金属离子对滑石浮选行为的影响及机理研究

滑石常存在于硫化矿中影响硫化矿浮选精矿的质量。为了解金属离子对滑石浮选行为的影响和作用机制,考察了Ca²⁺、Mg²⁺、Cu²⁺、Fe³⁺对滑石纯矿物浮选、滑石表面ζ电位及滑石与气泡之间诱导时间的影响。结果表明：Ca²⁺、Mg²⁺、Cu²⁺、Fe³⁺均可在滑石表面形成吸附;Ca²⁺对滑石可浮性影响不大;添加Mg²⁺后,当pH＞10时,滑石可浮性降低;添加Cu²⁺后,滑石在pH=4~10范围被抑制,并且在pH值为6左右时Cu²⁺对滑石抑制作用最强;Fe³⁺在pH=3~9的范围内能够抑制滑石,并且在pH值为7左右时对滑石抑制作用最强。溶液化学计算结果表明,溶液中的金属络合离子可以改变滑石的表面电位,而氢氧化物沉淀吸附在滑石表面会降低滑石的可浮性。静电作用能计算结果表明：当pH值低于氢氧化物的零电点时,金属离子形成的氢氧化物沉淀会特定地吸附于滑石表面,产生多相凝聚,导致滑石表面亲水性增强,可浮性降低;当pH值大于氢氧化物的零电点时,凝聚现象减弱,滑石表面疏水性增强,可浮性提高。试验结果对含滑石硫化矿中滑石的抑制和分离有一定的指导作用。     

金属离子对十二烷基磺酸钠浮选蓝晶石的影响

通过单矿物浮选试验,考察了Na+、K+、Ca²⁺、Mg²⁺、Fe³⁺、Al³⁺这6种金属离子在酸性条件下对十二烷基磺酸钠（SDS）浮选蓝晶石的影响,结果表明：一价离子Na+、K+对蓝晶石的浮选基本没有影响;二价离子Ca2+、Mg2+对蓝晶石的浮选有抑制作用,且Ca2+的抑制能力更强;三价离子Fe³⁺、Al³⁺对蓝晶石的浮选有活化作用,且Al3+的活化能力更强。以Ca²⁺和Fe³⁺分别为二价离子和三价离子的代表,通过溶液化学分析了它们的抑制机理和活化机理,结果表明：钙离子在酸性介质中的主要水解组分为Ca²⁺,Ca²⁺易与SDS中的磺酸基形成难溶物,从而使SDS被消耗大量而产生抑制作用;铁离子在酸性条件下对蓝晶石起活化作用的有效水解组分因pH值不同而变化,pH<2.5时FeOH²⁺和Fe(OH)₂⁺是起活化作用的有效水解组分,pH≥2.5时Fe(OH)_3(s)是起活化作用的有效水解组分。     

Determination of the concentrations of calcium and magnesium released from fluid inclusions of sphalerite and quartz

This study investigates the morphology of fluid inclusions trapped within a natural sphalerite and its closely intergrown quartz, and determines the total concentrations of calcium (Ca) and magnesium (Mg) released from the inclusions after grinding. The results indicated that numerous fluid inclusions with sizes from few microns to dozens of microns exist in the sphalerite and quartz. The inclusions contain abundant Ca and Mg. However, the concentrations of Ca and Mg in the inclusions of quartz are significantly lower than those of sphalerite. The inclusions were broken during the grinding process, releasing Ca and Mg to the solution; these released concentrations increased with the increase of grinding time. The maximum concentrations of Ca and Mg released from the fluid inclusions were 61.19 ppm and 5.23 ppm for sphalerite, and 3.28 ppm and 0.21 ppm for quartz, respectively. This study provides new understanding for the source of Ca and Mg in flotation pulp.     

不同价态杂质离子对黄铜矿浮选的影响机理研究

随着淡水资源的匮乏,选矿回水逐渐用于浮选黄铜矿,回水中存在的杂质离子会影响黄铜矿浮选指标。因此,以Na+、Ca2+、Al3+为例,研究不同价态的杂质离子对黄铜矿浮选的影响及其作用机理。试验结果表明:NaCl对黄铜矿可浮性有较强的促进效果,高浓度CaCl2对黄铜矿可浮性有明显抑制作用,而AlCl3对黄铜矿可浮性有一定抑制作用,但影响不显著。黄铜矿表面接触角、Zeta电位及物相图表明:高浓度NaCl阻碍气泡兼并,增加矿浆起泡性,压缩矿物表面双电层,减小气泡到达矿物表面的能量壁垒,促进气泡-颗粒的附着,提高黄铜矿可浮性;CaCl2对黄铜矿浮选的抑制作用是在溶液中形成了亲水的Ca2+羟基络合物(Ca(OH)+),通过很强的亲和力吸附于黄铜矿表面,降低了黄铜矿表面的Zeta电位负值,进而降低其表面疏水性,抑制黄铜矿浮选;AlCl3对黄铜矿浮选的抑制作用主要是因为形成的亲水氢氧化铝沉淀附着于黄铜矿表面,导致黄铜矿表面疏水性减弱,但由于形成沉淀浓度较低,对黄铜矿表面电位和浮选作用有限。     

New source of unavoidable ions in galena flotation pulp: Components released from fluid inclusions

The present work investigated the trace and component release of fluid inclusions in natural pure galena. The investigation results indicated that the composition of the inclusion trace was characterized by a lower Pb content compared to the theoretical composition of galena; nonetheless, these inclusions were rich in lead and chlorine ion. The inclusions were liberated through a grinding process where their compositions were released into solution. It was found that the lead concentrations (C_PbT) released from the inclusions through the grinding process reached 8.25 × 10⁻⁶ mol/L in the experiment with conditions of 2 g galena placed into 40 ml pure deionized water under an inert environment, which was much higher than the C_PbT found through experimental dissolution (1.12 × 10⁻⁶ mol/L). Therefore, it was concluded that the release of Pb from the fluid inclusions in galena was an important new source of the Pb concentration in the solution. This finding sheds new light on the source of unavoidable ions in the flotation pulp. The residual position domain after the release of the inclusions causes the morphology difference in the galena surface composition and roughness. This study provided a new understanding of the unavoidable ion source that is found in the flotation theory and environmental geochemistry.     

Surface morphologies and floatability of sand-blasted quartz particles

Significance of morphological properties of minerals in flotation has been recognized for several decades but sufficient research efforts have not been devoted to this problem. In this study, a special design laboratory scale blasting equipment was used to produce quartz particles with different shapes and roughness values, and develop a new method by which flotation characteristics of quartz particles could be enhanced. For this purpose, micro-flotation experiments were carried out with un-blasted and blasted quartz particles, and the results were correlated with their shape and roughness values analyzed with SEM, BET, and Image analysis methods. The results indicated that the blasted quartz particles with more angular and rougher surfaces gave better floatability compared to the un-blasted quartz particles.     

Towards a new process for the flotation of quartz

Results obtained from flotation experiments performed on three different quartz concentrates demonstrate that quartz can be floated in diluted solutions of hydrofluoric acid (HF) simply by the aid of frothers alone. The recovery was found to be highly dependent on the choice of frother and strongly positively correlated with the concentration of both frother and HF, as well as with the HF conditioning time. Experiments using HNO₃ instead of HF showed no flotation of quartz. Of the five different frothers tested, Brij 58 was found to produce the highest recovery. Good recoveries were also obtained for Dowfroth 400 and Flotanol C07, whereas Dowfroth 200 and MIBC failed to float any quartz. From experiments in which a given feed material were tested at two different particle size distributions it was found that highest recoveries were obtained for the finer feed. Chemical analysis of the floated products showed that these were significantly purer than their corresponding feed materials, and that most of the contaminating elements were concentrated in the sink fraction that remained in the cell. Contact angle measurements corresponded well with flotation recoveries.     

十二胺浮选体系下硅线石和石英的浮选性能

以硅线石反浮选脱硅体系为载体,通过纯矿物浮选试验考察了十二胺对硅线石和石英浮选行为的影响。在十二胺浮选体系中,中性及弱碱性条件下,硅线石和石英的天然可浮性均较好;强酸和强碱性条件下,石英的天然可浮性较好,硅灰石的天然可浮性较差。金属阳离子对纯矿物可浮性影响试验表明:Fe~(3+)和Al~(3+)对硅线石和石英有明显的抑制作用,且在弱碱性条件下抑制作用明显;Ca~(2+)、Mg~(2+)对硅线石和石英可浮性影响较小。调整剂对纯矿物可浮性影响试验结果表明:水玻璃、六偏磷酸钠、淀粉对Al~(3+)或Fe~(3+)作用后硅灰石都有不同程度的抑制作用,柠檬酸对Al~(3+)或Fe~(3+)作用后硅灰石有一定的解抑作用。     

湖南某钾钠长石矿选矿试验

湖南某长石矿矿物组成复杂,主要有用矿物为长石和石英。为开发利用该矿石,对其进行了选矿试验研究。结果表明：在磨矿细度为-0.074 mm占62.36%时,原矿经脱泥-脱石英浮选后,以硫酸为调整剂、N-烷基丙撑二胺+石油磺酸钠为捕收剂经1粗2扫长石-石英分离浮选,获得了Al₂O₃含量为18.68%的长石浮选精矿和SiO2含量为98.35%的石英浮选精矿;长石浮选精矿经1粗1精磁选除铁获得了Al₂O₃含量为18.68%、Fe₂O₃为0.18%、Na₂O+K₂O为12.28%的长石精矿,达到了陶瓷工业的一级质量标准;石英浮选精矿在0.35 T条件下磁选除铁后获得了SiO₂含量为98.35%、Fe₂O₃为0.076%的石英精矿,满足玻璃工业二级质量要求。     

新型阳离子捕收剂DBA-2浮选石英的研究

针对铁矿石反浮选过程中药剂使用时所需矿浆温度高,开发了适合捕收细粒级石英的阳离子捕收剂。通过一系列浮选试验及接触角、Zeta电位和红外光谱检测考察了此阳离子捕收剂对石英的捕收性能和两者的作用机理。结果表明,温度为18℃和p H=9.45时,阳离子捕收剂DBA-2对38μm粒级石英有很高的浮选回收率;在此条件下,对74~38μm粒级石英浮选效果不佳,阳离子捕收剂DBA-2更适用于微细粒铁矿反浮选中应用。接触角测量结果说明,添加DBA-2使石英表面接触角增大,可浮性增强,在20~30°之间,接触角发生的微小变化会对回收率产生巨大影响。Zeta电位测试结果表明,在纯水中石英的零电点为p H=2.26,与DBA-2作用后,零电点偏移至9.47,说明DBA-2在石英表面有吸附作用的发生。通过红外光谱检测分析,DBA-2在石英表面的吸附主要是静电吸附和氢键吸附。     

Geometrical optimization of xanthate collectors with copper ions and their response to flotation

Quantum chemical calculations have been employed to understand the nature of interaction between xanthate and Cu—as part of an ore and Cu—as part of a slag. A semi-empirical parameterized model, (PM3) is used to study ethyl xanthate, propyl xanthate, iso-propyl xanthate, iso-butyl xanthate and amyl xanthate. The total interaction energy, E, is interpreted in terms of the highest occupied molecular orbital (HOMO) energy of the individual collectors with copper ions. The electron density map along with the change in heat of formation, binding energy and dipole-moment, indicate that amyl-xanthate binds to surface of copper ions strongly in comparison to other xanthates. The numerical results obtained with potassium amyl xanthate also support the experimental data on recovery of copper values from a copper ore by flotation.     

Biosorptive flotation of copper ions from dilute solution using BSA-coated bubbles

Copper adsorption was carried out using the novel material known as air-filled emulsion (AFE). AFE is a stable colloidal system containing microscopic protein-coated bubbles (<10 μm) dispersed through an aqueous solution, resulting in an increased specific surface area and contact time between extractant and metal ions. Bovine serum albumen (BSA) generated emulsion concentration had a significant impact on copper removal, with maximum metal uptake obtained at 2.5 g/l of BSA-coated bubbles. It was shown that copper sorption was rapid over the first 10 min, and equilibrium conditions were reached within 40 min. Separation of the copper-loaded microcells from the aqueous solution was also investigated. Micro-flotation was employed to remove the microbubbles by means of attachment to the surface of larger air bubbles. In absence of a cationic surfactant, approximately 0.5% copper recovery was obtained at pH ranging from 5 to 8 due to the lack of hydrophobic groups on the surface of Cu-loaded BSA emulsions. Due to the fine sizes of the emulsion bubbles (<10 μm) a cationic flocculant was used to induce coagulation of the bubbles leading to easier phase separation. A combination of collector and flocculant at a concentration of 3 × 10⁻⁴ M and 0.025 g/l, respectively, led to an increase in copper recovery to nearly 35% at pH 7.     

镁剂在重金属离子脱除方面的应用研究进展

对以氧化镁、氢氧化镁为代表的镁剂在废水中重金属离子脱除方面的应用进展进行了评述,包括含铬废水、含镍废水、含铅废水、含镉废水、含铜铁等工业废水中单一重金属离子的去除以及多种重金属离子的同时脱除,并探讨了其对重金属离子的去除机理,展望了应用前景。     

栗木锡尾矿中云母、长石、石英浮选分离试验

栗木锡矿选矿厂重选尾矿经强磁选脱铁,非磁性物中石英、钠长石、钾长石及云母矿物含量合计达98%,为充分、高效利用该二次资源,进行了浮选分离工艺研究。结果表明,在不磨矿、硫酸调酸的情况下,采用1次云母浮选、1粗3扫3精浮选长石、中矿顺序返回流程处理矿样,获得了K_2O与Na_2O总含量达10.18%、长石矿物含量达90%的长石精矿,SiO_2含量达93.71%、石英矿物含量达85%的石英精矿,以及云母矿物含量达90%的云母精矿。石英精矿、长石精矿、云母精矿品质均满足工业应用要求。探索了一条实现栗木锡矿非金属矿物绿色、高效资源化利用的途径。     

改性木屑对镉铬混合离子的吸附研究

以木屑为原料,经环氧氯丙烷交联,通过与丙烯酰胺接枝,制备出木屑丙烯酰胺接枝黄原酸盐（SCX-g-AM）。用SCX-g-AM处理Cd²⁺和Cr³⁺的混合模拟废水,在Cd²⁺和Cr³⁺浓度均为10 mg/L时,其最适宜的吸附条件为投加量3.33 g/L、pH=7、温度25 ℃、吸附时间30 min,此时Cd²⁺和Cr³⁺的去除率均达95%以上。试验结果能很好地符合准二级动力学模型。     

Flotation of pyrochlore from low grade carbonatite gravity tailings with benzohydroxamic acid

The beneficiation of a low grade niobium tailings by flotation using benzohydroxamic acid (BHA) as a collector and sodium hexametaphosphate (SHMP) as a modifying agent has been studied. A concentrate containing approximately 3% Nb₂O₅ (with an upgrade ratio of 12) was obtained with nearly 80% Nb recovery in 6.5% of the mass after only one rougher flotation stage. After four rougher stages, a final concentrate containing 1.54% Nb₂O₅ with 93% Nb recovery in ∼15% of the mass was obtained. A Box–Behnken experimental design was employed to analyze the effects of collector dose and dispersant dose and pulp temperature and to model the concentrate grade and niobium recovery during rougher–scavenger flotation. The results indicate that temperature has no significant effect on recovery at the 95% or 90% confidence level. Statistical insignificance of the temperature effect has been attributed to the collector mechanism, which essentially does not require BHA species beyond a maximum monolayer capacity that is potentially achievable within the solubility limit at room temperature. SHMP plays an important role in the selective recovery of pyrochlore. Its dispersing function is distinguished from its depressing function in the rougher stages through a positive interaction term together with BHA in both the recovery model and the grade model. The main negative effect of SHMP on niobium recovery emerges in the scavenger stages as a result of depressing action (e.g., targeting primarily the middlings). The effect of reagent dose and temperature on the grade and recovery are presented using 3D graphs from statistical models developed. Negative quadratic terms of the statistical models are discussed in reference to possible overdosing of SHMP on the middlings (involving pyrochlore and gangue) as well as a postulated change of orientation mode of BHA, also due to its overdosing.     

类水滑石/膨润土对水中重金属离子的吸附研究进展

类水滑石、膨润土均为具有特殊层状结构的黏土材料,其中类水滑石具有良好的阴离子交换特性,而膨润土具有良好的阳离子交换特性.近年来这两类材料在水处理方面备受关注.主要概述了类水滑石和膨润土的结构与性质,并着重介绍了类水滑石、膨润土及其改性材料在含重金属离子(如Pb2+、Cd2+、Zn2+、Cu2+及HAsO42-、Cr2 ...     

溶剂萃取富集回收金矿氰化废水中铜氰络合离子的研究

采用三辛基甲基氯化铵(N263)-磷酸三丁酯(TBP)-正辛醇-磺化煤油协同萃取体系从金矿氰化废水中富集和回收有价金属,主要研究了N263与TBP的浓度、振荡时间、水相初始pH、相比(O/A)对铜氰络合离子萃取率的影响及协同萃取反应机制。研究表明,采用N263(20 vol.%)-TBP(15 vol.%)-正辛醇（10 vol.%）-磺化煤油体系在室温,O/A为1:1,pH值为10、混相时间为5min的条件下,废水中铜离子的单级萃取率可达到为98.9%,饱和萃取容量为19576 mg/L。饱和负载有机相经1 mol/L NaOH+5 mol/L NaSCN溶液反萃,在相比（O/A）为2:1的条件下,单级反萃液中Cu离子浓度可达到23000 mg/L,实现了废水中铜氰络合离子的有效富集。萃取过程中铜氰络合离子优先与TBP结合从而失去亲水性,随后再与N263阳离子发生离子缔合反应进入有机相。     

Quantification of Changes in Metal Loading from Storm Runoff,Merse River (Tuscany,Italy)

The Merse River in Tuscany is affected by mine drainage and the weathering of mine wastes along several kilometres of its catchment. The metal loading to the stream was quantified by defining detailed profiles of discharge and concentration, using tracer-dilution and synoptic-sampling techniques. During the course of a field experiment to evaluate metal loading to the Merse, such data were obtained for both storm and pre-storm conditions, providing a unique opportunity for comparison. Iron, Cu, and Mn were chosen to illustrate changes resulting from the storm. The total-recoverable load of Fe increased 21-fold, while loads of Cu and Mn increased by 8- and 7-fold, respectively, during the storm runoff. The increases most likely resulted from flushing particulates from near the stream, resuspension of colloidal material from the streambed, and increased ground-water inflow to the stream. The increases in Cu and Mn loads results from their association with colloids. It is possible that in-stream colloids had relatively more Cu than Mn, while near-stream colloids had relatively more Mn. Each of the metals also increased as a result of increased ground-water discharge during the storm. Despite great increases in load, the filterable concentrations of these metals did not increase substantially, remaining below chronic levels of toxicity.     

高钙高硅铜矿中铜及伴生金银浮选回收试验研究

高钙高硅铜矿中元素铜及伴生金银的回收价值高,但实际生产中这些有价成分的回收指标较低,导致企业经济效益不理想。针对矿石性质,采用石灰和硫化钠为矿浆调整剂,丁基黄药与丁基铵黑药联合使用作为捕收剂,在磨矿细度-74μm粒级含量占70%的基础上,进行了浮选药剂优化和闭路试验。在石灰用量1 000g/t、硫化钠用量400g/t、丁基黄药用量400g/t、丁基铵黑药用量50g/t、松醇油用量84g/t的药剂制度下,采用两次粗选、两次精选、一次扫选、中矿顺序返回的浮选闭路流程,最终获得Cu品位21.45%、回收率90.46%,Au品位7.92g/t、回收率79.39%,Ag品位453.50g/t、回收率81.82%的铜精矿。与生产现场指标相比,不仅提高了矿石中铜的浮选回收率,而且极大地提高了矿石中伴生金银的回收效果,浮选指标较为理想。