CN103380234A - 通过同时的阴极和阳极沉积从沥滤液电解回收金和银 - Google Patents
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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Abstract
本发明涉及处理金和银的采矿和矿物或材料处理工业。具体而言，本发明涉及利用同时在阳极和阴极发生的电解从硫代硫酸盐或硫脲溶液回收金和银的方法。本发明相对于现有技术的优势在于速度增加并且极大降低与常规电解池中所见的那些相关的能量消耗。
Description
技术领域
本发明涉及用于处理含有金和银的矿物和材料的采矿工业。具体而言，本发明涉及利用同时的阳极和阴极电沉积法从沥滤液回收金和银的方法，之后贫溶液被再循环至沥滤阶段。
背景技术
通过多种方法进行了自矿物中回收金和银，其中最常用的是高温冶金处理，其中在添加大量能量之后，部分矿物被氧化，以这种发生释放出贵金属。这种大量的能量是该方法的主要不便之处，其最终反映在操作成本上。
另一方面，湿法冶金法的特征在于其高选择性和相对较低的试剂和能量成本。100多年来已经通过一种这样的方法得到金和银：其分别利用氰化物和氧气作为络合剂和氧化剂。尽管该体系具有高效性，但是对复杂矿物的处理以及环境限制促进了对能够与氰化物竞争而没有其缺点的其他沥滤系统的研究。
在铜存在下，硫代硫酸盐以及硫脲与甲脒化二硫的组合(Poisot-Diaz,M.E.,González,I.and Lapidus,G.T.(2008),“Effect ofCopper,Iron and Zinc Ions on the Selective Electrodeposition of Doréefrom Acidic thiourea Solutions”,Hydrometallurgy2008,Eds.C.A.Young,P.R.Taylor,C.G.Anderson y Y.Choi,Society for Mining,Metallurgy andExploration,Inc.(SME),Littleton,Colorado,U.S.A.,ISBN:978-0-87335-266-6,pp.843-848and Alonso-Gómez,A.R.and Lapidus,G.T.(2008),“Pretreatment for Refractory Gold and Silver Minerals beforeLeaching with Ammoniacal Copper Thiosulfate”,Hydrometallurgy2008,Eds.C.A.Young,P.R.Taylor,C.G.Anderson y Y.Choi,Society for Mining,Metallurgy and Exploration,Inc.(SME),Littleton,Colorado,U.S.A.,ISBN:978-0-87335-266-6,pp.817-822.)是两种从已证实氰化作用对其无效的矿物中沥滤金和银的化学体系。以同样的方式，已显示利用直接电沉积能够从两种体系回收金和银金属(A.Alonso.G.T.Lapidus and I.González,A strategy to determine the potential interval for selective silverelectrodeposition from ammoniacal thiosulfate solutions Hydrometallurgy,Volume85,Issues2-4,March2007,Pages144-153)；然而，这种发现在几何学复杂的反应器中完成(F.C.Walsh,C.Ponce de Leon and C.T.Low,The rotating cylinder electrode(RCE)an its application to theelectrodeposition of metals,Australian Journal of Chemistry,58,(4),246-262and A.Alonso,G.T.Lapidus and I.González,Selective silverelectroseparation from ammoniacal thiosulfate solutions using a rotatingcylinder electrode reactor(RCE),Hydrometallurgy,Volume92,Issues3-4,June2008,Pages115-123)，而且从经济和财政立场而言，能耗使得其不具吸引力。
在这点上，重要的是提及硫脲和硫代硫酸盐系统的特性：这两种络合剂均可在银的还原电位下氧化(图1和2)。这两种与金的配体的图表是类似的。这源于形成了窄电位区，其中Ag(I)和Au(I)离子是可溶的，而且由于这个原因，应精确地控制两种沥滤以及电分离条件。相对于其他系统这意味着极大缺点，而且其促成了采用膜反应器，以避免这些溶液与阳极接触。
发明目的
本发明的一个目标是提供一种通过同时的阳极和阴极电沉积从硫代硫酸盐或硫脲溶液分离金和银的方法，通过这种方式提高了该过程的速度。另一目的是利用受到最低限度影响的溶液组合物完成该方法，使得该溶液组合物可被再循环回到沥滤阶段。又一目标是促进有效的能量利用。
根据对下述描述和图（其包括在本文中的目的是阐述而非限制）的研究，应用所述原理且源自本发明的其他目标和优势可以是显而易见的。
发明内容
本发明意图解决从硫代硫酸盐和硫脲沥滤液分离金和银的问题，其相比正在使用的传统电化学反应器提供了改进。该改进特征在于该新型方法利用商购铜片作为阳极且利用钛片作为阴极，在一个隔间反应器中在阳极和阴极上同时沉积金属。
根据对图1的分析选择允许该技术操作的条件，其中在金属银稳定区观察到可溶性复合物Ag(S2O3)2 3-区。当电位降低至-110mV以下时，Ag(I)物种在典型的电解过程中被还原成Ag0。然而，该图最令人感兴趣的方面在于当电位小于-50mV时，部分硫代硫酸盐氧化，使可溶性复合物失稳并形成金属银。本发明利用了该现象，而且先前并没有报告该配体或其他配体。
采用同时的金和银阳极-阴极电沉积使得可在没有膜的简单几何学的电化学反应器中更有效地利用电能；另外，该分离过程在小于常规电化学反应器所需的时间内发生。
为了更好地理解本发明的特征，通过图表和附图进行下述描述，其构成本发明的组成部分，而且其意图是阐述性而非限定性的，并且在下述章节进行描述。
附图简述
图1是Pourbaix-型图表，其中显示了可溶性物种Ag(S2O3)2 3-(硫代硫酸盐-银复合物)和金属银Ag0的主导性区域。
图2是Pourbaix-型图表，其中显示了可溶性物种AgTu3 +(硫脲-银复合物)和金属银Ag0的主导性区域。
图3显示了利用本发明用于获得金和银的沥滤-电沉积方案。
图4是显示包括电化学反应器的再循环系统的图。
图5是其中实现同时的阳极和阴极沉积的电化学电池的示意图。
图6是银浓度随沥滤时间变化的图示。
图7是是银浓度随电解时间变化的图示，其中存在同时的阳极和阴极电沉积。
图8是比较利用相同溶液的沥滤1、2和3中银浓度的变化的图。
图9显示了在利用相同溶液的电解1、2和3过程中银浓度的比较。
具体实施方式
在本发明中提到的同时的电沉积法在图3中阐述。
·将开始于沥滤阶段(100)并且进行过滤(200)之后的富含金和银离子的硫代硫酸盐或硫脲溶液引入电化学反应器(300)中。
·电沉积结束后，从反应器移出阴极(312，图5)和阳极(313，图5)，并机械刮擦，以取下金属金和银。然后将溶液再循环回到沥滤阶段(301)。
电沉积在图4图解的再循环方案中进行，其中溶液从其被泵送的贮器(320)加料至电化学反应器(310)，然后通过重力返回该贮器。
实施例
实施例1
为更好地理解本发明，对很多实验中的一个作为实例进行了详述，其利用诸如在图3-5中所图解的系统。使用60cm2(暴露的几何面积)钛板作为阴极，而具有相同暴露面积的铜板作为阳极。
如图3中所示，第一阶段是金和银从矿物或精矿中沥滤，在这种情况中利用的是硫代硫酸盐溶液，其组成呈现于表1中。用NH4OH将pH调节至10.0。
表1.沥滤液的组成
| 组分 | 组成(mol/L) |
| (NH4)2S2O3 | 0.2 |
| CuSO4 | 0.05 |
| EDTA | 0.025 |
| (NH4)2HPO4 | 0.1 |
采用去离子水(1×1010MΩcm-1)利用试剂级化学品制备溶液。使500mL该溶液放置成与3.75g浮选精矿相接触，该精矿粒度小于10μm，含有21kg/吨银。连续搅拌6小时之后，通过过滤使溶液与固体分离，并将其置于诸如在图4和5所呈现的反应器中。
在电沉积过程中，利用1.1L/min流量，电池电压为100mV；该电压下，对标准氢电极(NHE)，阴极的电位为-260mV，其足够在该电极上获得选择性银沉积物。
图6显示了银浓度相对于沥滤时间的图示。在120分钟内达到最大值，该时间之后浓度保持相对恒定。
电解过程中银浓度的变化示于图7中。在首个15分钟内，观察到尖锐的下降，然后其逐渐降低至10mg/L以下的值。在该实验过程中产生的电流为0.01A，其连同电池电压一起转变成0.004W-h。鉴于所沉积的银质量为0.065g，则沉积每克银的能耗为0.062W-h。
在完成电沉积之后，将溶液再循环回到沥滤阶段，在那里，在先前所述的相同条件下，使其与新鲜的未沥滤精矿接触。重复整个步骤，直到完成三个循环。
图8显示了所有三个循环的沥滤结果的图示；在第二和第三沥滤中可观察到相对于第一沥滤而言沥滤速度增加和最大银浓度，这可能是由于硫代硫酸盐与Cu(II)和Cu(I)离子之间的平衡稳定。
另一方面，第二和第三电解(图9中的虚线和点线)显示了与第一（实线）电解类似的趋势，仅有的区别在于初始值，其取决于先前的沥滤阶段。在所有三种情况中，均在约4小时内达到10mg/L以下的值。
这些结果清楚地显示，在电沉积阶段后，硫代硫酸盐溶液可被再循环回到沥滤阶段至少三次，而无需重调或处理。另外，在三次电解期间，电流维持在0.01A的恒定值，保持了与第一循环相同的能量消耗。在三次电沉积循环之后，阳极消耗是可忽略的。
最后，重要的是提及阳极和阴极沉积物的X-射线衍射分析显示，所述沉积物仅由银组成。
Claims (2)
1.从硫代硫酸盐或硫脲沥滤液回收银的电解法，其特征在于通过在电势区操作，同时在阳极和阴极表面实现金属沉积，其中所述电势区允许在阴极发生银或金还原且在阳极发生配体氧化。
2.从硫代硫酸盐或硫脲沥滤液回收银的电解法，其特征在于所述沥滤液含有下述其他组分：
。
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| MXMX/A/2010/013717 | 2010-12-13 | ||
| PCT/MX2011/000151 WO2012081952A2 (es) | 2010-12-13 | 2011-12-09 | Electrorecuperación de oro y plata a partir de soluciones lixiviantes mediante depósito catódico y anódico simultáneo |
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| CN113652554A (zh) * | 2021-07-16 | 2021-11-16 | 武汉理工大学 | 一种基于电容去离子技术回收溶液中贵金属的方法 |
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|---|---|---|---|---|
| WO2016018409A1 (en) * | 2014-07-31 | 2016-02-04 | Hewlett-Packard Development Company, L.P. | Process image according to mat characteristic |
| CA3046585A1 (en) | 2016-12-08 | 2018-06-14 | Metoxs Pte, Ltd. | Recovery of gold and silver from precious metals-containing solids |
| US10807085B2 (en) * | 2017-11-17 | 2020-10-20 | University Of Massachusetts | Silver recovery as Ag0nanoparticles from ion-exchange regenerant solution |
| CN113621995B (zh) * | 2021-07-16 | 2023-12-26 | 武汉理工大学 | 一种基于电化学联合催化技术回收硫代硫酸盐浸出液中贵金属的方法 |
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2010
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- 2011-12-09 AU AU2011341844A patent/AU2011341844A1/en not_active Abandoned
- 2011-12-09 EP EP11813915.3A patent/EP2653590A2/en not_active Withdrawn
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- 2011-12-09 CN CN2011800674437A patent/CN103380234A/zh active Pending
- 2011-12-09 WO PCT/MX2011/000151 patent/WO2012081952A2/es active Application Filing
- 2011-12-09 JP JP2013544412A patent/JP2014505788A/ja active Pending
- 2011-12-09 RU RU2013132451/02A patent/RU2013132451A/ru not_active Application Discontinuation
- 2011-12-09 US US13/993,247 patent/US20140076735A1/en not_active Abandoned
- 2011-12-09 PE PE2013001408A patent/PE20140494A1/es not_active Application Discontinuation
- 2011-12-09 BR BR112013014874A patent/BR112013014874A2/pt not_active IP Right Cessation
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| WO2009113842A1 (es) * | 2008-03-14 | 2009-09-17 | Universidad Autónoma Metropolitana | Proceso de lixiviación y recuperación de plata y oro con soluciones de tiosulfato amoniacales de cobre |
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| CN113652554A (zh) * | 2021-07-16 | 2021-11-16 | 武汉理工大学 | 一种基于电容去离子技术回收溶液中贵金属的方法 |
| CN113652554B (zh) * | 2021-07-16 | 2022-12-27 | 武汉理工大学 | 一种基于电容去离子技术回收溶液中贵金属的方法 |
Also Published As
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| WO2012081952A3 (es) | 2012-12-06 |
| PE20140494A1 (es) | 2014-04-30 |
| US20140076735A1 (en) | 2014-03-20 |
| WO2012081952A2 (es) | 2012-06-21 |
| AU2011341844A1 (en) | 2013-08-01 |
| BR112013014874A2 (pt) | 2016-10-18 |
| CA2821421A1 (en) | 2012-06-21 |
| EP2653590A2 (en) | 2013-10-23 |
| CO6801793A2 (es) | 2013-11-29 |
| WO2012081952A4 (es) | 2013-01-24 |
| AU2011341844A2 (en) | 2013-10-17 |
| RU2013132451A (ru) | 2015-01-20 |
| MX2010013717A (es) | 2012-06-13 |
| JP2014505788A (ja) | 2014-03-06 |
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