摘要
我国滇东南地区拥有丰富的矿产资源,富含锡、银、铟、铅、锌、钨、铜等有价金属,滇东南多金属矿床主要分布在个旧、白牛厂、都龙3个矿区。本论文以云南蒙自白牛厂含锡难处理铅锌硫化矿物为研究对象,全面详细地考察了各种硫化矿物的浮选行为以及锡矿物的浮选性能,在此基础上,对此类矿石的浮选分离流程结构进行了设计,形成了滇东南含锡难处理铅锌矿选矿关键技术,并成功用于生产实践,为矿山实际生产提供理论指导和可行依据。
对白牛厂铅锌硫化矿的硫化矿物方铅矿、铁闪锌矿、磁黄铁矿黄铁矿和毒砂浮选行为进行研究,基本查明了五种矿物浮选行为:丁基黄药、乙硫氮、丁铵黑药、苯胺黑药对五种矿物表现不同的捕收能力,在弱碱性条件下,使用苯胺黑药作捕获收剂,对方铅矿具有良好的选择性能;乙硫氮在高碱条件下对方铅矿捕收能力强,而对其它硫化矿物捕收能力弱;丁铵黑药选择性最差。浮选行为与矿浆电位的关系研究表明:以苯胺黑药为捕收剂,0.05-0.02mV电位区间有利于方铅矿与其它四种硫化矿分离;以乙硫氮为捕收剂,石灰调节矿浆pH=12.0,电位低于0.175V时,方铅矿可以与其它四种硫化矿物分离。应用电化学测试、红外光谱测试、循环伏安法测试等多种现代表面测试技术,研究了矿物在有捕收剂存在条件下的表面氧化机理,探讨了捕收剂与矿物表面的吸附反应和矿物表面生成物的种类。
锡石试验研究表明,水杨羟肟酸对微细粒锡石的捕收效果好,且用量也少,但水杨羟肟酸对石英的捕收能力也很强;选择木质素作石英、方解石抑制剂,此药剂抑制效果明显,对锡石的浮选影响不大。重选分级所有溢流样,经过浓缩脱泥脱硫,通过浮选,锡精矿锡的品位45.71%,锡的回收率73.46%。采用浮选柱,锡精矿的品位可以达到42.68%,回收率82.87%。与浮选机相比,不仅选矿指标好,且工艺流程及药剂制度简单,选矿成本大大降低。重选试验结果表明,白牛厂矿由于含硫高,需脱完硫之后再重选效果比较好,锡精矿的品位和回收率都要高,大部分的硫精矿也得到了回收,有利于资源综合回收。
针对白牛厂矿区主要产出两种不同类型的铅锌硫化矿,一种矿银含量高(100g/t),另一种矿银含量低(65g/t)。开发出了低碱电位调控浮选与高碱电位调控浮选。高碱电位调控浮选是在矿浆pH大于12,矿浆电位在130mV左右,使用黄药与乙硫氮作捕收剂,石灰作pH调整剂,使铅矿物与其它矿物达到浮选分离的目的。高碱流程药剂制度简单,但对于含银高的铅锌矿,使用此方法银的回收率低。使用苯胺黑药与乙硫氮作选铅的捕收剂,硫酸锌与亚硫酸钠作抑制剂,在低碱电位调控下选铅,银的回收率大副度提高。两种生产工艺流程铅锌都获得了较好的生产指标,2010年1-11月份二选厂主要处理含银高白羊段铅锌矿,铅精矿品位达52.62%,铅回收率83.67%,银回收率60.47%;锌精矿品位达44.70%,锌回收率93.59%。三选厂2010年6-11月份主要处理含银低的对门山段铅锌矿,铅精矿品位达56.13%,铅回收率80.15%,银回收率51.12%;锌精矿品位达45.31%,锌回收率91.24%。铅锌精选作业采用浮选柱与浮选机相比,铅精矿品位提高了8%,锌精矿品位提高5%。
通过本论文的研究,更加全面和深刻的了解复杂硫化矿的电化学浮选行为,有助于推动电位调控浮选技术在生产实践中的应用,形成新的多金属复杂铅锌硫化矿浮选分离先进技术。
本研究得到了中南大学产业化基地—蒙自矿冶有限责任公司的大力支持。
Southeast region of Yunnan province has abundant mineral resources, which are rich in tin, silver, indium, lead, zinc, tungsten, copper etc., southeast polymetallic deposits of Yunnan mainly locate in Gejiu, Bainiuchang and Dulong. This thesis studied on refractory lead-zinc mineral containing tin from Mengzi Bainiuchang, Yunnan province, the electrochemical flotation behavior of various sulfides and flotation performance of tin mineral were detailedly investigated. On this basis, flotation separation process of the ore has been designed and forms the key technology of mineral processing of refractoty lead-zinc sulfides containing tin of southeast region of Yunnan. The technology has successfully applied to production practice, providing theoretical guidances and feasible basises for mine practical production.
The flotation behavior of galena, marmatite, pyrrhotite, pyrite and arsenopyrite of Bainiuchang were investigated and ascertained. Butyl xanthate, diethyldithiocarbamate, ammonium butyl aerofloat and aniline aerofloat have different collecting abilities to these five kinds of lead-zinc sulfides. On the weak basic condition, aniline aerofloat as collector has favarable selective performance to galena. On the alkaline condition, diethyldithiocarbamate have better selective performance only to galena, and the selective performance of ammonium butyl aerofloat is worst. The relationship between pulp potential and flotation behavior was studied, the results indicate that aniline aerofloat as collector, potential ranging from0.05mV to0.02mV is propitious to separate galena from the other sulfides. Diethyldithiocarbamate as collector, when lime conditions pulp pH=12.0and potential is lower than0.175V, galena can be separated from the other sulfides. Electrochemical testing, infrared spectroscopy, cyclic voltammetry testing were applied to study the oxidation mechanism of mineral surface in the presence of collector, probe into the adsorption reactions between collector and minaral surface, and their resultants on mineral surface.
Experimental results of cassiterite show that, Benzohydroxamic acid collects micro-fine cassiterite effectively and its dosage is also small, but its collecting ability to quartz is also very strong. Ligninas inhibitor of quartz and calcite has significantly inhibitory effect, and has little effect on the flotation of cassiterite. The overflow sample of classification of gravity separation are deslimed and desulfurized by concentration. By flotation, the grade and recovery of tin concentrate reach45.71%,73.46%, respectively. With flotation collumn, the grade and recovery of tin concentrate reach42.68%,82.87%, respectively. Comparing to flotation machine, not only the mineral processing index is better but also technological process and reagent system are simpler, thus the mineral processing cost reduces greatly. The results of gravity separation indicate that the ore of Bainiuchang need to be desulfurizes before gravity separation due to its high sulfur concentration, therefore, higher grade and recovery of tin concentration can be achieved, sulfur concentration also can be recovered. These are beneficial to comprehensive recovery of resources.
Bainiuchang mainly produces two different types of lead-zinc sulfides, one is with silver concentration of100g/t, the other is with silver concentration of65g/t. Base on these two types, potential-controlled flotations of low base and high-alkali were developed. When pulp pH is greater than12, pulp potential is about130mV, xanthate and diethyldithiocarbamate as collector and lime as regulator of pH, flotation separation of vanadium from other mineral can be achieved. The reagent system of high-alkali process is simple, but to lead-zinc ore, the recovery of silver is slow with this method. Aniline aerofloat and diethyldithiocarbamate as collector, zinc sulfate and sodium sulfite as inhibitor, under the condition of potential-controlled flotations of low base, the recovery of silver is enhanced greatly. Two production processes have gained favorable production targets of lead and zinc. In2010, the second plant mainly processed lead-zinc ore with high concentration of silver, the grade of lead concentrate reached52.62%and its recovery reached83.67%, the recovery of silver reached60.47%; the grade of zinc concentrate reached44.70%and its recovery reached93.59%. In2010, the third plant mainly processed lead-zinc ore with low concentration of silver, the grade of lead concentrate reached56.13%and its recovery reached80.15%, the recovery of silver reached51.12%; the grade of zinc concentrate reached45.31%and its recovery reached91.24%. using flotation collumn instead of flotation machine, the grade of lead concentration increased by8%, the grade of zinc concentration increased by5%.
Through this study, the electrochemical flotation behavior of complex sulphides has been complehensively and profoundly understood, which is helpful to promote the application of potential-controlled flotation and form a new advanced technology of flotation separation of complex poly-metallic lead-zinc sulfides.
This study was strongly supported by industrialization base of Central South University-Mengzi Mining limited liability company
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