Temperature sensitive polymers as efficient and selective flotation collectors

This study investigates both the efficacy and selectivity temperature responsive of poly(N-isopropylacrylamide) PNIPAM as a flotation collector. The results of this study showed that charged poly(N-isopropylacrylamide) polymers selectively increased both the probability particle/bubble attachment as well as the floatability of coarse alumina and quartz particles respectively. These results provide a basis for considering PNIPAM as both an effective and selective collector in a flotation system. Coupled with previous studies that demonstrate the efficacy of PNIPAM as a flocculant in mineral suspensions, these results clearly demonstrate the potential use of PNIPAM as a dual function reagent which acts as both selective flotation collector and flocculant in the flotation of ultrafine particles.     

Flocculation/flotation of hematite fines with anionic temperature-responsive polymer acting as a selective flocculant and collector

A novel approach to the recovery of valuable fines is the use of temperature-responsive polymers such as poly (N-isopropyl acrylamide) (PNIPAM). These polymers act as dual-function flocculants and collectors to form hydrophobic aggregates improving particle–bubble collision and attachment. The aim of this study is to investigate the flotation performance of anionic PNIPAM for an iron ore sample containing fines compared to sodium oleate, an industrial collector for hematite. PNIPAM conditioned at room temperature (25 °C, below the lower critical solution temperature (LCST)) and floated at 50 °C (above the LCST) was found to provide improved hematite grade and recoveries for particles above 20 μm, compared to sodium oleate. This was attributed to the increased selectivity and hydrophobicity of PNIPAM. Turbidity testing confirmed the flocculation of fines with PNIPAM, which deslimes the surface of the coarser particles. Below 20 μm, the hematite fines were almost completely recovered with PNIPAM. However, this recovery was not selective, attributed to the entrapment of gangue in the hydrophobic aggregates. Furthermore, conditioning of the polymer above the LCST resulted in significant losses in grade and selectivity, as the polymer self-aggregates hydrophobically and precipitates unselectively onto the closest surface.     

Influence of liberation on bubble–particle attachment time in flotation

Flotation is controlled by the bubble–particle attachment mechanism which depends on the particle surface properties i.e., the particle composition, the surface liberation of valuable minerals and collector adsorption. This paper focuses on using the bubble–particle attachment method to understand the factors affecting attachment time. The attachment time measurements were performed with sized concentrates obtained by flotation of a copper sulphide ore (Northparkes Mine, Australia) in a mechanically agitated batch flotation cell. Quantitative mineral liberation analysis was used to determine the mineralogy of flotation concentrates. The results showed that the higher the amount of highly and moderately liberated copper minerals in flotation concentrates, the lower the attachment time. By using attachment time and collector dosage, we defined a non-linear empirical correlation to estimate Cu grade. The proposed empirical correlation has shown a satisfactory agreement between the calculated and the experimental Cu grade. These results showed that attachment time measurements are related to the Cu grade. This relationship may be used in the future to develop a practical method (without assays) to monitor changing grade for a specified system (flotation plant). It also may be possible to infer potential grade if mineralogy samples are available, but not enough samples are available for conventional flotation tests. However this requires a significant amount of further work.     

颗粒气泡黏附科学——宏观尺度下颗粒气泡黏附研究进展及困境

颗粒气泡黏附指从颗粒与气泡相遇开始到液膜发生薄化破裂最后至三相润湿周边铺展形成稳定矿化气絮体的过程,是浮选中的核心作用单元。然而浮选颗粒气泡黏附机理至今仍不明确。黏附过程主要受颗粒气泡的表面物理化学性质及溶液化学条件影响,表面力及流体作用力协同支配微纳尺度下颗粒气泡间液膜薄化破裂行为。排液过程中气液界面的变形效应进一步增加了系统复杂性,上述因素使得颗粒气泡黏附的理论研究及试验探索步履维艰。早期关于颗粒气泡黏附的研究主要聚焦于黏附概率,其中宏观尺度下的诱导时间测试占据主导地位,通过诱导时间结果计算黏附概率。对国内外宏观尺度下颗粒气泡黏附概率模型及研究技术手段进展展开全面综述,并对现有技术瓶颈及局限进行分析。诱导时间测量仪及高速动态摄影技术大大促进了浮选工作者对颗粒气泡黏附的理解,“诱导时间与实际浮选回收率具有着良好的相关关系”也已经被广泛证明。然而因微纳尺度下的表面力及液膜薄化动力学信息的缺失导致宏观诱导时间并不能从基础层面揭示颗粒气泡的黏附机理,微纳尺度下颗粒气泡间相互作用力及液膜薄化动力学的定量测试表征是技术发展的必然趋势,其可为浮选微观矿化反应过程提供新的理论视角,同时也为难浮煤及难选矿浮选过程强化提供理论支撑。     

Interaction mechanism of miscible DDA–Kerosene and fine quartz and its effect on the reverse flotation of magnetic separation concentrate

In this study, a modification of oil assisted flotation processes of quartz particles has been proposed, which is based on introduction of miscible Dodecylamine (DDA)-Kerosene as collector with DDA cationic surfactant coated on kerosene to the hydrophilic quartz particles in the pulp. The property of miscible DDA–Kerosene emulsion was investigated. Due to the adsorption of DDA at kerosene/water interface, a smaller and uniform kerosene emulsion formed. Addition of cationic surfactant to the kerosene emulsion changed the zeta potential value from negative to positive, which resulted in enhancing the adhesion of the oil droplets to negatively charged quartz. The results showed that agglomeration and flotation process can be realized simultaneously with DDA–Kerosene. The agglomeration of fine quartz minerals in the presence of miscible DDA–Kerosene led to the formation of very large compact agglomerates resulting in increasing hydrophobicity of the particles and inducing a higher probability of collision and adhesion to air bubble. Experimental data indicated that miscible DDA–Kerosene had better selectivity and stronger collectability to quartz than DDA–HCl, which can be used as an efficient collector in the reverse flotation of magnetic separation concentrate of TISCO. At the same DDA dosage (60 g/t), separation efficiency got to 18.53% when using DDA–HCl as collector; while a better result was obtained with DDA–Kerosene, the efficiency of separation reached 59.07% which was identical with 120 g/t DDA–HCl.     

Fundamental aspects of bubble–particle attachment mechanism in flotation separation

Analysis of bubble–particle mechanism is important for improving our understanding of flotation process. The research presented integrates microflotation experiments, bubble–particle attachment time measurements, and colloid and surface characterization and analysis. The bubble–particle attachment time was inversely related to the flotation recovery and the minimum attachment time matched the maximum flotation recovery, which occurred around mutual isoelectric point for the glass particles and air bubbles. Bubble–particle force measurements, performed with an Atomic Force Microscope (AFM), showed a similar trend. Additionally, the adsorption isotherm of the glass–dodecyl amine hydrochloride (DAH) system indicated that there are the three adsorption regions, and the flotation recovery reached its maximum value in the second region of DAH adsorption on the glass surface. All results obtained in this study showed the important role of colloidal forces affected by surfactant adsorption in bubble–particle attachment.     

Application of reactive oily bubbles to bastnaesite flotation

Reactive oily bubble, defined as air bubbles covered with a thin layer of kerosene containing collectors, was used to float a major rare earth mineral, bastnaesite from rare earth ores. Both fatty acid and hydroxamic acid were used to generate reactive oily bubbles. The flotation of bastnaesite with reactive oily bubble was investigated by zeta potential, zeta potential distribution and induction time measurement and micro-flotation tests. The results showed a quicker attachment to bastnaesite and a stronger collecting power of reactive oily bubbles containing 100 ppm fatty acid than conventional air bubbles, resulting in an enhanced bastnaesite recovery. The flotation recovery of bastnaesite by reactive oily bubbles containing hydroxamic acid is lower than that by conventional air bubble flotation where the bastnaesite was pre-conditioned by hydroxamic acid in aqueous phase. During induction time measurement, no attachment is observed between bastnaesite particles and reactive oily bubbles containing hydroxamic acid, illustrating the importance of collector type in reactive oily bubble flotation technology. These findings suggest the superior performance of reactive oily bubble technique than conventional bastnaesite flotation method only when proper collector is used to generate the reactive oily bubbles.     

浮选法对非晶微硅粉提纯效果的研究

为确定效果最优的纳米石英浮选工艺条件,采用浮选法对微硅粉分离提纯,考察了捕收剂用量、不同金属阳离子活化剂种类、矿浆pH值、搅拌强度、引入纳米气泡等条件对纳米石英提纯效果的影响.结果表明:在浮选机转速为2 000 r/min、矿浆pH值为12、捕收剂(油酸钠)用量为1.5g/L、活化剂(CaCl2)用量为5×10-3mo...     

Surface chemistry features in the flotation of KCl

Despite the successful industrial practice to recover KCl by flotation, the adsorption state of collectors at KCl salt surfaces is still not fully understood. In this paper, the flotation behavior of KCl and NaCl using different collectors and captive bubble contact angle measurements at KCl and NaCl crystal surfaces in their saturated solutions are reported. The influence of collector concentration and collector structure is considered. The results show that both cationic and anionic collectors produce a hydrophobic state at the structure breaking KCl salt surface, with finite contact angle values of between 30° and 60°. In contrast, the contact angle at the structure making NaCl salt surface is zero at all collector concentrations, suggesting that no collector adsorption occurs, a supposition that is supported by results from molecular dynamics simulation (MDS). Further, it appears that the presence of surface defects such as edges and corners promote the adsorption of collectors at the KCl surface, and that the flotation is achieved by bubble attachment at the edges/corners of KCl particles with the formation of aeroflocs.     

Fundamental study of reactive oily-bubble flotation

A novel concept of reactive oily bubbles (i.e., bubbles covered by a thin layer of oil containing oil-soluble collectors) as a carrier in flotation is proposed. In addition to the role of fine particle agglomeration by oily films, the surface properties of air bubbles coated with a thin oil film can be better controlled for the desired selectivity by adding certain types and concentrations of water insoluble collectors into the oil phase. Oily bubbles attain a much higher contact angle than air bubbles, ensuring a strong collecting power, favorably for floating both coarse and fine particles. The reactive oily bubble flotation can eliminate the addition of collector to the aqueous phase, avoid undesired synergetic interactions among collectors, activators, depressants and dispersants present in slurry, minimize undesired activation of gangue particles and significantly reduce the amount of collectors needed.The electrokinetics of kerosene droplets in aqueous collector solutions was measured as a function of solution pH. The results clearly showed that the surface charge and hence the surface properties of oil droplets can be finely tuned by controlling the type of the collectors to suit the desired flotation needs. The attachment of collector-containing oily bubbles on silica, sphalerite and galena surfaces was investigated with contact angle measurement. The concept of using reactive oily bubble to achieve selective flotation was demonstrated in microflotation tests.     

CFD modelling of bubble–particle collision rates and efficiencies in a flotation cell

Computational fluid dynamic (CFD) modelling of a Denver-type flotation cell has been performed. Bubble–particle collision rates in different parts of the cell have been calculated from the local turbulent velocities, and the size and number concentrations of bubbles and particles obtained from CFD modelling. The probability of collision due to streamline effect of fine particles moving around the bubble has also been estimated. The local attachment rate based on the collision rate and collision probability is then calculated and found to decrease as particle size decreases. This is consistent with the decrease in flotation recovery of fine particles as observed in flotation practice. The magnitudes of the collection rate constants obtained from CFD modelling indicate that transport rates of the bubble–particle aggregates to the froth layer may contribute quite significantly to the overall flotation rate in plant-scale equipment.     

EDTA在铌铁矿和石英浮选分离中的选择性抑制作用机理

由于石英容易被金属阳离子活化,导致羟肟酸捕收剂浮选体系下铌矿物和脉石矿物石英的可浮性差异减小,增加了有用矿物和石英之间的分选难度。采用EDTA作为铌铁矿浮选中的石英抑制剂,通过单矿物试验、人工混合矿浮选试验、Zeta电位测试、接触角测试以及X射线光电子能谱仪检测等研究了铌铁矿以及石英的浮选行为和表面性质。当使用辛基羟肟酸(OHA)作为浮选捕收剂时,EDTA对活化后石英有较强的选择性抑制作用,因为EDTA对石英表面金属离子的络合溶解作用减少了OHA在石英表面的吸附,从而实现了铌铁矿和石英的有效分选。浮选试验结果表明,针对铌铁矿和石英质量比为1∶1的人工混合矿,在FeCl₃·6H₂O浓度为20 mg/L、EDTA用量为0.2 mmol/L、矿浆pH值为9.0、OHA浓度为0.05 mmol/L的条件下,可较好地实现铌铁矿和石英的浮选分离,铌铁矿精矿中Nb₂O₅的品位为56.84%,Nb₂O₅的回收率为72.54%,石英的品位为13.17%,石英的回收率为12....     

炼焦中煤的尺度效应及对浮选的影响

为了考察煤泥粒度变细对浮选效果的影响,从不同细度颗粒的几何特征、润湿热及浮选行为3方面探讨了炼焦中煤的尺度效应。使用BET比表面测定仪、微量热仪分别研究了炼焦中煤粒度减小对其比表面积、总孔容和平均孔径及润湿热的影响,用Young-Laplace方程分析了基于毛细管作用捕收剂吸附的变化,通过半经验公式计算了颗粒粒径及润湿性对上浮概率的影响,并进行了不同细度超低灰精煤的浮选试验。研究表明,随着炼焦中煤粒度的变细,其比表面积和总孔容呈数倍增大,Ⅱ类孔增多,平均孔径增加;基于毛细管作用的捕收剂吸附增强,对去离子水的润湿热值急剧降低;存在最佳粒度范围使颗粒的上浮概率最大,中等紊流强度的浮选环境中,控制疏水颗粒粒径在-200+45 μm或亲水性颗粒粒径在-10 μm或+45 μm均可强化浮选回收。相同浮选药剂条件下,煤泥粒度越细,煤的回收率越难以保障,并且水回收率呈增加趋势,浮选效率降低。     

CFD modelling of bubble–particle attachments in flotation cells

In recent years, computational fluid dynamic (CFD) modelling of mechanically stirred flotation cells has been used to study the complexity of the flow within the cells. In CFD modelling, the flotation cell is discretized into individual finite volumes where local values of flow properties are calculated. The flotation effect is studied as three sub-processes including collision, attachment and detachment. In the present work, these sub-processes are modelled in a laboratory flotation cell. The flotation kinetics involving a population balance for particles in a semi-batch process has been developed.From turbulent collision models, the local rates of bubble–particle encounters have been estimated from the local turbulent velocities. The probabilities of collision, adhesion and stabilization have been calculated at each location in the flotation cell. The net rate of attachment, after accounting for detachments, has been used in the kinetic model involving transient CFD simulations with removal of bubble–particle aggregates to the froth layer.Comparison of the predicted fraction of particles remaining in the cell and the fraction of free particles to the total number of particles remaining in the cell indicates that the particle recovery rate to the pulp–froth interface is much slower than the net attachment rates. For the case studied, the results indicate that the bubbles are loaded with particles quite quickly, and that the bubble surface area flux is the limiting factor in the recovery rate at the froth interface. This explains why the relationship between flotation rate and bubble surface area flux is generally used as a criterion for designing flotation cells. The predicted flotation rate constants also indicate that fine and large particles do not float as well as intermediate sized particles of 120–240 μm range. This is consistent with the flotation recovery generally observed in flotation practice. The magnitude of the flotation rate constants obtained by CFD modelling indicates that transport rates of the bubble–particle aggregates to the froth layer contribute quite significantly to the overall flotation rate and this is likely to be the case especially in plant-scale equipment.     

Electrokinetic properties of pyrite,arsenopyrite and quartz in the absence and presence of cationic collectors and their flotation behaviour

This paper contains the results of Hallimond tube flotation tests conducted with pyrite arsenopyrite and quartz using a cationic type collector called hexyl thioethylamine, as well as the results of electrophoretic mobility (E.M.) tests for the same minerals measured under various conditions. The purpose of this study is to investigate the effect of surface charge of sulphide minerals on the attachment mechanism of a cationic collector. In this regard, the influence of pH and collector concentration on the electrophoretic mobilities of pyrite, arsenopyrite and quartz were monitored. The mobility measurements at various pH values were made in the absence and presence of collector, and the effect of collector concentration on the electrophoretic mobility was determined at constant pH. The results were evaluated in terms of flotation, electrophoretic mobility, adsorption and IR data. The experimental results indicate that flotation of pyrite induced by hexyl thioethylamine is not dependent on the surface charge of the particle.     

气泡、油泡和活性油质气泡在浮选中的应用和机理探讨

浮选是高效回收矿产资源应用最广泛的技术方法。气泡作为浮选载体在浮选过程中有着举足轻重的作用。以气泡-油泡-活性油质气泡为线索,对比了传统气泡与改性后油泡(气泡表层包裹一薄层油性捕收剂)、活性油质气泡(气泡表层包裹一薄层含有捕收剂的中性油)的浮选特性。通过浮选动力学分析了气泡与油泡、活性油质气泡浮选的区别,传统气泡浮选与改性后的油泡浮选均为2步反应,而活性油质气泡实现了1步浮选,大大降低了气泡与矿物颗粒间的黏附功,提高了浮选效率。从油-水界面表面活性剂解离度这个角度分析了活性油质气泡的表面性质,指出活性油质气泡的表面电性由表层中性油中添加的捕收剂和p H决定。通过DLVO理论计算了不同气泡与矿物颗粒间的相互作用能,从理论上解释了活性油质气泡浮选指标更好的原因。活性油质气泡在选矿中的成功应用表明,活性油质气泡与矿物表面的作用均强于传统气泡与矿物表面的作用,即活性油质气泡对矿物具有更强的捕收能力,相较于气泡和油泡的浮选,活性油质气泡浮选有利于提高浮选效率,降低捕收剂用量。活性油质气泡作为浮选载体从气泡这一特殊视觉为浮选行业开辟了一个崭新的研究领域。     

新型阳离子捕收剂对石英的捕收性能及作用机理

用东北大学研制的新型高效阳离子捕收剂DBA-1对石英纯矿物进行了药剂用量、浮选温度、合适酸碱度试验,并借助Zeta电位测定、红外光谱分析和接触角测定对DBA-1浮选石英的机理进行了分析,以检验DBA-1对石英的捕收性能及效果。结果表明：①0.074～0.038 mm粒级石英纯矿物在pH=8.5、矿浆温度为18 ℃、药剂用量为75 mg/L的情况下可获得97.3%的回收率。②在无DBA-1的矿浆中,石英零电点的pH=2.26,而与DBA-1作用后的零电点偏移至10.10,说明DBA-1可以以阳离子形式在石英表面发生静电吸附;DBA-1与石英作用前后的红外光谱分析表明,二者间存在氢键吸附。③DBA-1的添加可大幅度提高石英表面的接触角,增强其表面的疏水性和可浮性,接触角在12.6°～27.0°范围内的小幅增大都会引起回收率的大幅度提高。     

低阶煤颗粒-气/油泡间的诱导时间研究

为表征低阶煤颗粒-气/油泡间矿化过程的差异,通过Sutherland理论下固体颗粒进入泡沫产品的总概率(E)和浮选速率常数(k)之间关系,并结合低阶煤颗粒-气/油泡的浮选速率试验,求得了低阶煤颗粒-气/油泡间的诱导时间。浮选实验研究表明,在相同的捕收剂消耗量下低阶煤-油泡浮选产率均高于低阶煤-气泡浮选产率。诱导时间测试表明,低阶煤颗粒-油泡间的诱导时间(35 ms)要明显低于低阶煤颗粒-气泡间的诱导时间(93 ms)。上述实验结果表明,油泡表面的疏水性要强于传统浮选气泡表面的疏水性。然而,进一步利用Sutherland理论中固体颗粒进入泡沫产品的总概率和浮选速率常数之间的数学关系,并结合低阶煤颗粒-气/油泡的浮选速率试验求得的低阶煤颗粒-气/油泡间的诱导时间分别为9.67和8.46 ms,其与诱导时间测试仪分别测量的诱导时间差异很大。这主要是由于在实际浮选过程中气/油泡的上升速度分别为23.26和22.68 cm/s,其远高于2015EZ型诱导时间仪测试过程中气/油泡碰撞速度(2.0 cm/s)。因此,诱导时间理论计算表明气泡-颗粒间的碰撞速度对颗粒-气泡间的诱导时间影响很大。上述研究...     

胶磷矿浮选泡沫稳定性研究

以贵州福泉氟磷灰石、石英、白云石和方解石纯矿物浮选泡沫为研究对象,分析胶磷矿浮选泡沫稳定性,通过泡沫稳定性测试、三相接触角测量和泡沫光学图像观察,研究胶磷矿中四种主要矿物在不同捕收剂浓度、矿物颗粒粒度和质量浓度下的浮选泡沫稳定性,并考察白云石和方解石溶解产生的Ca2+、Mg2+对泡沫稳定性的影响。研究结果表明：氟磷灰石、白云石和方解石分散体系的三相泡沫稳定性均随着十二胺浓度的增大而增加,接触角变化幅度不大。石英颗粒的泡沫稳定性先增加后降低,接触角在十二胺浓度1.5×10-4mol·L-1后大于90°,表现出极强的疏水性;四种矿物颗粒体系的三相泡沫稳定性均随着颗粒粒度的增大而逐渐减小,随着颗粒质量浓度增大而增加。通过泡沫图像发现,矿物颗粒黏附在泡膜表面,液膜变厚,提高了泡沫稳定性;白云石和方解石溶解产生的Ca2+、Mg2+对泡沫稳定性具有促进作用。     

新型常温捕收剂DX-1浮选司家营铁矿混磁精矿试验研究

针对司家营铁矿使用常规捕收剂浮选矿浆温度高,热能消耗大等问题,研制出新型常温阴离子反浮选捕收剂DX-1。为验证该药剂对实际矿物的浮选效果,以司家营铁矿品位40.05%的混合磁选精矿为研究对象进行了反浮选试验。试验结果表明:该新型捕收剂可适应20 ℃低温环境,在pH=11.5时,经过1粗1精3扫闭路试验流程,可得到品位65.23%、回收率83.55%的铁精矿。最终产品的SEM和EDS能谱分析结果表明:DX-1对石英、白云石等脉石矿物的捕收具有较好的选择性;产品中未完全单体解离的粗颗粒是影响进一步提高精矿品位的主要原因,尾矿中夹带微细粒铁矿物的现象,影响了金属回收率。