CN1090827C - 从用过的镍－金属氢化物蓄电池中回收金属的方法 - Google Patents
从用过的镍－金属氢化物蓄电池中回收金属的方法 Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 238000009434 installation Methods 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical group [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
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Abstract
在循环回收用过的镍-金属氢化物蓄电池时，将电池废料通过磁选及风选选出除去粗的部分，再用硫酸溶解。先用选择性沉淀法从获得的溶液中除去稀土(来自负极的贮氢合金)以及铁、铝，然后用溶剂萃取在规定的条件(pH值，溶剂选择，各相的体积比)下使镍及钴定量地及在水相中保持与废料中相同的原子比而分离出。这样就有可能使它们同时进行电解回收，析出的产物形成母合金，可以与沉淀出且通过电冶金方法加工获得的稀土结合制造新的贮氢合金。
Description
本发明涉及从用过的镍-金属氢化物蓄电池中回收金属的方法，在该方法中，从蓄电池废料的酸分解溶液中以硫酸复盐的形式分离出稀土金属，再提高pH值除去铁，然后对铁沉淀的滤液用有机萃取剂进行液-液萃取以回收其他金属，例如锌、镉、锰、铝以及残留的铁及稀土。
镍-金属氢化物蓄电池是电化学贮能装置，与别的蓄电池例如铅蓄电池或镍-镉蓄电池相比，它的贮能容量更大。因此这种贮能系统不仅以钮扣电池形式在娱乐性电子设备、游戏机等中用作不受电网限制的能量供应装置，还在交通工具的驱动方面以大尺寸的蓄电池形式日益推广使用。
镍-金属氢化物蓄电池的气密性铜质外壳内装有一个或若干正电极、一个或若干负电极以及隔板、密封材料及电解质。
正电极通常由载体及活性物质组成。按照电极的类型，载体可以是网状、板网、带孔的板、纤维网或高孔率的金属泡沫材料。载体材料是镍或镀镍的铁。活性物质为氢氧化镍及氧化钴的混合物，有时还含有钴金属。除粘结剂及导电材料外，混合物中还含有数量较少的其他金属，例如氢氧化物形式的锌。
负电极也是由载体及活性物质组成。这里的活性物质是贮氢合金。贮氢合金是金属间化合物，它们可按简单母合金LaNi5之故而列入AB5-型或按简单合金TiNi2列为AB2-型。
一般情况下，镍-金属氢化物蓄电池中使用的AB5-型贮氢合金由45～55％Ni，30-35％稀土(SE)，5-15％Co，2-5％Mn及1-4％Al组成。
这种蓄电池所含的有用物质使得从废弃的电池中回收它们成为一种特别迫切的任务。
处理这些用过的蓄电池，特别是针对酸性的铅蓄电池已有许多已知的方法。但其中处理酸性铅蓄电池的方法在这里意义不大，因为它与本
发明的内容相差甚远。
但是常见回收方法的大部分准备步骤都是相同的，其中例如将收回的旧电池按一定项目分类，例如电池大小、电池形状(圆形电池，柱形电池，钮扣电池)等，在破碎机中粉碎，在粉碎后，有时还将经过洗净的废料用磁铁除去来自电池壳的铁(及镍)，最后对粉碎的物料用酸进行湿法化学处理。然后经过一系列分步沉淀以及萃取过程从有价值物质的分解溶液中分离出存在的金属，最后通过电解法析出以进行回收。
如果从未分类的废电池开始，则还需考虑在碱性蓄电池中不存在的铜、汞之类的物质，这种分离过程是十分复杂的，如在DE-OS4224884中所述。在这些方法中，为选择性分离出分解溶液一部分中的Zn-离子，需采用液-液萃取法，其中在混合-沉淀-装置中加入有机萃取剂作为选择相。Ni及Cd则留在不含Zn的溶液中。
在其他已知用于处理镍/镉电池的方法中，液-液萃取也起着重要的作用。
按照WO92/03853，Ni/Cd电池废料过滤后的盐酸分解溶液用75％(体积)三丁基磷酸酯(TBP)及25％(体积)脂族烃的混合液进行对流溶剂萃取除去Cd，然后再通过所谓反向萃取(再进入含水的酸相中)以适于电解析出的要求。
在EP-A-585701中，提出了一种萃取分离法将Ni及Cd从用HCl溶解细废料获得的溶液中分离，在这里除分离出一部分磁性物料(Fe及Ni)外，还通过风选得到轻物质如塑料(外壳，隔离层，粘结剂)。
US-PS 5 129 945中的回收方法特别涉及从废合金中回收稀土及过渡族金属。其中先通过氢氧化物沉淀再从分解液的滤液进行溶剂萃取以分离出残余的Fe，这种情况下水相中剩余的是Co。
在所有这些已知的方法中，所用措施的目的都是为了将金属组分系统地逐一分离，将以盐或氢氧化物形式分离出的金属化合物用还原剂制成纯金属回收。最后一个步骤中适用的有金属热还原法或电解法。
采用这些方法虽然可以将回收的铁送回炼钢厂加工；镍、钴和镉分别送回电池制造厂；但是分离的各种金属在制造新的电极材料时还要从纯态进行相应的混合加工。
据此，本发明的任务是，从用过的镍-金属氢化物蓄电池中回收特别适用于制造贮氢合金的制品。
按本发明，从用过的镍-金属氢化物蓄电池中回收金属的方法，包括下列步骤：
蓄电池废料用酸溶解，稀土金属以硫酸复盐形式分离；
经提高滤液pH值而沉淀铁；和
对铁沉淀的滤液用有机萃取剂进行液/液萃取，萃取在其原始溶液pH值为pH3及pH4之间的条件下进行，以回收其他金属，如锌、镉、锰、铝和残留的铁和稀土，选择的萃取剂及pH值使得在萃取后，只有金属镍及钴完全溶解在水相中并保持与蓄电池废料中相同的原子比例。
按照本发明，进行液-液萃取时考虑选好萃取剂以及分解溶液的pH值，使金属镍及钴完全溶解在水相中，并且同时保持与蓄电池废料中的相同的原子比例。
本发明所采用的措施在备料阶段与前面最后介绍的US-PS5129945中所述基本一致。
因此，废料中所含的稀土大部分用2-2.5M H2SO4浸滤进入溶液中，其中溶液中除稀土外还含有其他过渡金属，特别是铁、镍及钴。
为了防止在后述的稀土硫酸复盐沉淀时碱式硫酸铁同时沉淀，必须将存在的Fe3+还原。采取的措施是使分解溶液多次流过用机械方法分离出的金属铁，即磁性部分(粗部分)。
通过加入NaOH或NH4OH将强酸性溶液的pH值提高到1.5到2.0，稀土即以组成为(SE)2(SO4)3·Na2SO4·xH2O的极难溶的硫酸复盐形式沉淀。
过滤后的沉淀物溶解在酸中，再从该溶液中获取稀土氯化物或氧化物，经过电冶金法还原成稀土金属或几种稀土金属的混合物(混合金属)。
硫酸复盐沉淀的滤液中，还含有不属于稀土族的过渡金属以及铝，有时也还含有少量的稀土残余。再将pH值提高到4到4.5，首先沉淀出碱式硫酸铁(黄钾铁矾)或氢氧化铁形式的铁，有时还沉淀出Al(OH)3。为了保证所有铁以三价形式沉淀，溶液中事先加入氧化剂，优选H2O2。
Fe、Al沉淀之后，接着是萃取步骤，它将清除所有残余的及杂质金属组分(误选)，该步骤只将Co及Ni分离至水溶液中，所有不希望有的元素都分离。作为萃取剂优选含磷的阳离子交换剂与有机溶剂结合。
为了能在处理过程中获得可直接用以制造新的贮氢电极的最终制品，按本发明，优选的是，在Fe、Al氢氧化物沉淀之后接着进行液-液萃取。萃取时，只有镍和钴留在水相中，而且具有与所处理的废料中这两种金属相同的原子比。结果，所有未被除去的附带金属，无论是来自镍-金属氢化物电池或个别误选的电池(碱-锰，NiCd，含AB2-合金的NiMeH电池等)，特别是Zn、Cd、Mn、Cr以及遗留下的Fe、Al和稀土在萃取过程中都进入有机物相中。含有所述元素的盐类的有机相将按已知的方法进一步处理以回收这些金属。
如果分解溶液中原来的铁含量大于0.05g/l，则可能对萃取过程产生干扰。因此无论如何必须事先减少溶液中的铁(及铝)的含量。
本发明的溶剂萃取是一种“净化萃取过程”，其中除不包括在内的金属镍及钴以外，溶液中所有遗留的金属残余都完全清除。实施这种萃取时，将碱加入分解溶液(Fe、Al氢氧化物沉淀后的滤液)中调节到pH3到pH4，优选约为3.5，并使溶液反复地，特别是在多级对流设备中与由二乙基己基磷酸、异十三烷醇以及作为溶剂的一种脂族烃构成的混合物强烈地接触，混合比为30∶10∶60。还在一个混合器中加以搅拌以促进其接触效果。按照本发明，水相与溶剂相的体积比应为1∶1或稍大些。
通过按照本发明采取上述措施后，Mn、Cd、Fe、Al、Zn、Cr以及稀土等元素已定量地完全从分解溶液中除去，其中稀土的主要部分已通过过程开始时的硫酸复盐沉淀，而Fe及Al的主要部分通过氢氧化物沉淀而分离除去，这样可将Ni及Co从水相中共同回收。
关于Ni，Co-回收，下面介绍的方法原则上适用。
可以通过加入氢氧化钠及/或碳酸钠将水相的pH值进一步提高到约10。这样金属完全以氢氧化物或碳酸盐的形式沉淀出。在进行进一步处理之前，先将沉淀物在干燥箱中于100℃到200℃干燥，然后在400℃到1000℃煅烧，最后在电弧炉中用如铝或碳之类的还原剂，也就是通过金属热还原方法或碳热还原方法熔化成Ni/Co合金。
另外可能的是，采用同时电解法进行回收。因为Ni及Co的电化学析出电位十分接近，可从水溶液中以它们在溶液中的浓度比电析出两种元素的合金，再通过热处理制成母合金。
无论是从还原性熔化或是通过同时电解法都可获得适合于制造贮氢合金的产物，因为两种元素的混合比与用过的镍-金属氢化物蓄电池中的贮氢合金所含的混合比相同。因此，它们可以直接供给合金制造者用来制造所需母合金。在电解析出这种产物时，没有必要像专利DE-PS3123833中所述的那样采取特殊措施在电解过程中控制Ni2+/Co2+的比值以析出完全均一的合金材料，因为在再次熔化过程中母合金会达到均一程度。
母合金在电弧炉中熔化后就可与从硫酸复盐沉淀获得的稀土一同在真空感应坩锅炉中或真空电弧炉中熔化成贮氢合金，然后就可用它制造新的镍-金属氢化物蓄电池。
稀土硫酸复盐先在酸中溶解，再沉淀为碳酸盐，钠则留在溶液中。将碳酸盐溶解在HCl中，通过蒸发得到稀土的氯化物，再通过熔融电解还原成混合金属。
镍及钴的含水电解液可在一种带隔膜的电解槽(称为Hybinette电解槽)中进行电解。用大工业中在Hybinette电解槽中电解镍的通常条件，获得Ni/Co合金，电流得率超过90％。
采用本发明的液-液萃取法回收和以适于贮氢合金的母合金形式回收Ni及Co，使得从废料中制造新的镍-金属氢化物蓄电池具有十分有利的经济基础。
从回收物料制造电池的其他元件的可能性也属于本发明的范围。特别是指正电极的制造，只要是其中的活性物质也含Ni及Co，其含量与贮氢合金负电极中类似。
为了使这种回收方法也能用来处理这些电池成分，按照本发明，还可将溶剂萃取后的部分弱酸性分解溶液分别处理以回收其中的金属镍及钴。镍与钴可按已知的方法同样通过液-液萃取进行分离。
有机相中收集的元素可通过“反向萃取”再转到一种含酸的水相中，然后从水相中用电解法析出或以碳酸盐形式沉淀出来。再从后者用铝还原或碳热还原法获得纯金属。
用经过一种“净化萃取”步骤的新方法回收镍和钴首先特别适合于循环回收镍-金属氢化物蓄电池的有价值部分，也就是其中负电极内的贮氢合金。也可以任选单独回收镍以制备新的氢氧化镍及载体材料，不然电池制造者还需从别的来源购买这种原料。钴也一样，它是正电极材料中的添加物。这就说明本发明也可对废料中的夹杂物进行处理，例如旧的Ni/Cd电池或碱-锰电池等。当这些物质由于漏检混入的量不大时，对回收的操作也没有多大的影响。
在液-液-萃取或溶剂萃取之后分别回收镍及钴时，可以用通常的电解设备得到这些金属，这也是本发明的优点。
Claims (10)
1.从用过的镍-金属氢化物蓄电池中回收金属的方法，其特征在于，
将蓄电池废料用酸溶解，稀土金属以硫酸复盐形式分离；
经提高滤液pH值而沉淀铁；和
对铁沉淀的滤液用有机萃取剂进行液/液萃取，萃取在其原始溶液pH值为pH3及pH4之间的条件下进行，以回收其他金属，选择的萃取剂及pH值使得在萃取后，只有金属镍及钴完全溶解在水相中，并保持与蓄电池废料中相同的原子比例。
2.按照权利要求1的方法，其特征在于有机萃取液由阳离子交换剂及稀释剂组成。
3.按照权利要求2的方法，其特征在于有机萃取液由二乙基己基磷酸与异十三烷醇及脂族烃以30∶10∶60比例混合而成。
4.按照权利要求1的方法，其特征在于所述其他金属为锌、镉、锰、铝和残留的铁和稀土。
5.按照权利要求4的方法，其特征在于溶剂萃取在pH3.5进行。
6.按照权利要求1-4之一的方法，其特征在于从用萃取剂处理后的水相中，金属镍及钴以镍钴合金形式同时析出。
7.按照权利要求6的方法，其特征在于两种元素的合金按其在溶液中的浓度比例析出。
8.按照权利要求6的方法，其特征在于析出合金中镍与钴的比例对应于处理镍-金属氢化物蓄电池过程中两种元素的比值。
9.按照权利要求6的方法，其特征在于镍钴合金除以混合金属形式外、也可以母合金形式用于新的贮氢合金。
10.按照权利要求1-4之一的方法，其特征在于从液-液萃取的水相中分别回收镍和钴。
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| KR970007520B1 (ko) * | 1993-04-05 | 1997-05-09 | 산도쿠긴조쿠 고교 가부시키가이샤 | 니켈수소 2차 전지로부터의 유효금속회수법 |
| US5429887A (en) * | 1994-05-16 | 1995-07-04 | The United States Of America As Represented By The Secretary Of The Interior | Process for treating AB5 nickel-metal hydride battery scrap |
-
1994
- 1994-12-20 DE DE4445496A patent/DE4445496A1/de not_active Withdrawn
-
1995
- 1995-12-01 JP JP51945696A patent/JP3918041B2/ja not_active Expired - Fee Related
- 1995-12-01 EP EP95940265A patent/EP0800710B1/de not_active Expired - Lifetime
- 1995-12-01 CA CA002207575A patent/CA2207575C/en not_active Expired - Fee Related
- 1995-12-01 DE DE59503738T patent/DE59503738D1/de not_active Expired - Fee Related
- 1995-12-01 CN CN95196964A patent/CN1090827C/zh not_active Expired - Fee Related
- 1995-12-01 DK DK95940265T patent/DK0800710T3/da active
- 1995-12-01 WO PCT/EP1995/004735 patent/WO1996019840A1/de active IP Right Grant
- 1995-12-01 ES ES95940265T patent/ES2122701T3/es not_active Expired - Lifetime
- 1995-12-01 AT AT95940265T patent/ATE171568T1/de not_active IP Right Cessation
-
1997
- 1997-06-16 US US08/896,512 patent/US5858061A/en not_active Expired - Fee Related
-
1998
- 1998-06-10 HK HK98105127A patent/HK1005965A1/xx not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4041125A (en) * | 1973-06-15 | 1977-08-09 | Forskningsgruppe For Sjeldne Jordarter | Process for separation of the lanthanides |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1005965A1 (en) | 1999-02-05 |
| CA2207575A1 (en) | 1996-06-27 |
| JP3918041B2 (ja) | 2007-05-23 |
| EP0800710A1 (de) | 1997-10-15 |
| CN1171170A (zh) | 1998-01-21 |
| ATE171568T1 (de) | 1998-10-15 |
| ES2122701T3 (es) | 1998-12-16 |
| WO1996019840A1 (de) | 1996-06-27 |
| JPH10510878A (ja) | 1998-10-20 |
| DK0800710T3 (da) | 1999-06-14 |
| DE4445496A1 (de) | 1996-06-27 |
| EP0800710B1 (de) | 1998-09-23 |
| US5858061A (en) | 1999-01-12 |
| CA2207575C (en) | 2006-10-10 |
| DE59503738D1 (de) | 1998-10-29 |
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