CN1267338A - 从硫化物矿石材料中氯化物辅助湿法冶金萃取铜 - Google Patents
从硫化物矿石材料中氯化物辅助湿法冶金萃取铜 Download PDFInfo
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Abstract
一种从硫化物矿石或精矿中萃取铜的方法,它包括下列步骤:在氧气和含卤化物和硫酸根离子的酸溶液的存在下加压氧化矿石或精矿,形成加压氧化的淤浆;对该淤浆进行液/固分离,形成加压氧化的滤液和含不溶的碱式金属矿酸盐的固体残余物;用酸性硫酸盐溶液第二次浸提所述的碱式金属硫酸盐,以溶解所述碱式金属盐,形成溶液中含金属硫酸盐(如硫酸铜)的浸提液和固体残余物;从所述固体残余物中分离所述浸提液;对所述浸提液进行溶剂萃取,形成金属浓缩液和金属萃余液;以及至少将部分萃余液循环至加压氧化步骤。
Description
发明的领域
本发明涉及湿法冶金处理金属矿石或精矿(concentrates)的方法。更具体地说,本发明涉及在卤素离子(如氯离子)的存在下从硫化物矿石或其它精矿中萃取金属(如铜、锌、镍和钴)的方法。
发明的背景
在氯离子的存在下对硫化物精矿进行加压氧化的湿法冶金处理方法是已知的。例如可参见美国专利4,039,406、5,645,708和5,650,057。
本发明的目的是提供一种从硫化物矿石中萃取金属的改进方法。
发明的概述
本发明提供一种从硫化物铜矿石或精矿中萃取铜的方法,它包括下列步骤:在氧气和含卤化物和硫酸根离子的酸溶液的存在下加压氧化矿石或精矿,形成加压氧化的淤浆;对该淤浆进行液/固分离,形成加压氧化的滤液和含不溶的碱式硫酸铜盐的固体残余物;用酸性硫酸盐溶液第二次浸提加压氧化形成的碱式硫酸铜盐,以溶解所述碱式铜盐,形成溶液中含硫酸铜的浸提液和固体残余物;从所述固体残余物中分离所述浸提液;对所述浸提液进行溶剂萃取,形成铜浓缩液和铜废萃余液;以及至少将部分萃余液循环至加压氧化步骤。
在本文中,术语“精矿”指与天然矿石相比,其金属元素含量已被提高至较高的重量百分数的任何材料,它包括人造硫化物矿石(如冰铜(matte))以及作为固体沉淀的金属元素(如氢氧化物和硫化物)。
由下面本发明较好实例的描述可理解本发明的其它目的和优点。
附图简述
图1是本发明一个实例的湿法冶金金属萃取方法的流程图;
图2是本发明另一个实例的湿法冶金金属萃取方法的流程图。
较好实例的详细描述
用于本发明方法的原料矿石或精矿可含有一种或多种碱性金属铜、镍、钴和锌的硫化物矿物,它们通常结合有铁,有时结合有其它元素,如As、Sb和Ag。
在图1中,标号10泛指本发明一个实例的湿法冶金法。方法10包括加压氧化步骤12、大气浸提步骤14、溶剂萃取步骤16、蒸发步骤20和中和步骤22。
在加压氧化步骤12前,先研磨铜精矿,以将粒径降至约2%+325目。
在含硫酸盐、氯化物和最好含铜离子的酸性溶液的存在下,在高压釜中对精矿进行加压氧化步骤12。
加入加压氧化步骤12的酸的量应使得当以连续的方式在pH高于2.0,通常pH为2.3-3.8的条件下进行操作时足以保持(maintain)从高压釜中流出的溶液。
高压釜中溶液中的氯离子浓度应保持在约8-20g/l,较好约12g/l。
加压氧化步骤12是在约115-175℃,较好在约130-155℃的温度下,在约800-2200kPa的压力下进行的。所述压力是氧气压力加上蒸汽压力的总压力。
滞留时间约为0.5-2.5小时,并且该步骤通常是在高压釜中以连续的方式进行的。但是,如有必要,该步骤也可以间歇的方式进行。
在加压氧化步骤12,所有的铜矿物均被转化成碱式硫酸铜CuSO4.2Cu(OH)2,即在加压氧化步骤12,所有要回收的铜均富集在固相。
在反应釜中固体的量保持在约12-25%,即150-300g固体/l,这由热平衡和粘度限制所决定。
高压釜中制得的淤浆通过一组一个或多个闪蒸罐(图中未显示)出料,从而将压力降至大气压力,将温度降至约90-100℃。淤浆的液体部分被称为加压氧化步骤12的产物溶液,并以标号21表示。
如过滤步骤24所示,过滤闪蒸罐中流出的淤浆,彻底洗涤形成的滤饼,以尽可能除去夹杂的产物溶液。
过滤步骤24后,在大气浸提步骤14中在pH约1.2-2.2的条件下处理加压氧化步骤12中形成的固体,使用来自溶剂萃取步骤16的酸性萃余液溶解碱式硫酸铜。浸提步骤14的温度约为40℃,滞留时间约为15-60分钟。加入浸提步骤14的原料中的固体百分含量通常约为3-15%,即约30-170g/l,尽管该步骤可以在超出该范围的条件下进行操作。在浸提步骤14中随着碱式硫酸铜的溶解,固体百分含量显著下降。因此,每升产物中的固体克数比每升原料中的固体克数少一半。
在大气浸提步骤14中,只要小心将pH保持在1.2-2.2,较好保持在pH为1.5-2.0,碱式硫酸铜就几乎完全溶解,并且存在于精矿中的铁很少进入溶液。
来自大气浸提步骤14的淤浆31有时会难以过滤,即便不是不可能,但沉淀良好。由于需要很彻底地清洗浸提的固体,因此将淤浆31泵至逆流倾析(CCD)洗涤步骤(circuit)34中。在CCD步骤34中,将固体通过一系列沉降槽,并反向加入洗涤水。用这种方法,对固体进行洗涤并除去夹杂的溶液和溶解于其中的可溶性金属。需要3-7个沉降槽(图中未显示),洗涤比(水比固体)约为2-5,从而将最终残余物中夹杂的液体减少至溶解的铜含量小于100ppm。
从最后一个沉降槽中流出的淤泥是固体含量约50%的最终残余物流35。可处理这种淤泥以回收贵金属(如金或银),或者作为尾渣。
料流35的主要成分是赤铁矿和元素硫,如果市场条件许可,可用其它方法回收硫,如通过浮选并浸提到特殊的硫溶剂(如全氯亚乙基硫)中。
第一个沉降槽的上清液是产物溶液33,如图所示它被送入溶剂萃取步骤16。
在溶剂萃取步骤16通过两步萃取(图中未显示)从产物溶液33中萃取铜。
如分离步骤38所示,将萃余液37分成三股料流40、41和42。约占2/3萃取液37的料流40如上所述被循环至大气浸提步骤14。料流40的实际体积取决于如上所述浸提步骤14中用于溶解碱式硫酸铜所需的酸并使这种酸稍微过量(即pH 1.5-2.0,相当于约1-5g/l硫酸)的总酸量。料流40所需的酸少于萃余液37所含的总酸量,部分多余的酸用于加压氧化步骤12作为反应的酸来源。这种酸由料流42提供。将萃余液37中未被料流40或42使用的酸视为过量的酸(料流41),它将被中和。通常料流41和42各占萃余液37的约1/6。料流42在中和步骤22被石灰块中和,经液/固分离步骤43后形成石膏,可将该石膏丢弃,并将洗涤水循环至CCD洗涤循环34中作为洗涤水。
来自过滤步骤24的液体21与料流42一起进入蒸发步骤20以除去水,形成更浓的酸和氯化物溶液44,并将其循环至加压氧化步骤12。
由于这种溶液具有很高的腐蚀性,所以在循环前蒸发这种溶液是很成问题的,即蒸发时的高酸度(50g/l游离酸)、高氯化物含量(12g/l)和高温,这些难题使之不能使用大多数(即便不是全部的话)一般通过金属薄壁进行间接传热的市售蒸发器,如通常用不锈钢制成的套管蒸发器。钛较为合适,但是在这种用途中需要较大的用量时它太贵。
但是,这个问题可用直烧蒸发法得到解决,即使用燃料在溶液44中的浸没燃烧并使用钛材料。
为了缩小蒸发器的尺寸并将操作和投资成本降至最小,可将要蒸发的水的量减至最少。为了达到该目的,与没有蒸发的12g/l相比,可将料流31中的铜浓度保持在较高的水准,即约30-50g/l,最好约35g/l。这将形成更浓的酸流42,它含有约48g/l硫酸而非仅含18g/l硫酸。通过将同样量的酸加入较小体积的水中可有效地减少要蒸发的水的体积,从而减小了蒸发器的尺寸,因此适合使用钛并节约直烧蒸发器运行所需的燃料成本。直烧蒸发器不具备产生蒸气的多效性的优点。这种优点一般能降低间接蒸发器中的燃料成本,从而适合蒸发大体积的水。
参见图2,该图显示本发明另一个实例的方法100。
方法100同样包括加压氧化步骤12、大气浸提步骤14、CCD洗涤步骤34、溶剂萃取步骤16、蒸发步骤20和中和步骤22。
在方法100中,除了固体以外,部分要回收的金属元素还富集在加压氧化液21中。如参照图1所示,对所述固体进行大气浸提14。在图2中,给予与图1对应的方法步骤以相同的标号。
对来自过滤步骤24的液体21进行铜溶剂萃取步骤50,以回收铜元素。
应注意,尽管将步骤24称为过滤步骤,但是可使用任何合适的液/固分离方法。
过滤步骤24是用于加压氧化步骤12的高氯化物含量液体(该液体如图所示进行循环)和进入大气浸提步骤14的低氯化物含量或不含卤化物的液体的分离点。过滤步骤24通常是用水、循环的低卤化物含量的水或两者的浓缩物进行洗涤,以尽可能多地从固体(滤饼)中除去卤化物。其目的是将氯化物从高氯化物步骤中传输至低氯化物步骤中的转移量减至最少,阻止氯化物在低氯化物步骤中积聚。
尽管对过滤步骤24制得的固体残余物进行洗涤,但是约0.1重量%的少量氯化物通常会进入大气浸提步骤14。因此,在低氯化物步骤中氯化物的浓度会上升,因为它基本是封闭的步骤,很少与外界交流(bleed)。
这个问题可通过将一股料流从低氯化物步骤循环至高氯化物步骤而得到解决。图2中该料流用标号42表示,以便与图1中的料流42对应,图1中也包括从低氯化物步骤至高氯化物步骤的循环。
如参照图1所示,在循环至加压氧化步骤12之前,料流42也进行蒸发步骤20。但是,在这种情况下,无需从低氯化物步骤循环酸,因为铜溶剂萃取步骤50中以萃余液63的形式产生足量的酸。事实上,通常在循环萃余液63之前,如中和步骤64所示需要中和萃余液63中的部分酸。如分离步骤65所示,对中和产物进行液/固分离,形成可丢弃的固体石膏和液体66,在循环前将其进行蒸发步骤20。
由于无需从低氯化物步骤中循环酸,因此来自溶剂萃取步骤16的萃余液37仅被分成两股料流,即2/3作为用于大气浸提步骤14的料流40,1/3作为料流41,经过中和步骤22和液/固分离步骤43后形成可丢弃的固体石膏及料流45。如分流步骤46所示,料流45被分成作为洗涤水进入CCD步骤34的料流和进入蒸发步骤20的料流42,以进一步循环至加压氧化步骤12。料流42用于使氯化物从低氯化物步骤循环到高氯化物步骤。
尽管本文仅详细描述了本发明较好的实例,但是本发明不受此限制,在所附的权利要求范围内可对其进行改进。
Claims (17)
1.一种从硫化物铜矿石或精矿中萃取铜的方法,它包括下列步骤:
在氧气和含卤化物和硫酸根离子的酸性溶液的存在下加压氧化矿石或精矿,形成加压氧化的淤浆;对该淤浆进行液/固分离,形成加压氧化的滤液和含不溶性碱式硫酸铜盐的固体残余物;
用酸性硫酸盐溶液第二次浸提加压氧化形成的碱式硫酸铜盐,以溶解所述碱式铜盐,形成溶液中含硫酸铜的浸提液和固体残余物;
从所述固体残余物中分离所述浸提液;
对所述浸提液进行溶剂萃取,形成铜浓缩液和铜废萃余液;以及
至少将部分萃余液循环至加压氧化步骤。
2.如权利要求1所述的方法,它还包括在循环前蒸发萃余液以除去水的步骤。
3.如权利要求2所述的方法,其特征在于所述蒸发是用直烧蒸发法进行的,它包括燃料在要循环的萃余液中的浸没燃烧。
4.如权利要求2所述的方法,它还包括将萃余液分成至少两部分的步骤,其中一部分循环至加压氧化步骤,另一部分循环至第二浸提步骤。
5.如权利要求1所述的方法,它还包括将加压氧化滤液循环至加压氧化步骤的步骤。
6.如权利要求5所述的方法,它还包括在循环至加压氧化步骤之前,蒸发加压氧化滤液以除去水的步骤。
7.如权利要求6所述的方法,其特征在于所述蒸发是用直烧蒸发法进行的,它包括燃料在要循环的萃余液中的浸没燃烧。
8.如权利要求5所述的方法,它还包括在循环加压氧化滤液前,对其进行溶剂萃取,以形成另一铜浓缩液和另一铜萃余液,并将该萃余液循环至加压氧化步骤。
9.如权利要求8所述的方法,它还包括在循环至加压氧化步骤之前,对该萃余液进行中和的步骤。
10.如权利要求1所述的方法,其特征在于加压氧化是在pH高于约2的条件下进行的。
11.如权利要求10所述的方法,其特征在于在加压氧化步骤的pH约为2.3-3.8。
12.如权利要求1所述的方法,其特征在于所述第二次浸提是在pH约为1.2-2.2的条件下进行的。
13.如权利要求12所述的方法,其特征在于所述第二次浸提的pH约为1.5-2.0。
14.如权利要求1所述的方法,其特征在于在低于元素硫的熔点的温度下将所述加压氧化淤浆闪蒸至大气压力。
15.如权利要求1所述的方法,其特征在于所述卤化物选自氯化物或溴化物。
16.如权利要求1所述的方法,其特征在于在浸提液中铜浓度保持在约30-50g/l。
17.如权利要求16所述的方法,其特征在于在浸提液中铜浓度保持在约35g/l。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101792864B (zh) * | 2009-11-17 | 2012-06-27 | 灵宝金源矿业股份有限公司 | 一种联产硫酸钙晶须的硫化铜矿高压氧酸浸工艺 |
CN105339511B (zh) * | 2013-06-07 | 2018-01-23 | 奥图泰(芬兰)公司 | 回收铜和贵金属的方法 |
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