LIX63和Versatic10萃取体系中镍钴锰的协萃机制研究

采用斜率法研究了Versatic10(HA_1)、LIX63(HA2)及二者协同萃取体系对Ni~(2+)、Co~(2+)、Mn~(2+)的萃取机制,考察了LIX63和Versatic10协同萃取Ni~(2+)、Co~(2+)、Mn~(2+)时分配比随温度的变化,并计算相关热力学参数。结果表明:LIX63与Versatic10的物质的量比在1/4～4/1范围内,该协萃体系对Ni~(2+)、Co~(2+)有明显的协萃效应,其中对Ni~(2+)的协萃效果更好,对Mn~(2+)基本没有协萃效应;Versatic10萃取Co~(2+)、Ni~(2+)、Mn~(2+)时形成的萃合物可能为Co(A_1)_2、Ni(A_1)_2、Mn(A_1)_2;LIX63萃取Ni~(2+)、Co~(2+)、Mn~(2+)形成的萃合物可能为[Ni(A2)2]、[Co(HA2)SO4]和[Mn(HA2)SO4];LIX63和Versatic10协同萃取Ni~(2+)、Co~(2+)、Mn~(2+)时形成的萃合物可能为Ni(A_1)_2(HA_2)_2、Co(A_1)_2(HA_2)_2、Mn(A_1)_2(HA_2)_2;协同萃取Ni~(2+)时吸热,协同萃取Co~(2+)、Mn~(2+)时放热;协同萃取Ni~(2+)的反应过程中增熵,协同萃取Co~(2+)、Mn~(2+)的反应熵小于零,表明萃取过程中水相金属离子脱水过程引起的熵变大于形成萃合物过程中所引起的熵变。     

不同萃取体系分离微生物浸出液中低含量镍钴

采用P507一Cyanex272混合萃取体系分离微生物浸出液中的镍钴,实验结果表明该体系具有较好的协萃效应.结合低含量镍钴的微生物浸出液体系高酸度、低钴镍比的特点,对比了P507、Cyanex272和P507-Cyanex272三种萃取体系对镍钴的萃取分离效果,确定了在初始pH值1.5~2.2、对应的平衡pH值4.00~5.25条件下P507-Cyanex272协萃体系有较好的镍钴分离效果.系统考察了室温28℃下协萃体系各影响因素对镍钴分离的影响,确定协同萃取的最佳工艺为:P507与Cyanex272摩尔比3:2,皂化率60%,萃取剂体积分数10%,有机相(由萃取剂与煤油组成)和水相体积比1:4.在此条件下钻的一级萃取率为99.16%,镍钻分离系数为932.59.     

离心萃取器在镍钴分离中的应用

采用P507溶剂萃取深度净化镍电解液,得到符合镍电解工艺要求的低钴电解液和富钴溶液.利用离心萃取器,在流量1 L/h,相比(Vo/Va)=2/1,离心转速4 000 r/min,水相料液pH=5.0的最佳条件下,用P507从镍电解液中萃取钴,钴萃取率为92.56%,钴、镍分离系数为4 353.离心萃取器可以作为镍钴高效分离设备,有良好的工业应用前景.     

从钴冰镍浸出液中回收镍钴

以Na2S为沉淀剂,采用硫化沉淀法从钴冰镍三段浸出液中回收其中的钴、镍等有价金属。通过单因素试验,考察了Na2S的加入量、酸度(pH)、反应温度和时间等因素对浸出液中铁、镍、钴沉淀率的影响。结果表明,适宜工艺条件为Na2S的过量系数3.0,pH=3.0～3.5,反应温度60℃,反应时间2h,钴、镍、铁的沉淀率分别为99%、98%、90%。     

离子交换法分离高镁低镍硫化矿生物浸出液中的镍镁

高镁低镍硫化矿细菌浸出液中有价金属镍离子浓度为300 mg·L-1左右,杂质金属镁离子浓度高达10~20 g·L-1,过高的镁离子浓度使细菌大量死亡,浸出无法继续,且常规方法难以对镍离子进行提取。本文采用离子交换树脂CN-27对浸出液进行吸附,镍镁吸附比例约为1∶10,小于原液中的镍镁比例1∶50。利用不同浓度硫酸溶液进行树脂解吸,当硫酸浓度为9 g·L-1时,镁离子首先从树脂上洗脱下来,而镍离子几乎不被洗脱;当硫酸浓度为36 g·L-1时,镍离子开始从树脂上洗脱下来。实验测得该条件下树脂对镍离子的穿透交换容量为0.487mmol·g-1(0.613 mmol·ml-1)。用较高浓度的硫酸对吸附在离子交换树脂上的镍离子进行解吸,其流出液中镍离子平均浓度为4.84 g·L-1,富集比在8倍以上,镍离子的解吸率达到97.47%。     

转炉渣富钴镍浸出液镍钴分离工艺研究

以某厂镍电解生产净化工序氯气除钴产生的钴渣为氧化剂,除去转炉渣浸出液电积脱铜后液中的钴,实现转炉渣富钴镍浸出液中镍钴分离。结果表明,在钴渣含三价镍与钴量摩尔比为4～5,反应温度70～80℃,反应时间120min,终点pH 4.8～5的条件下,分离富集钴后的二次钴渣镍钴比可降为1～1.5,可用于生产钴产品。除钴后液可直接并入镍电解系统。     

溶剂萃取法脱除锰矿浸出液中钙镁的研究

研究了低品位氧化锰矿经还原焙烧、硫酸浸出得到的原料液中钙镁杂质的祛除工艺。研究结果为：用30％的P507加70％的磺化煤油作为萃取剂;控制原料液初始pH值0.2左右;相比1：1;常温五级逆流萃取镁、钙的萃取率分别为72．06％和48．97％,锰的损失为6．35％。既有效脱除了钙镁,又抑制锰的损失,同时还避免了通常所用的氟化物沉淀法腐蚀设备的缺点。     

用P507从硫酸镍溶液中萃取分离钙镁的研究

研究了用P507从硫酸镍溶液中萃取分离钙、镁，给出了萃取分离的最佳工艺条件为：温度60摄氏度，水相平衡pH6.00，相比1：1，P507的体积分数10％，皂化率20％，在此条件下，以P507和磺化煤油组成的有机相萃取分离效果较好。     

火焰原子吸收光谱法测定铜钴矿中镍、锌、锰、钙和镁量

研究了用火焰原子吸收光普法测定铜钴矿中镍、锌、锰、钙、镁，选择了测定的最佳条件，方法简便可靠，加标回收率98．8％－103．5％，相对标准偏差＜5．2％。     

ICP-MS法测定钢铁中痕量镁和钙含量

建立了电感耦合等离子体质谱法测定钢铁中痕量镁和钙元素含量的分析方法。在优化的仪器工作条件下,采用内标法与加入校正法相结合,在补偿基体效应的同时．提高了测定结果的稳定性。该方法加标回收率为90．0％～110．0％,相对标准偏差小于10．0％．该方法准确、快速,满足冶金行业对钢铁中痕量镁和钙元素的测试需要。     

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.     

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.     

P507分馏萃取分离钴镍的研究

高钴低镍原料用P507分馏萃取分离钴镍,萃取段5级,洗涤段5级,硫酸介质。串级模拟实验结果:可获得含镍小于0.03%的高纯钴有机相和含钴小于0.03%的高纯镍水相,钴、镍的收率均大于99.9%。     

多波长分光光度法同时测定钴精矿中钴和镍

探讨了在pH 7.8时,Co(和Ni(与二甲酚橙(XO)显色的反应条件,建立了K-矩阵分光光度法同时测定钴和镍的分析方法。钴和镍的络合物表观摩尔吸光系数分别为2.42×106L.mol-1.cm-1,1.63×105L.mol-1.cm-1;方法相对标准偏差分别为4.8%,3.9%;平均加标回收率分别为110.0%,94.1%。方法已用于不同比例合成样品和钴精矿中钴和镍的定量分析。     

原子吸收光谱法测定钴粉中镍

研究了萃取分离原子吸收光谱法测定钴粉中镍的方法。在pH8～9氨性介质中,以柠檬酸作为稳定剂,用三氯甲烷萃取丁二酮肟 镍的络合物,盐酸反萃取后用原子吸收光度法测定反萃取液中镍含量。试液经萃取分离后基体和共存元素对镍的测定没有干扰,方法的检出限为0002%(质量分数),镍的质量浓度在04～150 μg/mL范围内与其吸光度呈线性关系,相关系数大于0999 6。方法已用于钴粉中微量镍的测定,测定结果与电感耦合等离子体原子发射光谱法（ICP AES）的结果相符,相对标准偏差( RSD, n=11)小于27%。     

红土镍矿微波水热法浸提镍钴

采用微波水热盐酸浸出方法对腐泥土型红土镍矿提取镍钴进行了研究,详细探讨了焙烧预处理、微波水热浸出温度和浸出时间对镍钴浸出率的影响.对于300℃焙烧预处理后的红土镍矿,微波水热温度为50℃,浸出时间为1 h时,镍的浸出率高达93.65%,钴的浸出率为87.86%.红土镍矿的微波水热浸出体系与普通水热浸出体系相比,镍和钴的浸出效果更好.研究表明,扩散过程是镍、钴浸出过程的主要限制环节.     

火焰原子吸收光谱法测定催化剂中高含量钴和镍

提出了用火焰原子吸收光谱法测定加氢精制催化剂中高含量钴和镍的方法。在聚四氟乙烯高压釜内,用王水溶解样品。钴、镍的最灵敏吸收线波长分别为240 .7nm,232.0nm。空气-乙炔火焰测定高含量钴、镍时,用波长分别为352 7nm,341 5nm的次灵敏线,可提高测定的精密度、又能使工作曲线的线性范围变宽。钴量在0～70μg/mL、镍量在0～150μg/mL范围内呈良好线性关系。对催化剂样品进行分析时,相对标准偏差为1.15%～3.85%。对样品进行加标回收实验,回收率在98.1%～101.5%。方法的精密     

连续光源火焰原子吸收光谱法测定氧化镍中钴铜锌铁钙镁

采用盐酸溶解样品,选择Co 240.72nm、Cu 324.75nm、Zn 213.86nm、Fe 248.33nm、Ca 422.67nm、Mg 202.58nm作为分析谱线,钴、铜、锌、铁选择3个像素点,钙、镁选择9个像素点,建立了连续光源原子吸收光谱法(CS-AAS)同时测定氧化镍中的钴、铜、锌、铁、钙、镁的方法。实验表明:在100mL测定液中加入2mL 200g/L氯化锶溶液,可消除测定介质(体积分数为2%的盐酸)对待测元素的影响;基体镍对测定的干扰可忽略。在优化的实验条件下,钴、铜、锌、铁、钙、镁的校准曲线相关系数均不低于0.999 0,且其方法检出限在0.002~0.092μg/mL之间。按照实验方法对氧化镍样品中钴、铜、锌、铁、钙、镁分别平行测定11次,钙和镁的测定值在0.1%~0.4%之间,其对应的相对标准偏差(RSD)不大于2%;钴、铜、锌、铁的测定值在0.003%~0.04%之间,其对应的相对标准偏差均小于10%。将实验方法应用于电真空镍光谱标准样品(该标样为氧化镍状态)中上述各元素的测定,结果与认定值基本一致。     

示波极谱法连续测定精锑中微量钴和镍

提出了一个连续测定精锑中微量镍和钴的新方法 ,在丁二酮肟 -NaNO2 -NH3·H2 O -NH4Cl体系中 ,示波极谱法同时测定了精锑中微量镍和钴 ,结果良好。