【作者】 刘润清；

【导师】 王淀佐； 胡岳华；

【作者基本信息】 中南大学 ， 矿物加工工程， 2010， 博士

【摘要】 铜、铅、锌作为关系国计民生的主要金属矿产品,可用于工农业生产的诸多领域。随着经济的发展,铜、铅、锌矿产资源得到大规模开采利用,使得资源量日益紧缺,矿石的处理难度日益加大,尤其是铜铅、铜锌矿物的浮选分离更加困难；同时,人们开始对环境保护、资源利用和降低能源消耗越来越重视。为此,开发低成本、高效的药剂,实现复杂多金属矿的有效分离有着非常重要的意义。本文以工业废液杂醇油和纸浆废液为原料合成了捕收剂杂醇黄药和抑制剂LSC、FCLS,并通过浮选实验、红外光谱分析、吸附量测定、动电位测试以及电化学测试,考察了黄铜矿、黄铁矿、方铅矿和铁闪锌矿在不同捕收剂和抑制剂体系中的浮选行为及作用机理。浮选试验结果表明：丁黄药作捕收剂时,在pH 2～10的范围内,四种矿物均具有良好的可浮性；杂醇黄药作捕收剂时,四种矿物也均具有良好的可浮性。LSC作抑制剂时,在pH 2～12范围内,黄铁矿受到强烈的抑制,黄铜矿的浮选几乎不受影响,方铅矿和铁闪锌矿受到微弱的抑制,说明LSC可以选择性抑制黄铁矿。FCLS作抑制剂时,在整个实验pH范围内,方铅矿和铁闪锌矿都受到强烈的抑制；pH〈3时,FCLS对黄铜矿和黄铁矿有很好的抑制效果,当pH>3, FCLS抑制能力较弱,FCLS对黄铜矿和黄铁矿的抑制能力随pH的增大有所降低。丁黄药作捕收剂,FCLS作抑制剂时,在较低的矿浆电位下黄铜矿和黄铁矿的可浮性较好,而方铅矿和铁闪锌矿的可浮性在实验矿浆电位范围内都很差,说明在较低的矿浆电位下可能实现黄铜矿、黄铁矿与方铅矿和铁闪锌矿的分离。采用杂醇黄药浮选平江铜铅锌矿石,与丁黄药相比发现,杂醇黄药对铅的捕收能力强于丁黄药,但对铜的捕收能力弱于丁黄药。FCLS与重铬酸钾相比,对铜铅分离效果好,并且对环境几乎没有影响,因此可以代替重铬酸钾实现铜铅分离。丁黄药在四种矿物表面的吸附发生在较宽的pH范围；LSC和FCLS在矿物表面吸附量的趋势与矿物浮选行为一致；FCLS在四种矿物表面吸附量大小顺序为：铁闪锌矿>方钳矿>黄铁矿>黄铜矿。ζ-电位测定表明,黄药的加入使矿物表而ζ-电位更负,表明黄药在矿物表而发生了吸附；LSC和FCLS的加入,矿物表面电位进一步降低,说明这两种药剂也在矿物表而发生了吸附。红外光谱分析发现,黄铁矿与黄药作用,表面疏水产物为双黄药,黄铜矿、方铅矿和铜活化的铁闪锌矿与黄药作用,表面产物为黄原酸盐；黄铜矿、黄铁矿和方铅矿与LSC作用后,矿物表面出现明显的LSC吸收峰,说明LSC在矿物表面发生了吸附；矿物与黄药及LSC混合药剂作用后,LSC与黄药在矿物表面出现竞争吸附。黄药在黄铜矿表面的吸附强于LSC,而在黄铁矿和方铅矿、铁闪锌矿表面,LSC吸附强于黄药。黄铜矿、黄铁矿与黄药和FCLS混合药剂作用后,黄原酸铜和双黄药特征峰仍然存在,出现微弱的FCLS特征峰。方铅矿和铁闪锌矿与黄药和FCLS混合药剂作用后,黄原酸盐特征峰明显减弱,并且出现明显的FCLS特征峰,说明FCLS与黄药之间存在竞争吸附,FCLS对矿物的抑制是通过阻止捕收剂在其表面吸附。XPS结果表明,与FCLS作用后,方铅矿表面Pb和S存在的化合态没有发生改变,但是峰的强度明显减弱,FCLS在方铅矿表面发生罩盖。黄铜矿与FCLS作用后,表面铜和铁的化合态也没有发生改变,峰的强度略有降低,说明FCLS在黄铜矿表面吸附较弱。循环伏安曲线研究表明,黄铜矿与FCLS作用后,黄铜矿氧化还原峰位置没有发生变化,氧化电流有所降低,说明FCLS在黄铜矿表面发生罩盖使得其表面电阻增大。黄药与FCLS同时存在时,黄铜矿优先与丁黄药发生电化学反应,因此,FCLS存在时,黄铜矿仍然可浮。FCLS与方铅矿作用后,方铅矿表面氧化还原反应没有发生变化,FCLS的抑制作用可归因于其化学吸附。黄铁矿与LSC及丁黄药作用的循环伏安曲线表明,无论是在LSC溶液中,还是在LSC和BX的混合溶液,黄铁矿伏安曲线几乎重合,表明有LSC存在时,捕收剂和黄铁矿表面的电化学反应不能发生,LSC与黄铁矿优先发生电化学反应。极化曲线研究表明,FCLS的存在对方铅矿表面电化学反应类型没有影响,只是改变其反应电流。FCLS对方铅矿的抑制作用是由于FCLS在方铅矿表面罩盖所致。更多还原

【Abstract】 Copper, lead and zinc, as main mentallic minerals, can be used for industrial and agricultural fields. With the development of economy, the extensive exploitation and utilization of copper, lead and zinc mineral resources cause the shortage of resource, which increase the difficulty to separate the minerals, especially the separation of copper-lead, copper-zinc minerals. Simultaneously, the enviromental protection and the reduction of energy consumption have being drawn much more attention. Consequently, it is very important to exploit low-cost and high performance reagents to effectively separate complex polymetallic mineral. In this study, fusel xanthate collector and lignosulfonate calcium (LSC), ferric chromium lignin sulfonate (FCLS) depressants were synthesized from fusel oil and paper pulp effluent. Flotation behavior and mechanism of chalcopyrite, pyrite, galena and marmatite in the presence of different collectors and depressants have been studied based on flotation tests, FTIR analysis, adsorption measurements, X-ray Photoelectron Spectroscopy (xps) and electro-chemical measurements.Flotation results showed that chalcopyrite, pyrite, galena and marmatite exhibited very good flotation response in pH 2-10 range by using butyl xanthate, fusel xanthate as collector and remained good floatable. Chalcopyrite exhibited good floatability while pyrite was inhibited extensively in pH 2～12 using LSC as a depressant, galena and marmatite were slightly inhibit, indicated that LSC has selectively depress for pyrite. The float of galena and marmatite were intensively restrained in wider pH range when FCLS used as depressant, chalcopyrite and pyrite was slightly depressed in a wide pH region and its recovery increased as the pH increased, indicated FCLS could be used to separate the chalcopyrite-galena and chalcopyrite-marmatite. The floatability of chalcopyrite and pyrite is better at lower pulp potential, while the floatability of galena and marmatite is very poor in wider potential range. It indicates that the flotation separation of chalcopyrite, pyrite from galena and marmatite may be possible at lower pulp potential.Batch flotation tests for Pingjiang copper-lead-zinc ore have been conducted. The results showed that in contrast to butyl-xanthate, flotation by fusel xanthate have better collecting capability for lead, but for copper was reverse. It is better for FCLS to seperate copper from lead than potassium dichromate, and it have hardly influence on environment. So FCLS can replace potassium dichromate to separate copper and lead.The adsorption of butyl xanthate on chalcopyrite, pyrite, galena and marmatite can take place in winder pH region. The adsorption of LSC and FCLS on minerals surface is corresponding to their flotation behavior. The adsorption density of FCLS on four sulfides minerals surface decreased according to the following order:marmatite>galena>pyrite> chalcopyrite. Zeat potential measurements showed that the addition of xanthate and LSC, FCLS make the zeta potential of minerals more negative indicated the adsorption of the collector and depressant on those four sulfide minerals.The formation of dixanthogen for BX has been observed on pyrite by FTIR. Xanthogenate is formed after the interaction of xanthate with chalcopyrite, galena and marmatite activated by copper ion. While obvious absorption peak of LSC appears on the surfaces of chalcopyrite, pyrite and galena interacted with LSC, which indicates that adsorption takes place on the surface of these minerals when interacted with LSC. Competitive adsorption emerges on the surfaces of minerals when interacted with the mixture of xanthate and LSC. The adsorption of xanthate is stronger than that of LSC on the surface of chalcopyrite, while the case is opposite on the surfaces of pyrite, galena and marmatite. When chalcopyrite, pyrite interacted with the mixture of xanthate and FCLS, characteristic peaks of xanthated cupric and dixanthogen still exit but that of FCLS does not. There is evident characteristic peaks of FCLS while characteristic peaks of xanthogenate become weaken when galena and marmatite were interacted with the mixture of xanthate and FCLS, which shows that FCLS and xanthate interactes with minerals by competitive adsorption.The XPS results shows that compounds of Pb and S on the surface of galena do not changes after interacted with FCLS, but the intensity of adsorption peak decreases sharply because of the covering produced when FCLS interacts on the surface of galena. When chalcopyrite interacted with FCLS, the compounds of Cu and Fe do not change also but the peak intensity decreased a little, which indicates the adsorption of FCLS on the surface of chalcopyrite is weak.Cyclic voltamnogram measurements showed that the postions of redox peaks don’t change and the current of oxidation is reduced. This indicates that FCLS covering on the surface of chalcopyrite leads to the increase of its surface resistence. When xanthates and FCLS coexist, chalcopyrite interacts with xanthate electrochemically in advance to FCLS. So chalcopyrite is still floatable even with FCLS. The surface redox reactions of galena don’t change when FCLS interacted with galena, the inhibition of FCLS can be arributed to its chemical adsorption.The polarization curves show that FCLS has no influence on electrochemical reaction type of surface of galena but change its current. The inhibition of FCLS to galena is due to FCLS covering over galena surface.更多还原