Article(id=1169295844034490463, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1169295841580819245, articleNumber=1009-2617(2025)03-0398-08, orderNo=null, doi=10.13355/j.cnki.sfyj.2025.03.014, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1722960000000, receivedDateStr=2024-08-07, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1756711453684, onlineDateStr=2025-09-01, pubDate=1750348800000, pubDateStr=2025-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1756711453684, onlineIssueDateStr=2025-09-01, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1756711453684, creator=13701087609, updateTime=1756711453684, updator=13701087609, issue=Issue{id=1169295841580819245, tenantId=1146029695717560320, journalId=1146120122248306696, year='2025', volume='44', issue='3', pageStart='283', pageEnd='431', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1756711453097, creator=13701087609, updateTime=1756711962360, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1169297977647571041, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1169295841580819245, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1169297977647571042, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1169295841580819245, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=398, endPage=405, ext={EN=ArticleExt(id=1169295844265177184, articleId=1169295844034490463, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Deep Purification Process of Crude Nickel Sulfate as By-product of Copper Electrolysis, columnId=1152626641181700664, journalTitle=Hydrometallurgy of China, columnName=Experiment Research, runingTitle=null, highlight=null, articleAbstract=

In order to reduce the content of impurities such as Cu, Fe, Zn and reduce the loss of Ni in crude nickel sulfate solution of copper electrolysis by-products, the process of selective precipitation of copper by Na2S2O3—deep extraction of zinc removal iron—evaporation crystallization was studied for deep purification of the solution, and the key process parameters were optimized. The results show that the precipitation rate of Cu can reach 99.89% and the loss rate of Ni is only 1.22% using Na2S2O3 as precipitator under the optimum conditions of Na2S2O3 excess coefficient of 2.0, solution pH of 5.0, reaction temperature of 85 ℃ and reaction time of 2 h. Using P204 as extracant, the extraction rates of Zn and Fe can reach 99.87% and 99.98%, respectively, and the loss rate of Ni is 2.24% under the optimal conditions of pH=3.0, P204 volume fraction of 25%, saponification rate of 50%, VO/VA=1.5/1, extraction temperature of 25 ℃ and extraction time of 10 min. Electroplating grade nickel sulfate crystal products are obtained by evaporation and crystallization of the deeply purified nickel sulfate solution. The quality can meet the national standard GB/T 26524—2023 Class Ⅱ indicators, and can be used as high-quality raw materials for electroplating and other industrial uses.

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为了降低铜电解副产品粗硫酸镍溶液中Cu、Fe和Zn等杂质含量并减少镍损失,研究了采用Na2S2O3选择性沉淀铜—萃取深度除锌铁—蒸发结晶工艺深度净化粗硫酸镍溶液,并优化了关键工艺参数。结果表明:以Na2S2O3作沉淀剂时,在Na2S2O3过量系数2.0、溶液pH=5.0、反应温度85 ℃、反应时间2 h最佳工艺条件下,Cu沉淀率可达99.89%,Ni损失率仅为1.22%;选择P204作萃取剂时,在控制萃原液pH=3.0、P204体积分数25%、皂化率50%、相比VO/VA=1.5/1、萃取温度25 ℃、萃取时间10 min优化条件下,Zn、Fe萃取率可分别达99.87%和 99.98%,Ni损失率为2.24%;深度净化后的硫酸镍溶液经蒸发结晶得到电镀级硫酸镍晶体产品,质量符合国家标准(GB/T 26524—2023)的Ⅱ类指标,可以用作电镀及其他工业用途的优质原料。

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蒋学先(1968—),男,硕士,副教授,主要研究方向为有色金属冶金及资源回收利用。E-mail:
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杨永明(1985—),男,本科,工程师,主要研究方向为有色金属冶金及资源回收利用。

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杨永明(1985—),男,本科,工程师,主要研究方向为有色金属冶金及资源回收利用。

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journalId=1146120122248306696, articleId=1169295844034490463, language=EN, label=Table 1, caption=

Main chemical components of crude nickel sulfate crystals %

, figureFileSmall=null, figureFileBig=null, tableContent=
Ni Cu Fe Zn Co Ca Mg
15.79 0.18 0.31 0.91 0.075 0.08 0.031
), ArticleFig(id=1172888184808682358, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=CN, label=表1, caption=

粗硫酸镍结晶的主要化学成分

, figureFileSmall=null, figureFileBig=null, tableContent=
Ni Cu Fe Zn Co Ca Mg
15.79 0.18 0.31 0.91 0.075 0.08 0.031
), ArticleFig(id=1172888184875791224, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=EN, label=Table 2, caption=

Comprehensive verification test results of removal of copper by precipitation

, figureFileSmall=null, figureFileBig=null, tableContent=
试验编号 Cu沉淀率/% Ni损失率/%
1 99.89 1.25
2 99.78 1.14
3 100.00 1.29
平均 99.89 1.22
), ArticleFig(id=1172888184980648825, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=CN, label=表2, caption=

沉淀除铜综合验证试验结果

, figureFileSmall=null, figureFileBig=null, tableContent=
试验编号 Cu沉淀率/% Ni损失率/%
1 99.89 1.25
2 99.78 1.14
3 100.00 1.29
平均 99.89 1.22
), ArticleFig(id=1172888185068729211, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=EN, label=Table 3, caption=

Comprehensive verification test results of extraction of zinc-removed iron by P204 %

, figureFileSmall=null, figureFileBig=null, tableContent=
试验编号 Zn萃取率 Fe萃取率 Ni损失率
1 99.78 100.00 1.92
2 99.95 99.94 2.06
3 99.89 100.00 1.99
平均 99.87 99.98 1.99
), ArticleFig(id=1172888185161003901, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=CN, label=表3, caption=

P204萃取除锌、铁综合验证试验结果

, figureFileSmall=null, figureFileBig=null, tableContent=
试验编号 Zn萃取率 Fe萃取率 Ni损失率
1 99.78 100.00 1.92
2 99.95 99.94 2.06
3 99.89 100.00 1.99
平均 99.87 99.98 1.99
), ArticleFig(id=1172888185261667199, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=EN, label=Table 4, caption=

Comparison between chemical composition content of nickel sulfate products and GB/T 26524—2023 standard requirements %

, figureFileSmall=null, figureFileBig=null, tableContent=
项目 GB/T 26524—2023标准 硫酸镍产品中wB
I类 Ⅱ类
≥22.08 ≥22.20 22.24
≤0.05 ≤0.001 0.000 3
≤0.000 5 ≤0.000 5 0.000 1
≤0.000 5 ≤0.000 5 0.000 2
≤0.000 5 ≤0.000 5 0.000 1
≤0.003 ≤0.002 0.001 7
≤0.003 ≤0.002 0.000 9
水不溶物 ≤0.001
), ArticleFig(id=1172888185332970369, tenantId=1146029695717560320, journalId=1146120122248306696, articleId=1169295844034490463, language=CN, label=表4, caption=

硫酸镍产品化学成分含量与GB/T 26524—2023标准要求的对比

, figureFileSmall=null, figureFileBig=null, tableContent=
项目 GB/T 26524—2023标准 硫酸镍产品中wB
I类 Ⅱ类
≥22.08 ≥22.20 22.24
≤0.05 ≤0.001 0.000 3
≤0.000 5 ≤0.000 5 0.000 1
≤0.000 5 ≤0.000 5 0.000 2
≤0.000 5 ≤0.000 5 0.000 1
≤0.003 ≤0.002 0.001 7
≤0.003 ≤0.002 0.000 9
水不溶物 ≤0.001
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铜电解副产品粗硫酸镍的深度净化工艺研究
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杨永明 1 , 朱文云 2 , 蒋学先 2, 3 , 李金丽 3 , 何宗庆 1 , 黄彩红 1 , 李中林 2 , 何贵香 2, 3
湿法冶金 | 试验研究 2025,44(3): 398-405
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湿法冶金 | 试验研究 2025, 44(3): 398-405
铜电解副产品粗硫酸镍的深度净化工艺研究
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杨永明1, 朱文云2, 蒋学先2, 3 , 李金丽3, 何宗庆1, 黄彩红1, 李中林2, 何贵香2, 3
作者信息
  • 1 广西南国铜业有限责任公司,广西 扶绥 532301
  • 2 桂林理工大学 材料科学与工程学院,广西 桂林 541004
  • 3 桂林理工大学南宁分校,广西 南宁 530001
  • 杨永明(1985—),男,本科,工程师,主要研究方向为有色金属冶金及资源回收利用。

通讯作者:

蒋学先(1968—),男,硕士,副教授,主要研究方向为有色金属冶金及资源回收利用。E-mail:
Deep Purification Process of Crude Nickel Sulfate as By-product of Copper Electrolysis
Yongming YANG1, Wenyun ZHU2, Xuexian JIANG2, 3 , Jinli LI3, Zongqing HE1, Caihong HUANG1, Zhonglin LI2, Guixiang HE2, 3
Affiliations
  • 1 Guangxi Nanguo Copper Co., Ltd., Fusui 532301, China
  • 2 Department of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China
  • 3 Guilin University of Technology at Nanning, Nanning 530001, China
出版时间: 2025-06-20 doi: 10.13355/j.cnki.sfyj.2025.03.014
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为了降低铜电解副产品粗硫酸镍溶液中Cu、Fe和Zn等杂质含量并减少镍损失,研究了采用Na2S2O3选择性沉淀铜—萃取深度除锌铁—蒸发结晶工艺深度净化粗硫酸镍溶液,并优化了关键工艺参数。结果表明:以Na2S2O3作沉淀剂时,在Na2S2O3过量系数2.0、溶液pH=5.0、反应温度85 ℃、反应时间2 h最佳工艺条件下,Cu沉淀率可达99.89%,Ni损失率仅为1.22%;选择P204作萃取剂时,在控制萃原液pH=3.0、P204体积分数25%、皂化率50%、相比VO/VA=1.5/1、萃取温度25 ℃、萃取时间10 min优化条件下,Zn、Fe萃取率可分别达99.87%和 99.98%,Ni损失率为2.24%;深度净化后的硫酸镍溶液经蒸发结晶得到电镀级硫酸镍晶体产品,质量符合国家标准(GB/T 26524—2023)的Ⅱ类指标,可以用作电镀及其他工业用途的优质原料。

粗硫酸镍  /  选择性沉淀  /  硫化  /  萃取  /  深度净化  /  铜  /  铁  /  电解

In order to reduce the content of impurities such as Cu, Fe, Zn and reduce the loss of Ni in crude nickel sulfate solution of copper electrolysis by-products, the process of selective precipitation of copper by Na2S2O3—deep extraction of zinc removal iron—evaporation crystallization was studied for deep purification of the solution, and the key process parameters were optimized. The results show that the precipitation rate of Cu can reach 99.89% and the loss rate of Ni is only 1.22% using Na2S2O3 as precipitator under the optimum conditions of Na2S2O3 excess coefficient of 2.0, solution pH of 5.0, reaction temperature of 85 ℃ and reaction time of 2 h. Using P204 as extracant, the extraction rates of Zn and Fe can reach 99.87% and 99.98%, respectively, and the loss rate of Ni is 2.24% under the optimal conditions of pH=3.0, P204 volume fraction of 25%, saponification rate of 50%, VO/VA=1.5/1, extraction temperature of 25 ℃ and extraction time of 10 min. Electroplating grade nickel sulfate crystal products are obtained by evaporation and crystallization of the deeply purified nickel sulfate solution. The quality can meet the national standard GB/T 26524—2023 Class Ⅱ indicators, and can be used as high-quality raw materials for electroplating and other industrial uses.

crude nickel sulfate  /  selective precipitation  /  vulcanization  /  extraction  /  deep purification  /  copper  /  iron  /  electrolysis
杨永明, 朱文云, 蒋学先, 李金丽, 何宗庆, 黄彩红, 李中林, 何贵香. 铜电解副产品粗硫酸镍的深度净化工艺研究. 湿法冶金, 2025 , 44 (3) : 398 -405 . DOI: 10.13355/j.cnki.sfyj.2025.03.014
Yongming YANG, Wenyun ZHU, Xuexian JIANG, Jinli LI, Zongqing HE, Caihong HUANG, Zhonglin LI, Guixiang HE. Deep Purification Process of Crude Nickel Sulfate as By-product of Copper Electrolysis[J]. Hydrometallurgy of China, 2025 , 44 (3) : 398 -405 . DOI: 10.13355/j.cnki.sfyj.2025.03.014
硫酸镍作为一种重要的化工原料,因具有优异的化学性质而广泛应用于电镀、催化剂制备、电池材料开发、陶瓷工业等多个领域[1-2]。随着这些行业的快速发展,对硫酸镍需求量不断攀升,市场对产品质量要求也越来越高[3-4]。因此,高效、合理地利用硫酸镍资源显得尤为重要。广西某铜冶炼企业的铜电解工序每年副产大量成分复杂的粗硫酸镍溶液,其中含有较高浓度的Cu、Fe和Zn等重金属杂质。为了充分利用该类镍资源,生产符合市场需求的高质量镍盐产品,提高产品附加值,降低生产成本,提升企业经济效益,研发无害化制备高纯硫酸镍的工艺技术具有重要应用价值。
粗硫酸镍的净化除杂方法主要包括化学沉淀法[5-6]、萃取法[7-8]、离子交换法[9]等,化学沉淀法和萃取法因具有操作简单、选择性好、回收效率高、适用范围广且工艺较成熟等优点,已成为工业上净化硫酸镍的主流方法[10-12]。离子交换法虽具有选择性好、分离效果优等优点,但受原料适应范围和树脂交换能力限制,目前应用较受局限[13]。在实际操作中,为了达到最佳净化效果,通常将化学沉淀法和萃取法联合处理粗硫酸镍溶液,并根据其中杂质种类和含量不同,选择具体的联合工艺[14-15]
试验针对广西某铜业公司铜电解液脱镍产生的粗硫酸镍晶体,研究了采用Na2S2O3选择性沉淀铜—萃取深度除锌铁—蒸发结晶工艺进行处理,确定了最佳工艺参数,旨在实现深度净化除杂,获得高纯度的精制电镀级硫酸镍。
试验以广西某铜业公司铜电解液脱镍产生的粗硫酸镍结晶为原料,其主要化学成分见表1
主要试剂:硫代硫酸钠、氢氧化钠、硫酸、氨水、P204、P507、C272、260#溶剂油(磺化煤油),均为分析纯。
主要仪器:DF-101S型集热式恒温加热磁力搅拌器,上海力辰邦西仪器科技有限公司;SHA-B型双功能水浴恒温振荡器,常州鸿泽试验科技有限公司;PHS-3C型pH计,上海仪电科仪有限公司;JA2003型电子天平,上海浦春计量仪器有限公司;GS-2000型X射线荧光分析仪,江西观世科技有限公司。
在硫酸镍溶液中加入Na2S2O3,作为沉淀剂,将Cu转化为CuS沉淀。Na2S2O3遇水生成H2S,与溶液中CuSO4反应生成CuS沉淀。生成的H2S可使溶液中的S2-均匀分布,避免局部S2-过量造成Ni的损失[16]。主要化学反应见式(1)、(2):
Na2S2O3+H2O=Na2SO4+H2S;
CuSO4+H2S=CuS↓+H2SO4
此外,Na2S2O3在溶液中除了与杂质Cu生成沉淀外,还会与其他金属离子发生共沉淀。但Cu与S之间具有较强的亲和力,二者之间易发生置换反应[16],即只要硫酸镍溶液中存在Cu2+,则生成的NiS、FeS和ZnS等沉淀就会重新溶解到溶液中,只有当溶液中的Cu充分沉淀后,Ni、Fe和Zn等才会开始沉淀,化学反应见式(3)~(6)。因此,需通过合理优化沉淀过程的反应条件,以避免Ni、Fe和Zn的损失,从而实现最佳分离回收铜的效果。
NiS+CuSO4=CuS↓+NiSO4;
FeS+CuSO4=CuS↓+FeSO4;
ZnS+CuSO4=CuS↓+ZnSO4;
CoS+CuSO4=CuS↓+CoSO4
针对硫化脱铜后的粗硫酸镍溶液,采用萃取法进行深度除杂。P204、P507和C272等萃取剂属于一元磷酸(HA),通过与金属离子(以二价金属离子Me2+为例)直接配合形成配位键,使酸根阴离子进入金属离子的配位层,形成中性配合物并转移至有机相中,完成萃取过程[17]。在非极性有机溶剂(如磺化煤油)中,HA与金属离子配合常以氢键二聚体结构存在,即H2A2。此外,随着萃取反应进行,水相酸度降低,会造成萃取效率下降。因此,在萃取前需对萃取剂进行加碱处理(以加入NaOH为例),通过皂化反应中和部分H+,减少酸性变化对萃取效率的不利影响。HA萃取金属离子Me2+的反应机制[18]见式(7)~(8):
NaOH(A)+H2A2(O) =NaHA2(O)+H2O(A);
$\mathrm{Me}_{(\mathrm{A})}^{2+}+n \mathrm{NaHA}_{2(\mathrm{O})}=\mathrm{Me}\left(\mathrm{HA}_{2}\right) n_{(\mathrm{O})}+n \mathrm{Na}_{(\mathrm{A})}^{+} $。
根据P204萃取金属性能差异,可将Ni与其他金属杂质离子有效分离。根据萃取剂在酸性介质中对一些金属的萃取先后顺序,即Fe3+>Zn2+>Ca2+>Cu2+>Co2+>Ni2+[19-20],以皂化P204+磺化煤油组成的有机相作为萃取剂,将锌、铁,以及微量的钙、钴离子都萃取至有机相中,而使镍离子留在水相中,从而实现镍与锌、铁等杂质的分离;之后再以硫酸为反萃剂从有机相中反萃回收锌、铁等杂质元素。
粗硫酸镍溶液的深度净化工艺试验流程如图1所示。
首先,称取一定质量的粗硫酸镍结晶,将其在室温下用蒸馏水搅拌溶解并过滤,去除不溶性杂质,得到镍质量浓度为118.2 g/L的粗硫酸镍溶液。将100 mL粗硫酸镍溶液转移至250 mL烧杯中,将烧杯置于双功能水浴恒温振荡器中,加热并开启振荡,振荡速度为400 r/min;加热至一定温度后,缓慢加入Na2S2O3溶液进行硫化除铜,得到CuS沉淀和沉铜后液。该过程中的金属沉淀率η按式(9)计算:
η = ( 1 - ρ 1 V 1 ρ 0 V 0 ) × 100 %
式中:ρ0ρ1—料液、沉铜后液中金属元素质量浓度,mg/L;V0V1—料液、沉铜后液体积,L。
其次,将P204和磺化煤油按体积比1∶3混合均匀,配制萃取有机相。随后,使用NaOH溶液对有机相进行皂化处理。根据设定的萃取条件,用硫酸调节沉铜后液(萃原液)的初始pH,将萃取有机相和萃原液按一定比例混合后,置于恒温振荡器中振荡一定时间。然后将混合液倒入分液漏斗中静置分相,使镍留在萃余液中,而锌、铁等杂质负载进入有机相。同时,用硫酸作为反萃剂对负载有机相进行反萃,反萃后的有机相经洗涤可循环利用。该过程中金属萃取率E按式(10)计算:
E = ( 1 - ρ 2 V 2 ρ 1 V 1 ) × 100 %
式中:ρ1ρ2—萃原液、萃余液中金属质量浓度,mg/L;V1V2—萃原液、萃余液体积,L。
最后,将萃余液倒入蒸发皿中加热,随着水分不断蒸发使溶液逐渐达到过饱和状态,硫酸镍开始以晶体形式逐渐析出,之后停止加热,自然冷却至室温,得精制硫酸镍晶体。
在溶液pH=5.0、反应温度 85 ℃条件下反应2 h,Na2S2O3过量系数(理论量的倍数)对Cu、Ni沉淀分离效果的影响如图2所示。可知,随Na2S2O3过量系数增加,Cu、Ni沉淀率逐渐升高。这是因为随Na2S2O3用量增加,H2S浓度增大,进而增加溶液中S2-,使其与Cu2+、Ni2+的接触概率增大,反应更加充分,有利于Cu2+沉淀。当Na2S2O3过量系数增至理论量的2倍时,Cu沉淀率达99.70%,Ni损失率仅为1.27%;继续增大Na2S2O3用量,Cu沉淀率升幅较小,趋于稳定,因为溶液中几乎没有游离Cu2+存在,继续增大Na2S2O3用量反而会造成Ni损失增加。综合考虑,选择Na2S2O3过量系数为2。
在Na2S2O3过量系数2.0、反应温度85 ℃、反应时间2 h条件下,溶液pH对Cu、Ni沉淀分离效果的影响如图3所示。
图3可知:溶液pH在2.0~5.0范围内,随pH升高,Cu沉淀率逐渐升高,溶液pH升至5.0后趋于稳定。这表明Na2S2O3在酸性环境中相对较稳定,能与Cu2+发生反应。但pH过低时,Na2S2O3会发生副反应生成S和SO2,导致其利用率下降;而pH过高时,溶液酸性减弱,会促进H2S发生分解反应,导致溶液中局部生成S2-概率增大,增大Ni损失。综合考虑,选择溶液pH为5.0。
在Na2S2O3过量系数2.0、溶液pH为5.0的条件下反应2 h,考察反应温度对Cu、Ni沉淀分离效果的影响如图4所示。
图4可知:随温度升高,Cu、Ni的沉淀率逐渐升高,温度为85 ℃时,Cu沉淀率为99.79%,Ni损失率为1.22%;进一步升高温度,Cu沉淀率变化不大,但Ni损失率上升明显。这主要是由于温度高于一定值时,Na2S2O3会与溶液中的Ni等其他金属离子发生副反应,减少与Cu2+的反应机会,从而造成Ni损失率增大。综合考虑,选择反应温度为85 ℃。
在Na2S2O3过量系数2.0、溶液pH=5.0、反应温度85 ℃条件下,反应时间对Cu、Ni沉淀分离效果的影响如图5所示。
图5可知:反应时间在1~3 h范围内,对Cu沉淀率影响较小,反应2 h时,Cu沉淀率达最大,为99.89%;而Ni损失率随反应进行先基本保持不变,2 h后呈明显增大趋势。这表明反应2 h时,大部分Cu2+已经与Na2S2O3反应生成CuS沉淀,进一步延长反应时间,会导致已形成的沉淀微量溶解,造成Cu沉淀率下降;同时,长时间加热搅拌会使得Ni活性增加,Ni2+更易与Na2S2O3发生反应,造成Ni损失。综合考虑,选择反应时间为2 h。
根据单因素试验确定最佳沉铜试验条件为:Na2S2O3过量系数2.0,溶液pH=5.0,反应温度85 ℃、反应时间2 h。在该条件下进行3组综合验证试验,结果见表2。可以看出,粗硫酸镍溶液中Cu平均沉淀率达99.89%,而Ni平均损失率仅为1.22%。说明以Na2S2O3作为沉淀剂能有效沉淀粗硫酸镍溶液中的铜,使铜镍得到有效分离。
粗硫酸镍溶液经硫化脱铜后,仍含有较多的杂质离子,需进一步采用溶剂萃取法深度净化,以获取高纯度的硫酸镍溶液。通过对比试验,在固定条件(萃余液pH=3.0、萃取相比VO/VA=1/1、P204体积分数25%、有机皂化率50%、25 ℃)下,考察P204、P507和C272萃取剂对Zn、Fe和Ni等杂质的萃取效果,并筛选出适宜的萃取剂进行后续试验,结果如图6所示。可知:相较P507和C272,P204对Zn、Fe萃取效果更好,且Ni损失率也较低。因此,选用P204萃取剂进行后续的萃取试验,以进一步优化硫酸镍溶液的纯化过程。
在萃原液pH=3.0、P204体积分数25%、有机相皂化率50%、25 ℃条件下萃取10 min,萃取相比对Zn、Fe和Ni萃取分离效果的影响如图7所示。
图7可知:随萃取相比VO/VA增大,Zn、Fe萃取率显著提高,当VO/VA超过1.5/1时,Zn、Fe萃取率趋于稳定;但Ni损失率在萃取相比考察范围内,随VO/VA增大而逐渐增加。这是因为在一定范围内,VO/VA增大则萃取剂用量增加,金属离子与萃取剂之间的相互作用增强,从而使Zn、Fe萃取率提高[21];当VO/VA增至一定值后,用于萃取Zn、Fe的萃取剂已足够,进一步增大萃取剂用量对于Zn、Fe的萃取效果几乎无影响,反而会增加有机相的溶解损失,导致Ni损失增加[22-23]。综合考虑萃取分离效果及萃取剂利用率等因素,确定萃取相比VO/VA以1.5/1为宜。
在萃原液pH=3.0、P204体积分数25%、有机相皂化率50%、萃取相比VO/VA=1.5/1条件下萃取10 min,萃取温度对Zn、Fe和Ni萃取分离效果的影响如图8所示。
图8可知:随温度升高,Zn、Fe萃取率降低,Ni损失率增大。这主要是因为升高温度会加剧有机相分子的热运动,减弱有机相和水相之间的界面张力,从而增大萃取剂在水相中的溶解度,导致萃取剂损失增多[21];此外,P204萃取Ni为吸热反应,升高温度会导致有机相中Ni浓度增加,造成Ni大量损失,从而影响Zn、Fe与Ni的分离效果[24]。综合考虑,选择在室温(25 ℃)下进行萃取试验。
在萃原液pH=3.0、P204体积分数25%、有机相皂化率50%、萃取相比VO/VA=1.5/1、25 ℃条件下,萃取时间对Zn、Fe和Ni萃取分离效果的影响如图9所示。
图9可知:萃取时间对Zn、Fe萃取率影响很小,表明P204对Zn、Fe萃取速度较快,萃取10 min时P204对铁、锌的萃取已达到平衡;随萃取时间延长,Ni损失率不断增大。综合考虑Zn、Fe与Ni的萃取分离效果及萃取效率,选择萃取时间为10 min。
根据单因素试验确定P204萃取沉铜后夜除铁、锌的适宜条件为:有机相皂化率50%,相比VO/VA=1.5/1,萃取温度25 ℃,萃取时间10 min。在该条件下进行3组综合验证试验,结果见表3。可以看出,在适宜条件下,Zn、Fe平均沉淀率分别为99.87%、99.98%,几乎沉淀完全,而Ni平均损失率较低,仅为1.99%。说明粗硫酸镍溶液经过沉铜后,再用P204可以深度去除其中的铁、锌,并使二者与Ni实现有效分离。
净化除杂后的硫酸镍溶液镍质量分数为22.09%,经加温蒸发浓缩至22.24%,通过自然冷却结晶得到精制六水合硫酸镍(NiSO4·6H2O),其化学成分含量和GB/T 26524—2023标准要求的对比结果见表4。可知,所得硫酸镍产品质量符合GB/T 26524—2023规定的Ⅱ类标准要求,适用于电镀及其他工业的优质原材料。
针对铜电解副产品粗硫酸镍溶液,首先以Na2S2O3为沉淀剂选择性沉淀铜,再用P204萃取剂去除锌、铁,最后通过蒸发结晶可获得高质量的硫酸镍产品。同时,该工艺还能实现铜的高效回收,其综合回收率高达99.89%,硫化铜渣可返回铜冶炼系统进一步回收铜。所得的硫酸镍产品的Ni质量分数为22.24%,Cu、Zn和Fe等杂质元素的含量均符合GB/T 26524—2023规定的Ⅱ类标准要求,镍综合回收率达96.79%,硫酸镍产品纯度达99.13%,可作为电镀及其他工业的优质原料。
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  • 广西科技重大专项(桂科AB21196046)
  • 崇左市科技计划项目(崇科20220601)
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2025年第44卷第3期
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doi: 10.13355/j.cnki.sfyj.2025.03.014
  • 接收时间:2024-08-07
  • 首发时间:2025-09-01
  • 出版时间:2025-06-20
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  • 收稿日期:2024-08-07
基金
广西科技重大专项(桂科AA22067077)
广西科技重大专项(桂科AB21196046)
崇左市科技计划项目(崇科20220601)
作者信息
    1 广西南国铜业有限责任公司,广西 扶绥 532301
    2 桂林理工大学 材料科学与工程学院,广西 桂林 541004
    3 桂林理工大学南宁分校,广西 南宁 530001

通讯作者:

蒋学先(1968—),男,硕士,副教授,主要研究方向为有色金属冶金及资源回收利用。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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