CN1061382C - 含铋硫化矿或这种矿的浓缩物的处理方法 - Google Patents
含铋硫化矿或这种矿的浓缩物的处理方法 Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
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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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
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Abstract
本发明涉及一种预处理具有对进一步加工这类矿石或浓缩物有干扰作用的高铋含量的硫化矿或硫化矿浓缩物的方法,以致能进一步加工这类矿石或浓缩物,回收其所含的有价金属,或至少有助于这种处理。本发明的特征在于,在预定的时间内在同时加热和pH低于2的条件下用硫酸浸出该矿石或浓缩物,此后,从浸出液中分离出呈产品形式的浸出渣,该产品与进料相比铋含量较低而其所含的有价金属更为富集。
Description
本发明涉及预处理其铋含量妨碍进一步加工这类矿石或浓缩物的硫化矿或硫化矿浓缩物的方法,以便能处理这类矿石或浓缩物,回收其所含的有价金属,或至少有助于这种处理。
现有的硫化矿和硫化矿浓缩物由于其铋含量高或不能用于回收所含的有价金属或至少必须精心地处理,例如掺入贫铋物料降低其含量。最显著的问题是,采用主要用来加工生产精炼铜的物料,无论火法冶金或湿法冶金都要进行电解处理过程,在该过程中铋有强烈的干扰作用且促使形成具有严重杂质夹杂物危害的泥渣/阳极泥。此外,精炼铜要求的最高铋含量为1ppm。还得知有关铅和锡产品中铋含量的极限对铅而言为50-100ppm,对锡为100-500ppm。
例如,在火法冶炼铜的生产过程中处理铋的可能性有限,因为铋是在自然界中以元素形式存在的较贵重元素。如果冰铜与气体之间能获得良好的接触且该熔体具有高的温度,则在加工铜的第一个步骤即熔融和转化步骤中能首先将铋以气态硫化物的形式分离。采用高品位的冰铜和供给过程的空气用氧富集到的程度对铋的提取并不有利。不管上述降低铋含量的可能性如何,通常在后面的加工步骤中都要进行分离铋的纯化步骤,例如真空精炼或苏打处理的加工步骤,然而通常的结果是铋的收率很低。在大多数铜冶炼厂中,用于电解精炼过程的铜阳极的最大允许铋含量低至50ppm,以便能在最大可能程度上避免上述形成泥渣和尤其是由此而造成意味着铋污染的严重杂质夹杂物的有关问题。上述的意思是必须限制将铋引入铜的加工过程,而且同样要限制含铋物料的引入。甚至需要排斥某些物料,因为虽然在火法冶金的处理过程中铋的提取相对地固定,但是收率都太低。不难理解,必须把注意力主要集中在生产率和过程的经济性上,这意味着如上所述在铜加工过程中的高品位冰铜和氧的富集都不是除去铋的最佳条件。
已有人提出预处理铜浓缩物,其用意是在进一步加工该浓缩物之前降低其中的各种有害杂质含量。可以采用部分焙烧的方法来降低砷的含量,但是,对铋含量仅有微不足道的作用。采用硫化钠浸出能降低砷含量、锑含量和汞含量,然而通过这种处理对铋含量没有显著的作用。Outokumpu在CA-A-1057310中建议在旋转炉中于750℃、硫蒸气气氛中进行预处理。该方法可除去100%的砷、50-60%的锑,但对铋含量仅为20-30%。
Boliden在EP-B-0138794中提出了一种从铜熔融物料中主要除去Sb的方法。该方法包括在450-750℃下于旋转炉中采用基本上为化学计算量的氯化剂的单独氯化步骤,其中也可在相当大的程度上除去Bi。还有人提出生物氧化预处理、生物浸出法从铜浓缩物中选择性浸出铋。然而,为此目的的生物浸出法的选择性和实用性似乎完全取决于浓缩物的矿物组成,因此,其应用局限于处理某种合适组成的特定浓缩物。
本发明的目的是提供一种方法,采用该方法可在一定程度上从硫化矿或硫化物浓缩物中除去铋,且对所含的有价金属具有选择性,致使该物料能普遍地用于上述物料的预处理,从而使所述物料能容易地处理且可回收其中所含的有价金属。
采用以下权利要求书中陈述的具有性能特征的方法实现了上述目的。于是,在给定的时间内于pH低于2、同时加热的条件下用硫酸浸出该矿石或有关的浓缩物。在预定的时间结束时,将浸出渣以产品的形式从浸出液中分离出,该产品中的铋比进料中的更纯,且其中所含的有价金属已被富集。该浸出过程优选在pH为0-1的范围内进行。为了能获得最佳的结果,优选浸出温度超过50℃。该浸出过程优选在互相按顺序串联的多级浸出设备中进行。使用过的浸出液可以方便地在通入空气的同时用石灰或石灰石处理,以便将浸出了的铋和可能的铁以氢氧化物形式与呈石膏形式的所含硫酸盐一起沉淀。
众所周知,浓硫酸或稀硫酸和空气能与元素铋反应生成Bi3+离子,其中硫酸被还原为SO2。然而,关于硫酸能同样地与硫化物型的铋化合物反应的作用早先在文献中没有公开。这或许都不是由于铋与硫的亲和力很强所致。尽管如此,在某些特定条件下用硫酸浸出仍然导致铋显著地除去,加之,可选择性地提取所含的有价金属必定认为是显著的和意想不到的。根据一种理论,上述结果可能是由于铋和例如铜和银的有价金属之间的矿物中的复杂置换反应所致。除了以元素铋形式存在以外,铋还可以例如呈下列几类硫化矿物形式的硫化物型的铜矿石存在如: 硫银铋矿 AgBiS2辉铋矿 Bi2S3银硫铋铅铜矿 Pb(Ag,Cu)Bi2S4重硫铋铜铅矿 Pb2Cu2Bi4S9辉铅铋矿 PbBi2S4硫铜铋矿 CuBiS2针硫铋铅矿 PbCuBiS3
本发明提供的铋的收率高达90%且甚至更高,而有价金属例如铜的浸出不大于至多2%,另一方面,铁在较大程度上被浸出所得收率至多为5-6%。
因此,本发明的预处理方法所得的产品就Bi而言比进料浓缩物的更纯(甚至对Sb和As也可达到一定的纯度),在适合的情况下还富集了有价金属,因为所有存在的铁即使程度有限也被除去。因此,预处理后的金属从有关加工其所含的有价金属的几方面而言特别具有吸引力。
现在,将部分参照说明包括溶液纯化的本发明优选实施方案的流程图以及参照说明在实验室规模进行的浸出试验的实施例对本发明作更详细的说明。
附图是说明根据本发明的方法浸出铋的流程图。带有适当水含量的铜浓缩物取自浓密机或过滤机,任选另外加水稀释后,其固体含量为50-70%,将其送入第一个浸出槽。将硫酸加入该槽中,使pH保持约为1。用来自外部的热源加热槽中的物料。适宜的温度为90℃。将该槽中的物料连续转送到串联的第二个槽,并从该处再转送到第三和第四个槽。槽的容积以及在各槽中的停留时间按照预定的浸出总时间选择。根据有关的浓缩物组成所期望的收率依次选择浸出时间。如果认为适宜或需要,可将SO2加入末段槽中以沉淀浸出了的铜。在固/液分离+洗涤步骤后,可分离出富集了的且不含铋的铜浓缩物以便在冶炼炉中进一步加工。如流程图中所示,将浸出液和补加的洗水分成两个部分,其中,含在一部分中的Bi3+、Fe2+/Fe3+在供给空气的同时,于pH3-5的条件下用石灰石将其沉淀。在固/液分离+洗涤步骤的下游将含有氢氧化铋、氢氧化铁和石膏的沉淀物分离。可将仍然可能含有呈Cu2+离子形式的铜的残余溶液作为补充溶液返回到浸出步骤。如果需要,铜可从取自该返回液流的排出液中沉淀。剩余的浸出液作为生产过程用的溶液返回到第一个浸出槽。
实施例:
在一系列的试验中,将主要由黄铜矿和黄铁矿矿物组成的来自Aitik的铜浓缩物进行浸出。该铋的含量为120g/t且以几种不同的矿物形式存在,即早先提及的硫银铋矿、辉铋矿、银硫铋铅铜矿、重硫铋铜铅矿、辉铅铋矿、硫铜铋矿和针硫铋铅矿。总铋中的小部分以元素铋的形式存在。
这些试验均在矿浆密度约为45%固体下进行。在不同条件下对浸出过程进行了20小时的研究。在每个试验中将取自Aitik的500克浓缩物与610毫升水混合。在试验过程中连续测定pH并用H2SO4或NaOH调节。按5个时间点:0.5、1.0、2.0、5.0和24小时采集浸出液样品。
下面的表中列出了试验条件及所得结果:表
试验编号 | pH | 温度℃ | Bi收率% | Cu收率% | ||||
2小时 | 5小时 | 24小时 | 2小时 | 5小时 | 24小时 | |||
1 | 0 | 25 | 36 | 35 | 35 | 0.3 | 0.4 | 0.7 |
2 | 1.0 | 25 | 28 | 26 | 34 | 0.2 | 0.3 | 0.4 |
3 | 0 | 90 | 70 | 80 | 83 | 0.6 | 0.9 | 1.7 |
4 | 1.0 | 90 | 72 | 80 | 92 | 0.3 | 0.4 | 0.6 |
5 | 0.5 | 55 | 40 | 54 | 75 | 0.4 | 0.6 | 1.3 |
6 | 0.5 | 55 | 40 | 54 | 75 | 0.4 | 0.6 | 1.3 |
7 | 1.5 | 90 | 35 | 48 | 42 | 0.2 | 0.3 | 0.3 |
8 | 2.0 | 90 | 4 | 2 | 0 | 0.2 | 0.3 | 0.3 |
9 | 2.5 | 90 | 0 | 2 | 0 | 0.1 | 0.1 | 0 |
10 | 3.0 | 90 | 0 | 0 | 0 | 0 | 0 | 0 |
这样,最佳的铋浸出条件在pH0-1和90℃的温度下,在此条件下经过2小时后铋的收率高至约70%,而在同样的时间铜的收率很低约为0.5%。在室温下铋的收率从未大于约30%。温度为55℃时该收率显著地增加。在pH=2或更高时,Bi或Cu几乎没有浸出。
通过适当的类似实验室试验确定了这类有关浓缩物的适宜浸出时间,然而这仅限于在所选择的浸出温度下的最佳条件。根据在浓缩物中所要求的最高剩余铋含量来控制必需的浸出时间。考虑到在处理过程中有价金属可能的损失,在可能时将铋含量降低到很低水平甚至可能是适当的且在经济上是有利的。换言之,浸出时间可以主要根据市场情况,即根据不同铋纯度的浓缩物价值确定。因此,甚至对组成多变的矿石或浓缩物,本发明的方法都能容易而极好地与当代技术或市场要求相适应。
Claims (6)
1.一种预处理具有对进一步加工这类矿石或浓缩物有干扰作用的高铋含量的硫化矿或硫化矿浓缩物的方法,以致能进一步加工这类矿石或浓缩物,回收其所含的有价金属,或至少有助于这种处理,其特征在于,在预定的时间内在同时加热和pH低于1.5的条件下用硫酸浸出该矿石或浓缩物,此后,将该矿石或浓缩物从浸出液中分离,成为铋含量较低而其所含的有价金属富集了的高品位的产品形式。
2.根据权利要求1的方法,其特征在于浸出在pH为0-1的范围进行。
3.根据权利要求1或2的方法,其特征在于在浸出过程中加热以便使温度保持在高于50℃。
4.根据权利要求3的方法,其特征在于在浸出过程中加热以便使温度保持在90℃。
5.根据权利要求1的方法,其特征在于浸出在两个或多个互相按顺序串联的多级浸出设备中进行。
6.根据权利要求1的方法,其特征在于取出浸出渣之后,在通入空气的同时用石灰或石灰石处理浸出液,以便将浸出了的铋和铁以氢氧化物形式与石膏一起沉淀。
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SE9503827A SE505255C2 (sv) | 1995-10-31 | 1995-10-31 | Förfarande för behandling av vismutinnehållande sulfidmalmer eller koncentrat av sådana |
SE9503827-9 | 1995-10-31 |
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EP (1) | EP0862658B1 (zh) |
CN (1) | CN1061382C (zh) |
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CN103397182B (zh) * | 2013-07-05 | 2015-07-15 | 浙江科菲科技股份有限公司 | 一种从单体铋矿中高效回收铋的方法 |
CA2927461C (en) * | 2013-10-21 | 2023-01-03 | Glencore Technology Pty Ltd | Leaching of minerals in the presence of lime and/or limestone and a complexing agent |
CN105420493A (zh) * | 2015-12-28 | 2016-03-23 | 云南云铜锌业股份有限公司 | 一种湿法冶金连续反应釜设备 |
CN109554539A (zh) * | 2018-12-26 | 2019-04-02 | 湖南柿竹园有色金属有限责任公司 | 一种加压酸浸分离铋精矿中铋和铜铁的方法 |
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FR2483463A1 (fr) * | 1980-06-03 | 1981-12-04 | Salsigne Mines Produits Chimiq | Procede pour la recuperation d'or et/ou d'argent et eventuellement de bismuth contenus dans des minerais sulfures et/ou de sulfoarseniures |
US4740243A (en) * | 1984-12-31 | 1988-04-26 | Ensci, Inc. | Metal value recovery from metal sulfide containing ores |
SE9101893L (sv) * | 1991-06-19 | 1992-12-07 | Boliden Mineral Ab | Foerfarande foer behandling av komplexa metallsulfidmaterial |
US5443622A (en) * | 1994-02-28 | 1995-08-22 | Kennecott Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
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DE69612298D1 (de) | 2001-05-03 |
CA2232935C (en) | 2002-02-12 |
EP0862658A1 (en) | 1998-09-09 |
CA2232935A1 (en) | 1997-05-09 |
SE9503827L (sv) | 1997-05-01 |
ATE200109T1 (de) | 2001-04-15 |
CN1200770A (zh) | 1998-12-02 |
AU7512196A (en) | 1997-05-22 |
EP0862658B1 (en) | 2001-03-28 |
RU2136768C1 (ru) | 1999-09-10 |
AU703891B2 (en) | 1999-04-01 |
WO1997016574A1 (en) | 1997-05-09 |
PL325867A1 (en) | 1998-08-17 |
SE9503827D0 (sv) | 1995-10-31 |
PT862658E (pt) | 2001-09-28 |
ES2157464T3 (es) | 2001-08-16 |
DE69612298T2 (de) | 2001-07-05 |
US5961940A (en) | 1999-10-05 |
SE505255C2 (sv) | 1997-07-21 |
GR3035794T3 (en) | 2001-07-31 |
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