CN101389442B - 用于金属的电解提炼的改进的合金以及阳极 - Google Patents
用于金属的电解提炼的改进的合金以及阳极 Download PDFInfo
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Abstract
本发明涉及其中添加钴的铅钙锡合金。所述合金可用于形成用于电解提炼池的阳极。包含所述钴合金的电解提炼池特别适于从硫酸电解质中电解提炼金属,例如铜。所述包含钴的阳极可以改进在电解提炼过程中在阳极上的氧释放的效率,并且减少阳极的腐蚀。
Description
背景技术
多年来已将铅钙锡合金用作铜电解提炼(electrowinning)的电解提炼阳极。Prengaman等在4,373,654中开发了首个轧制铅钙锡阳极。这些阳极从80年代初开始就已用于铜电解提炼。使用轧制铅钙锡合金的阳极具有长的使用寿命。钙和锡成分的组合以及机械加工可制备具有高机械强度的材料,以在使用期间防止变形(distortion)、翘曲(warping)和短路。锡和钙的组合降低了腐蚀速率,促进了导电的腐蚀层在阳极表面的形成,并改善了阳极的稳定性,由此提高了阳极的使用寿命。Prengaman在6,131,798中通过将轧制合金片附着在铜母线(bus bar)上而进行了改进。Prengaman等在5,172,850中通过将电沉积的铅层镀覆在铜母线上来保护铜母线不受损害,从而提高了耐酸性能。
尽管提高了铜电解提炼阳极的使用寿命,但阳极被电解提炼过程中生成的氧气腐蚀。Prengaman在“Improved Copper Electrowinning OperationsUsing Wrought Pb,Ca,Sn Anodes,”Cu 99 International Symposium,October1999中描述了所述阳极腐蚀。氧作为氧气释放(evolve)或通过阳极表面的腐蚀产物扩散至铅表面,并在此与铅合金反应以腐蚀阳极。重要的是在阳极的表面上制备完全均一的、紧密的、薄的、附着性的导电PbO2腐蚀层,以使得氧可以被有效地释放。
随着腐蚀产物变厚,其开始形成与阳极表面平行的细小裂纹。这些裂纹最终导致在阳极表面生成非附着性的薄片(flake)。随后,腐蚀产物可以被在阳极表面生成的氧气泡由所述表面上除去(dislodged)。如果所述薄片与阴极接触,则其可以被还原成金属铅并夹带在阴极中。
腐蚀速率与电解质温度以及电解提炼池的电流密度有关。电流密度和温度越高,腐蚀速率越快。除了电解提炼池的条件以外,电解质通常还包含锰。锰可以与氧化物表面的PbO2腐蚀产物反应,使其稳定性和附着性降低从而更易于脱落。所述内容由Prengaman描述于Cu 87第三卷和W.Cooper,G.Loyas,G.Vearte编辑的Electrometallurgy of copper,p.387。
为了降低阳极的腐蚀速率,增加氧气释放并降低锰的有害效果,将钴添加至铜电解提炼的电解质中。将钴添加至电解提炼溶液中首先描述于O.Hyvarinen,P&D thesis,1971和最近的Yu和O’Keefe,J.Electrochem Society,146(4),1999,p.1361,“Evolution of Lead Anode Reactions in Acid SulfateElectrolytes I.Lead Anodes with Cobalt Additives.”
钴使氧气释放反应去极化,从而使得氧气释放更为容易。其减少了阳极腐蚀,改善了铜阴极的质量并延长了阳极的使用寿命。钴离子被吸附至铅腐蚀产物上。对腐蚀产物的分析显示了钴的存在。
通常以50-300ppm的量将钴添加至电解质中。Jenkins等在cooper 99,Vol.IV, Hydrometallurgy of Copper Electrolyte Copper-Leach,SolventExtraction and Electrowinning World Operation Data”中调查研究了34个铜电解提炼车间的操作条件。为了保持电解质的钴含量,必须连续地添加钴以补偿电解质从此系统中的渗料(bleed),以控制电解质中的杂质。添加的钴在100-800g/吨铜阴极之间变化。渗料中的钴损失是铜车间操作中的主要成本。
发明内容
本发明涉及适于阳极的铅合金,所述阳极用于从硫酸溶液中电解提炼金属,特别是铜。本发明涉及将钴添加至用于电解提炼金属的阳极的常规铅钙锡合金中。所述合金还可以包含锶、钡、银和/或铝并优选为轧制。当用于电解提炼池时,与由不包含钴的合金制成的类似的阳极相比,所述阳极产生较低的氧过电压。本发明涉及所述合金、所述阳极、所述池、和使用包含所述阳极的池进行电解提炼的方法。
具体实施方式
本发明提供了适于用作用于电解提炼金属的阳极的合金。根据本发明,将钴添加至通常用于形成阳极的铅锡钙合金中。所述合金可以包含钡或锶以代替钙,或除钙以外还包含钡或锶。此外,可以存在银或铝。所述合金还可以包含存在于回收的铅中的痕量物质。
更具体地,所述合金为包含0.03-0.10%的钙、0.5-2.5%的锡和0.005-0.300%的钴的铅合金。应理解本发明中所有的百分数均指重量百分数。最优选地,锡与钙的比例为至少14∶1。
钙在所述合金中的量优选为至少0.05%。还优选钙不超过0.08%。
对于锡,所述合金优选包含至少1.0%。还优选锡不超过2.2%。
期望钴至少占所述合金的0.005%,更优选占所述合金的至少0.01%。期望钴在所述合金中的上限不超过0.100%,更优选为不超过0.040%。
特别优选的本发明的铅合金包含0.05至0.08%的钙,1.0至2.2%的锡和0.005至0.100%,更优选0.005至0.040%的钴。
所述合金还可以包含0.001-0.035%的铝。铝可以防止在加工过程中的钙氧化。优选地,铝不超过0.008%。
本发明的合金还可以包含0.002-0.10%,更优选0.002至0.080%的银。银可以减少腐蚀,增加机械性能,并增加阳极对高温下的结构改变的抵抗力。随着铜电解提炼中的电流密度的增加,电解质的操作温度的增加促进了阴极的沉积条件的改善。较高的温度提高了铅阳极的腐蚀速率,并且较高的温度增加了阳极材料中的再结晶或结构改变的可能性,其可能促进腐蚀。再结晶还会导致机械性能的损失。添加银可以限制晶粒间界运动,保持机械性能,减少所述合金中的蠕变和结构改变。如果银含量不足够高,则在所述材料中没有足够的银来限制高温下的晶粒间界运动。所用的银的含量比用于锌电解提炼的阳极的银含量低得多。
本发明最优选的合金是包含约0.07%的钙、约1.4%的锌、约0.015%的钴、约0.02%的银和约0.008%的铝的铅合金。
本发明的合金可以用作电解提炼金属,例如铜、镍或锰的阳极。为了形成本发明的阳极,可以将所述合金浇铸为坯锭或通过轧制至至少1.5∶1的缩减量使其变形。轧制使得晶粒结构重新取向(reorient)至轧制方向。与浇铸阳极相比,锻造的(wrought)材料对腐蚀和浇铸缺陷具有更好的抗性。最优选将所述材料轧制至变形比(deformation ratio)大于4∶1。
本发明的阳极可以用于电解提炼池和电解提炼方法。在优选的实施方案中,本发明包括改进的电解提炼池,所述电解提炼池包括阳极、阴极和硫酸电解质,其中所述改进包括使用上述的包含钴的阳极。本发明的阳极可以用于实现改进的金属(例如铜、镍和锰)电解提炼。所述阳极特别适于在硫酸电解质中电解提炼金属。本发明的改进方法特别适用于铜。本发明的阳极显示出更有效的氧气释放,因此显示出更高的抗腐蚀性。
已发现,与不含钴的相同的材料相比,当在硫酸电解质中被腐蚀时,包含铅、钙、锡和钴或铅、钙、锡、钴和银的阳极被去极化。所述去极化可以为20-100mV。由于钴掺入腐蚀层,因此人们相信当将钴添加至用于形成所述阳极的铅钙锡合金中时可以实现所述有益效果。因此,当腐蚀层在由本发明包含钴的合金制成的阳极上形成时,所述阳极的行为与在包含200 ppm钴的电解质溶液中操作的铅钙锡阳极(不含钴)的行为相似。与不包含钴的阳极不同,当使用本发明的阳极时,不需要为了实现钴对氧释放的有益效果而补充电解质中的钴。
此外,与不含钴的同样的材料相比,在所述包含钴的阳极中生成的腐蚀产物较薄,并且较少形成PbSO4(less subject to remission to PbSO4)。腐蚀层一旦形成就完全地被钴掺杂。随着腐蚀层碎裂(spall)和阳极被缓慢地腐蚀,形成新的被合金中的钴掺杂的腐蚀层,从而保持较低的氧释放电位。
实施例
样品材料
为了测定钴对氧释放的益处,评价了三种阳极合金:
样品1:包含0.078重量%的钙、1.35重量%的锌和0.005重量%的铝,并被轧制成0.250英寸厚的铅合金,其被用作用于比较各种阳极合金材料的行为的基础材料。
样品2:包含0.058重量%的钙、2.0重量%的锡、0.012重量%的银、0.0145重量%的钴、和0.005重量%的铝的铅合金,使用5∶1的压缩比将其轧制成0.250英寸厚。
样品3:包含0.059重量%的钙、2.15重量%的锡、0.015重量%的钴和0.062重量%的银和0.005重量%的铝的第三种合金,使用5∶1的压缩比将其轧制成0.250英寸厚。
如下所示,向所述阳极合金中添加钴可以降低腐蚀的量并提高氧释放效率。
氧化释放试验
将第一组所述三种阳极合金的试验样品抛光,并在180g/l H2SO4(电解质1)中,在30mA/cm2下氧化5小时。将第二组的三种样品抛光,并在包含0.2g/l Co的180g/l H2SO4(电解质2)中,在30mA/cm2下氧化5小时。
试验结果参见表1。
表1
阳极电位(伏)
基础合金合金 合金
腐蚀试验 1 2 3
(1)180g/l H2SO4 2.14 2.12 2.12
(2)180g/l H2SO4 2.05 2.06 2.06
+200 ppm Co
洗涤&干燥
循环试验
(1)180g/l H2SO4 2.13 2.08 2.03
(2)180g/l H2SO4 2.02 1.99 1.99
与不包含钴的同样的材料相比,在氧化形成腐蚀层的过程中,包含钴的样品显示出约20mV的去极化。当在200ppm钴的包含钴的溶液(电解质2)中氧化时,所有的样品被更高程度地去极化,样品之间未观察到显著差异。
洗涤并干燥样品,然后将样品在180g/l H2SO4中,在30mA/cm2下进行循环实验,以测定在PbO2腐蚀层形成的过程中发生的所述腐蚀层被锡、钴和银掺杂的效果。结果示于洗涤和干燥循环试验中。
基础样品显示出电位由2.14V降低至2.13V。这被认为是由于生成的腐蚀层被锡掺杂的结果。添加钴的样品2显示出40mV的去极化。样品3显示出90mV的去极化,并且与初始基值电位相比,显示出110mV的去极化。在200ppm钴溶液(电解质2)中氧化的样品显示出相似的极化,其中在含钴溶液中氧化的基础合金在循环后阳极电位降低约30mV。
结果显示腐蚀层在不包含钴的溶液中的形成显示出包含钴的阳极的显著去极化。在实施例3的情况下,所述去极化与腐蚀层在高钴含量的溶液中的形成的去极化几乎相同。
在包含钴的合金中,新形成的腐蚀层被钴掺杂,并且即使在洗涤、干燥和循环试验后,钴仍保持吸附在腐蚀层中。在阳极表面的腐蚀产物中钴的量比基础金属阳极的量少25-30%。经掺杂的腐蚀层几乎与由高钴含量的电解质生成的腐蚀层具有同样的活性。
随着腐蚀层碎裂,合金中的钴可以继续掺杂新生成的腐蚀层,从而提供用于保持阳极的去极化的钴。
Claims (18)
1.用于电解提炼阳极的合金,以重量百分比计,所述合金包含:
1.0%-2.5%的锡;
0.005%-0.300%的钴;
0.03%-0.10%的钙;
0.001%-0.035%的铝;
0.002%-0.10%的银;以及
余量的铅和不可避免的杂质。
2.如权利要求1所述的合金,其中所述合金包含0.05%-0.08%的钙。
3.如权利要求1所述的合金,其中所述合金包含1.0%-2.2%的锡。
4.如权利要求1所述的合金,其中所述合金包含0.005%-0.100%的钴。
5.如权利要求1所述的合金,其中所述合金包含0.01%-0.040%的钴。
6.如权利要求1所述的合金,其中所述合金包含:
1.0%-2.2%的锡;
0.005%-0.100%的钴;
0.05%-0.08%的钙;
0.001%-0.035%的铝;
0.002%-0.10%的银;以及
余量的铅和不可避免的杂质。
7.包含权利要求1所述的合金的电解提炼阳极。
8.包含权利要求2所述的合金的电解提炼阳极。
9.包含权利要求3所述的合金的电解提炼阳极。
10.包含权利要求4所述的合金的电解提炼阳极。
11.包含权利要求5所述的合金的电解提炼阳极。
12.包括权利要求6所述的合金的电解提炼阳极。
13.电解提炼池,包括电解质、阴极和权利要求7所述的阳极。
14.如权利要求13所述的电解提炼池,其中所述电解质为硫酸。
15.如权利要求13所述的电解提炼池,其中所述电解提炼池用于电解提炼选自铜、镍和锰的金属。
16.在电解提炼池中电解提炼金属的方法,该方法包括操作电解提炼池,所述电解提炼池包括电解质、阴极和权利要求7所述的阳极。
17.如权利要求16所述的方法,其中所述电解提炼在硫酸电解质中进行。
18.如权利要求16所述的方法,其中被电解提炼的金属选自铜、镍和锰。
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Application Number | Priority Date | Filing Date | Title |
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US11/361,146 US7704452B2 (en) | 2006-02-23 | 2006-02-23 | Alloy and anode for use in the electrowinning of metals |
US11/361,146 | 2006-02-23 | ||
PCT/US2007/000143 WO2007106197A2 (en) | 2006-02-23 | 2007-01-04 | Improved alloy and anode for use in the electrowinning of metals |
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CN101389442A CN101389442A (zh) | 2009-03-18 |
CN101389442B true CN101389442B (zh) | 2013-03-27 |
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EP (1) | EP2024133A4 (zh) |
JP (1) | JP4864101B2 (zh) |
CN (1) | CN101389442B (zh) |
AR (1) | AR059478A1 (zh) |
AU (1) | AU2007225408B2 (zh) |
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WO2011040599A1 (ja) | 2009-10-02 | 2011-04-07 | シャープ株式会社 | 血管状態モニタリング装置およびモニタリング方法 |
US9173604B2 (en) | 2010-03-19 | 2015-11-03 | Sharp Kabushiki Kaisha | Measurement device, measurement method, measurement result processing device, measurement system, measurement result processing method, control program, and recording medium |
CN102465313A (zh) * | 2010-11-17 | 2012-05-23 | 北京有色金属研究总院 | 一种电积铜用铅基惰性阳极的预处理方法 |
FI125711B (en) * | 2012-12-21 | 2016-01-15 | Outotec Oyj | Electrode for the electrolysis process |
CN103668340A (zh) * | 2013-11-18 | 2014-03-26 | 广西南宁市蓝天电极材料有限公司 | 一种电解锰阳极板及制造方法 |
CN104611609B (zh) * | 2015-02-13 | 2016-08-24 | 昆明理工恒达科技股份有限公司 | 一种有色金属电积用低银铅合金多元阳极材料的制备方法 |
CN105755509A (zh) * | 2016-05-13 | 2016-07-13 | 广西宜州申亚锰业有限责任公司 | 一种电解锰阳极板及其制造方法 |
CN106400050A (zh) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | 一种从废铜液中制备高质量电积铜的方法 |
CN114232035A (zh) * | 2021-12-21 | 2022-03-25 | 贵州省新材料研究开发基地 | 湿法冶金用改性阳极及其制备方法 |
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EP2024133A4 (en) | 2010-10-06 |
JP2009527652A (ja) | 2009-07-30 |
MX2008010649A (es) | 2008-11-12 |
EP2024133A2 (en) | 2009-02-18 |
CA2641316A1 (en) | 2007-09-20 |
BRPI0707977B1 (pt) | 2014-02-04 |
AU2007225408B2 (en) | 2010-12-09 |
CN101389442A (zh) | 2009-03-18 |
PE20071053A1 (es) | 2007-10-28 |
JP4864101B2 (ja) | 2012-02-01 |
WO2007106197A2 (en) | 2007-09-20 |
AR059478A1 (es) | 2008-04-09 |
US7704452B2 (en) | 2010-04-27 |
US20070193879A1 (en) | 2007-08-23 |
CA2641316C (en) | 2012-03-13 |
BRPI0707977A2 (pt) | 2011-05-17 |
ZA200807033B (en) | 2009-06-24 |
AU2007225408A1 (en) | 2007-09-20 |
MY147635A (en) | 2012-12-31 |
WO2007106197A3 (en) | 2008-01-10 |
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