回收利用

以红土镍矿酸浸产生的废水为原料,采用氧化-中和水解法沉淀铁,氢氧化钙沉淀法沉镁制备无机填料,为红土镍矿酸浸废水中有价金属的回收利用提供依据。研究了沉铁过程中温度和反应终点pH值对沉铁率及镁损失率的影响,获得适宜的沉铁条件为:温度40 ℃、pH=4.0,此时沉铁率可达99.86%,镁损失率约为2%。同时研究了沉镁过程中反应时间、反应温度、搅拌速度、镁钙摩尔比对镁沉淀率和钙利用率的影响,结果表明:温度50 ℃、搅拌速度300 r/min、反应时间2 h、镁钙摩尔比1∶1.2时,沉镁率可达99.53%,钙利用率为96.46%。采用XRD和SEM分析了沉镁产物的组成和结构,表明其为[Mg(OH)₂-CaSO₄·2H₂O]混合物,可用作无机填料。     

废旧镍钴锰电池浸出液中镍钴锰元素选择性回收工艺研究

研究了废旧锂离子电池浸出液中金属离子的分离回收工艺，通过硫化物选择性沉淀实现了浸出液中镍、钴离子与锰离子的高效分离与回收。研究了pH值、硫化钠加入系数、沉淀温度、沉淀时间对镍、钴、锰离子沉淀率的影响。结果表明，在沉淀温度25℃、硫化钠加入系数1.5、pH值5.0、沉淀时间6 min条件下，镍、钴、锰、铝离子沉淀率分别为99.73%、100%、2.77%、1.24%;正交实验结果表明，各因素对镍离子沉淀率影响的主次顺序为：硫化钠加入系数>pH值>沉淀温度>沉淀时间；对钴离子沉淀率影响的主次顺序为：硫化钠加入系数>沉淀温度>pH值>沉淀时间。在沉淀温度70℃、硫化钠加入系数2.5、pH值6.0、沉淀时间12 min条件下，锰、铝离子沉淀率分别为99.77%、6.86%。     

印尼某红土镍矿常压浸出实验研究

以印尼某地红土镍矿为原料,考察了浸出时间、浸出温度、硫酸浓度、液固比等因素对硫酸常压浸出镍、铁的影响。结果表明,硫酸浸出红土镍矿的适宜工艺参数为: 初始硫酸浓度300 g/L、液固比6∶1、搅拌速度300 r/min、浸出温度85 ℃、浸出时间240 min,此优化条件下红土镍矿中Ni浸出率97%,Fe浸出率83%。对浸出渣进行XRD、SEM分析表明,红土镍矿晶型较稳定,浸出后形貌无较大变化; 浸出渣主要成分为铁氧化物、硅氧化物和铁酸镍、铁酸镁。     

硝酸浸出液中铝高效脱除的研究

本文以红土镍矿硝酸浸出液为对象,系统研究了硝酸浸出液中沉淀除铝环节,并提出一种高效沉淀除铝的新方法。详细考察了反应温度、陈化前pH值和陈化时间对沉淀除铝的影响,得到最佳工艺条件：反应温度为40℃、陈化前pH值为4.0~4.2和陈化时间为30 min。和常规沉淀法对比得出：最佳工艺条件下得到的铝渣镍、钴夹带率均小于1%,比常规沉淀法低3%以上;得到的沉淀矿浆固液分离容易,在负压0.04Mpa时,抽滤速度为0.22 m₃/(h.m₂),是常规沉淀法的12~13倍。本文成功解决了湿法冶金中铝沉淀后难过滤以及有价金属夹带多的难题,具有广阔的应用前景。     

赣南某红土镍矿常压酸浸液中杂质离子的除去

赣南某红土镍矿常压酸浸液中含有铁、镁、铜、铅、锌等杂质离子,且这些杂质离子与镍离子分离较困难。采用黄钠铁矾法去除铁离子,达到了99%的去除率;采用硫化钠沉淀法去除铜、铅、锌等重金属离子,达到了90%的去除率;采用氟化钠法去除镁离子,达到了90%的去除率;各作业段镍离子作业损失率分别为15%、12%、5%。     

高镁低品位铜镍矿氧压硫酸浸出液综合回收研究

针对高镁低品位铜镍矿氧压硫酸浸出液特点,提出“Lix984萃取提铜-MgO中和黄钠铁矾法沉淀除铁-MgO中和沉镍”综合回收工艺。结果表明,采用Lix984可选择性萃取99.79%的铜,其他金属离子基本不萃取,经模拟工业贫铜电解液反萃,铜反萃率达98.13%,得到富铜电解液,可电积制备金属铜; 萃铜余液通过MgO中和黄钠铁矾法沉淀除铁,铁沉淀率达99.20%,镍损失率仅0.60%; 沉铁后液通过MgO中和沉淀回收镍,镍沉淀率为99.91%,并得到镍含量24.13%的氢氧化镍粗产品; 沉镍后的高浓度硫酸镁沉淀后液,可用于回收镁。     

湿法炼锌高钴渣处理工艺研究

采用锌粉置换除钴得到的高钴渣,针对现有工艺的不足,提出了一段硫酸浸出-二段高钴渣中和-过氧化氢氧化除铁-锌粉置换除镉-新型活性硫化剂（简称除镍试剂）除镍-过硫酸钠选择性氧化除锰-过硫酸钠氧化沉钴的湿法冶金工艺,实现渣中钴和镍的分离回收。对工艺流程探究,得出了较优的实验结果。硫酸浓度为150 g/L,温度80℃条件下浸出120min,钴的浸出率为96.14%。锌、镍、镉、铁、锰的浸出率均大于99%。过氧化氢沉铁率达到99.8%以上,过硫酸钠除锰可使锰除到0.13mg/L,沉淀率达到99.98%,Co沉淀率达到99.99%,氧化渣中钴含量达到49.75%。     

褐铁矿型红土镍矿硫酸高压浸出的研究

研究了褐铁矿型红土镍矿硫酸高压浸出过程中浸出温度和时间、硫酸用量对镍、钴、锰、铁、铝、镁、硅、铬浸出的影响。在浸出温度为250℃,浸出压力3.9 MPa,浸出时间为40 min,硫酸用量240kg/t干矿的优化条件下,镍,钴,锰的浸出率分别为96.8%,96.6%,98.7%,铁、铝、镁、硅的浸出率分别降低到2.6%,16.9%,61.8%,1.9%,铬的浸出率降低到0.7%,浸出液中的铬以Cr~(3+)的形式存在,浸出液中没有Cr~(6+)。静置分离试验表明,在此浸出条件下的浸出矿浆固液分离效率较高。扫描电镜分别对30、40、60 min浸出渣相微观形貌的分析表明,浸出30 min时针铁矿中Fe~(3+)绝大部分溶出并经过水解重新沉淀,延长浸出时间只是使铁相的等粒-圆粒状颗粒分布趋于均化。浸出渣相的主要成分为Fe_2O_3,(H_3O)Al_3(OH)_6(SO_4)_2,KAl_3(SO_4)_2(OH)_6及Si O_2。     

从低品位氧化锰矿中综合回收镍钴

研究了从低品位氧化锰矿经还原焙烧、硫酸浸出得到的含钴镍原料液中回收钻镍的工艺.结果表明:控制原料液初始pH值低于2有利于防止钴镍及锰形成氢氧化物沉淀而损失.分别以Na2S,BaS,MnS作为沉淀剂沉淀镍、钴,在pH值分别大于3.5,4,2时,钴镍的沉淀率分别达到97%,86%,99%以上.但Na2S,BaS会引入杂质,同时会因所需的溶液初始pH值较高而造成钴镍和锰的损失,因此不适宜作为回收钴镍的沉淀剂;而MnS在pH值小于2条件下可将98%以上的镍钴沉淀回收,且不会引入新的杂质及造成溶液中钴镍和锰的损失,因此MnS是从含锰溶液中回收钴镍的较合适的沉淀剂.     

硅镁型红土镍矿烧结试验研究

对印尼某硅镁型红土镍矿进行了烧结试验的相关研究。通过扫描电镜得出此红土镍矿中镍元素和铁元素分布区域完全一致,表明镍元素主要赋存在铁矿物中。通过热重分析可以得到,当试样温度达到700℃时,大部分水分可脱除。分别进行了熔剂全部采用生石灰或石灰石时的烧结试验,得出此红土镍矿烧结混合料的适宜固定碳配比应该在7.5%左右,适宜混合料水分应该在19%~23%,得到的烧结利用系数在1.2~1.4 t/(m2·h),成品率可以达到75%左右。     

硝酸常压浸出红土镍矿特性及镍浸出动力学

采用ICP和XRD分析手段研究了某红土镍矿的元素及物相组成。采用硝酸常压浸出该红土镍矿。通过单因素条件实验和综合实验探究了硝酸浓度、固液比、搅拌转速、浸出时间、浸出温度在常压条件下对红土镍矿中Ni、Co、Fe和Mg浸出的影响,并求解了镍的浸出动力学。结果表明,该红土镍矿为硅镁型,在硝酸浓度5mol/L、固液比(g/mL)为1:12、搅拌转速250r/min、浸出时间150min、浸出温度85℃的条件下,Ni、Co、Fe和Mg的浸出率最佳,分别为98.75%、91.66%、81.45%、94.21%。镍的浸出过程符合收缩核模型,反应活化能为38.804kJ/mol,反应过程受化学反应和内扩散混合控制。     

Enhanced hydrochloric acid leaching of nickel

Dissolution rates of nickel in hydrochloric acid with and without the presence of thiourea have been studied by means of rotating disc methods with solution analysis. In the absence of thiourea an apparent activation energy value of 61.1 ± 12.1 kJ. mol⁻¹ was determined. Such a high value is inconsistent with a diffusion controlled process and this was supported by the lack of dependency of the dissolution rate on rotational speed. A reaction controlled process is indicated. In 8.4 mol. dm⁻³ hydrochloric acid the thiourea concentration range producing optimum dissolution rates was 10⁻³ to 10⁻² mol. dm⁻³. At 70° C the rate of leaching was enhanced by some 105 %. Tests using radiochemical labelling of the sulphur and of the carbon separately in the thiourea molecule confirmed previous proposals, for cobalt dissolution, that hydrogen sulphide is produced as a by-product of the cathodic depolarisation reaction involving the thiourea and is adsorbed on the metal surface in the molecular state, forming activated anodic sites which enhance anodic dissolution. At the 10⁻¹ mol. dm⁻³ thiourea concentration level stimulation of the nickel dissolution process gave way to its partial inhibition with a maximum diminution at 30°C of 50 %.     

High pressure acid leaching of a refractory lateritic nickel ore

This paper describes the experimental findings of the extraction of nickel and cobalt by high pressure acid leaching (HPAL) of a refractory limonitic nickel laterite ore from the Gördes region of Manisa in Turkey. By optimizing the basic HPAL process parameters: leaching at 255 °C with 0.30 sulfuric acid to ore weight ratio with a particle size of 100% −850μ for 1 h of leaching, it was found that 87.3% of nickel and 88.8% of cobalt present in the ore could be extracted into the pregnant leach solution (PLS). However, these extraction results were found to be relatively low compared with other similar studies. In order to understand the possible reasons for this relatively lower extraction, further investigations have shown that together with a problem related to the kinetics of the dissolution reactions, a persistent acid resistant refractory mineral present in this sample also limited the leaching process. Attempts were made with different additives to solve this problem. The effects of chemical additives such as HCl, Na₂SO₄, FeSO₄, Cu⁺ and sulfur were tested and the effect of each addition on the degree of extraction of nickel and cobalt was determined.     

硫化镍加压浸出研究进展与应用

硫化镍是镍冶炼的重要原料,加压浸出技术在硫化镍冶炼中占有重要地位。本文对硫化镍加压浸出研究及应用进行了简单的介绍。根据反应体系的不同,镍加压浸出分为酸性加压浸出和氨性加压浸出两大类,工业生产中氨性加压浸出应用较少,以酸性加压浸出为主。硫化镍加压浸出处理原料灵活多样,主要包括硫化镍精矿、镍锍、镍钴硫化物等。另外,其在镍冶炼渣、低品位复杂物料处理方面也有一定的研究应用。加压浸出工艺灵活,综合回收率高,可同时生产镍、钴、铜、铂族金属等多种产品,主产品即可为硫酸镍,也可为电镍或镍粉,产品质量高,环境污染小,具有一定的市场竞争力。     

某低品位氧化镍矿酸浸正交试验研究

利用L16(45)正交试验对低品位氧化镍矿酸浸过程中酸的浓度,液固比,浸出时间,浸出温度和搅拌速率等影响镍浸出率的较大因子进行了研究。通过极差分析和方差分析对试验结果进行了分析,结果表明,影响镍浸出率的因素显著性依次为液固比>浸出温度>硫酸浓度>浸出时间>搅拌速率。镍的浸出优化条件为液固比为4:1,浸出温度为100℃,硫酸浓度为5.2mol/L,浸出时间2.5h,搅拌速率为250r/min,在此条件下镍的浸出率可达98.23%。研究可为优化类似镍矿酸浸工艺提供参考。     

金川低品位氧化镍矿的酸法制粒堆浸工艺研究

对于金川有色金属公司低品位的氧化镍矿,目前的火法和湿法冶金工艺,生产成本高,难以回收利用。通过制粒预处理,加入润湿液与矿石中的耗酸组分作用,可以预先破坏碳酸盐和Ca、Mg的氧化物,降低硫酸浸出过程中CO2气体逸出对颗粒的损害。选择N603作为低品位氧化镍矿的黏合剂,有效地改善了堆浸的渗透性,浸出过程中,矿石颗粒未发现严重的破裂和泥化现象。预处理后矿石浸出,每t矿石总用酸量258.8kg,镍浸出率85%以上。如果利用该公司硫酸厂大量的低浓度硫酸来堆浸,则在经济上和环境保护方面都比较合理。     

The effects of mineralogy on the biological leaching of nickel laterite ores

The amenability of limonite ore, the iron rich nickel laterite phase, was observed to be less than saprolite, the silicate rich phase, when subjected to biological leaching with heterotrophic microorganisms. To understand this difference, controlled leaching of the various nickel laterite minerals was conducted using citric acid to mimic the chemical action of the organisms and subsequent characterisation of the leached residues. The raw ore and the leached mineral residues were examined using high-resolution synchrotron based X-ray diffraction and optical microscopy. The possible contribution of electrosorption and solid porosity was also considered. The results suggest that although electrosorption contributes to nickel and cobalt losses, it is the structural changes induced by the acid in the minerals which effects the recovery of the metals. Citric acid was found to dehydroxylate saprolite minerals resulting in an unstable nickel oxide and thus making it susceptible to acid attack. This behaviour was not observed in the limonite ore, which was found to be poorly leached by citric acid.     

Interfacial properties of liquid sulfur in the pressure leaching of nickel concentrate

The effects of sulfur dispersing agents in the oxygen pressure leaching of nickel concentrate at medium temperature were investigated by interfacial studies. Liquid sulfur–aqueous solution interfacial tensions and liquid sulfur–sulfide mineral contact angles were measured at 140 °C, 690 kPa overpressure by nitrogen. The effects of sulfur dispersing agents including lignosulfonate, Quebracho, o-phenylenediamine (OPD), and humic acid were evaluated by the calculation of the work of adhesion in the liquid sulfur–sulfide mineral–aqueous solution systems. It was found that the sulfide mineral surface is sulfophobic at pH from 4.1 to 4.5 due to the hydrolysis of nickel (II) ions to nickel hydroxide and the deposition of nickel hydroxide on the mineral surface. These findings apply to four different sulfide mineral systems, including pentlandite, nickeliferous pyrrhotite, pyrrhotite, and chalcopyrite. Lignosulfonate, Quebracho, and humic acid were found to significantly reduce the work of adhesion indicating they should be effective sulfur dispersing agents. OPD is ineffective in changing the work of adhesion of sulfur on the mineral sulfides indicating that it is not a good candidate for sulfur dispersion.     

A study of atmospheric acid leaching of a South African nickel laterite

Nickel and cobalt acid leaching from a low-grade South African saprolitic laterite using sulphuric acid was studied. Ore characterisation was performed by XRD and XRF. Batch agitation leaching tests were conducted at atmospheric pressure investigating main parameters: particle size and percent solids at 25 °C and 90 °C. Ore characterisation showed that the ore is a saprolitic laterite with nickel present in lizardite. Leaching tests showed that nickel and cobalt could be leached from the ore at atmospheric pressure. Nickel was found to be more leachable from the coarser −106 + 75 μm fraction, with 98% Ni being extracted at 90 °C after 480 min. Cobalt was not favoured by variation in particle size and increased percent solids. Increasing ore percent solids improved nickel extraction at 25 °C however at 90 °C extraction decreased due to a diffusion layer build-up as a result of amorphous colloidal silica. The co-dissolution of magnesium and iron was elucidated. Nickel leaching data at increased temperature and percent solids fit the shrinking core model equation, k_dt = 1−2/3x − (1 − x)^2/3 showing that nickel leaching reaction was diffusion controlled under the set conditions.     

Agglomeration and column leaching behaviour of goethitic and saprolitic nickel laterite ores

Processability of complex, low-grade nickel (Ni) laterite ores via heap leaching is very limited due to some intractable geotechnical and hydrological challenges such as poor heap porosity/permeability and structural stability. This work presents some investigations on laboratory batch drum agglomeration and continuous column leaching behaviour of saprolitic (SAP) and goethitic (G) Ni laterite ores as part of the quest for an effective ore pre-treatment process for enhanced heap leaching. As a focus, the effect of ore mineralogy/chemistry on the agglomeration and column leaching behaviour of −2 mm (crushed from −15 mm run-of-mine) G and SAP Ni laterite ores was examined. To produce ∼5–40 mm agglomerates in <15 min, the SAP ore required a higher H₂SO₄ (30 wt.%) binder dosage compared with the G ore, although both ores displayed substantially similar, coalescence-controlled agglomeration mechanism. The resulting G agglomerates were more robust than the SAP ones based upon their compressive strength and acidic solution soak test measurements. However, over 100 days of continuous column leaching, the structural stability of the SAP agglomerate bed was slightly greater than that of G agglomerates, reflecting a lesser slump of the former. The pregnant leach solution analysis revealed greater Ni/Co extraction rates from the SAP than the G agglomerates. Whilst the total mass of acid consumed per ton dry ore processed was greater for the SAP ore, the total kg acid per kg Ni extracted was markedly lower. Incongruent leaching of gangue minerals’ constituent elements (e.g., Fe, Mn, Mg, Al and Si) occurred and contributed significantly to the overall acid consumption. The findings show the relevance of agglomeration and column leaching tests for providing useful information for plant designing and optimization of Ni laterite heap leaching operations.