1、中图分类号:TD95Copper-zinc mixing-re-smelting desulfurization and separation of copper and zinc from high-sulfur copper-zinc ore WU Ji-zong1, XIE Hai-yun1*,TIAN Xiao-song2,XIAO Wei2 ,LIU Rong-xin1, GAO Li-kun1, TONG Xiong1(1.Faculty of Land Resource Engineering; Kunming University of Science and Technolo
2、gy, Kunming 650093, China2.Yunnan Diqing Mining Development Co.Ltd., Diqing, 674500, China)Abstract: The mixed flotation of high sulfur copper zinc ores has the advantages of high recovery and low cost, but the separation of copper-zinc-sulfur from the mixed coarse concentrate has been the key and d
3、ifficult point of metal dressing. This paper, aiming at the high sulfur copper zinc ore in Simao area of Yunnan province , it contain Cu3.03%, Zn3.90% and S27.44%, Full mixed flotation-regrinding desulfurization-copper zinc separation process was used in this study, and the influence of regrinding f
4、ineness, dosage of reagents and other factors on the separation of mixed flotation and copper-zinc-sulphur separation were analyzed. The flotation tailings of mixed flotation were 37.61%, the recovery rates of Cu, Zinc, and S were 96.34%, 98.37%, and 98.87% respectively in mixed coarse concentrate.
5、When the desulphurization of coarse concentrate regrind fineness is -38m 90%, the sulfur iron concentrate contained 45.74% S and S recovery rate was 74.43%. Copper-zinc separation closed-circuit test obtained copper concentrate containing Cu 24.01%, Cu recovery rate was 86.76%, zinc concentrate cont
6、aining Zn52.30%, Zn recovery rate was 87.12% It is shown that the minerals separation can be realized by the process of for the high sulfur copper-zinc ores.Keywords:copper-zinc sulfide ore; mixed flotation;desulfurization;copper-zinc separation分类号:引言我国有丰富的铜锌硫化矿资源,多具有嵌布粒度较细,各矿物连生包裹复杂等特点,导致浮选过程中各矿物分离
7、不彻底,且指标不稳定 1、2。对铜多金属矿可采用优先浮选或混合浮选流程。优先浮选要求给矿中目的矿物单体解离,即浮选前要直接细磨,缺点是入磨矿量大、磨矿成本高,且浮选过程中易出现泥化现象,恶化目的矿物间的分离效果3、4;与优先浮选相比,混合浮选可在较粗粒度下大量抛尾并产出混合精矿,大幅减少后续作业的矿量,降低磨矿及浮选作业成本5、6,但需解决混合精矿中铜、锌、硫高效分离的问题。云南思茅地区有大量难选铜锌硫化矿资源,其含硫量高,且铜锌矿物多呈微细粒浸染状与黄铁矿紧密嵌布7、8。与细磨后优先浮选相比,对其在粗磨条件下进行混合浮选,以硫化物集合体形式产出混合粗精矿后再进一步进行分离,具有成本低和回收率
8、高的双重优势。本文针对云南思茅地区高硫铜锌矿,采用“混合浮选-再磨脱硫-铜锌分离”工艺,进行较为系统的试验研究,目的是对类似微细粒嵌布型高硫铜锌矿的混合浮选、脱硫及混合精矿分离等方面提供一定的研究基础。1.材料和方法1.1矿样高硫铜锌矿取自云南思茅,其主要化学成分见表1,铜物相和锌物相分析分别见表2和表3。表1高硫铜锌矿多元素分析结果Tab.1 Multi-element analysis results of high-sulfur copper-zinc ore 组 分CuZnPbSFe2O3SiO2Al2O3CaOMgOAsAg*含量%3.033.900.1327.4422.986.22
9、5.061.173.590.1534.50注:*单位为g/t表2铜物相分析Tab. 2 Copper phase analysis结合铜%游离铜%次生铜%原生铜%总计%分布率(%)结合铜游离铜次生铜原生铜总铜0.0020.020.043.090.070.681.2697.99100.00表3 锌物相分析Tab.3 Zinc phase analysis硫酸锌%锌氧化物%硫化锌%硫酸锌锌氧化物硫化锌总锌0.143.914.080.543.53495.93从表1中结果可见,该高硫铜锌矿主要含Cu 3.03%、Zn 3.90%、Pb 0.13%,S含量为 27.44%,含Fe2O322.98%,含A
10、g 34.50g/t,有价元素主要为铜、锌、铅、硫、铁和银,且铜、锌和硫含量高。表2和表3的物相分析表明,铜主要以硫化铜存在,锌主要以硫化锌存在且氧化程度低。高硫铜锌矿中金属矿物主要为黄铜矿、闪锌矿、黄铁矿和方铅矿,非金属矿物主要为绿泥石、长石、石英等,铜矿物、锌矿物和硫矿物为主要回收目的矿物。1.2试验方法试验采用XMQ- 24090mm锥型球磨机进行磨矿,1.0L和1.5L XFD型单槽浮选机进行浮选,使用的浮选药剂主要有乙基黄药、丁基黄药、石灰、硫酸铜、硫酸锌、亚硫酸钠和松醇油。2 结果与讨论2.1 铜锌硫硫化矿浮选分离原理针对所研究的高硫铜锌矿,本论文采用“全浮选-再磨脱硫-铜锌分离”
11、工艺。原矿粗磨后用乙基黄药与丁基黄药浮选得到混合粗精矿,混合粗精矿再磨并添加石灰作为黄铁矿的抑制剂实现脱硫,铜锌分离采用抑锌浮铜工艺,硫酸锌和亚硫酸钠组合抑制闪锌矿,最后用硫酸铜活化闪锌矿。混合浮选时,黄药与硫化矿表面作用形成黄原酸盐或双黄药吸附于矿物表面,使硫化矿产生良好的可浮性后得以泡沫富集10-12;脱硫过程在石灰产生的高碱度条件下进行,黄铁矿表面易于被氧化生成Fe(OH)3和、Ca(OH)2和CaSO4等亲水性物质,使其可浮性大幅降低而被抑制13、14;铜锌分离时加入Na2SO3和ZnSO4,ZnSO4水解出与矿浆中的Fe2+生成亲水碱式硫酸铁,该物质易在闪锌矿表面发生沉积而使闪锌矿受
12、到抑制,加入Na2SO3后闪锌矿表面上的疏水薄膜被脱除,促进锌亲水性羟基化合物的形成,以上药剂共同作用使闪锌矿被抑制15、16。最后加入硫酸铜,在闪锌矿表面生成一系列铜的硫化合物活化组分,防止闪锌矿被过度氧化,从而被活化。2.2混合浮选磨矿细度试验对高硫铜锌矿首先采用“粗磨混合浮选”流程,着重考察磨矿细度对混合浮选效率的影响。试验流程和结果分别见图1和图2。图1 铜锌硫混合浮选试验流程Fig.1 Copper and zinc-sulfur mixed flotation test flow图2 磨矿细度对混合浮选的影响Fig.2 Effect of grinding fineness on
13、mixed flotation由图2结果可见,当磨矿细度为-74m 65%时混合浮选的综合指标较好。混合粗精矿中Cu品位4.25%,Cu回收率83.24%,Zn品位5.64%,Zn回收率86.99%。2.3混合浮选综合试验在磨矿细度试验结果的基础上,采用一粗一扫流程进行混合浮选,试验流程和结果分别见图3和表4。图3混合浮选综合试验流程Fig. 3 Mixed flotation comprehensive test process表4混合浮选综合试验结果Tab. 4 Mixed flotation comprehensive test results样品名称产率(%)品位(%)回收率(%)混合粗精矿63.29 4.82 6.18 42.85 97.54 98.34 98.84 尾矿36.71 0.21 0.18 0.87 2.46 1.66 1.16 原矿100.00 3.13 3.98 27.44 10
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