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。     

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.     

Role of oily bubbles in enhancing bitumen flotation

A recognized challenge in bitumen extraction is the reduced bitumen recovery when processing high-fine ores or “weathered” oil sand ores, collectively called poor processing ores. Preliminary lab tests demonstrated that bitumen flotation recovery from these ores could be greatly enhanced by using oily bubbles (air bubbles coated with a thin layer of oil or solvent) instead of air bubbles. In this study, dynamic contact angle of air/oily bubbles on bitumen surface and induction time of bitumen–air/oily bubble attachment in aqueous solution were measured to investigate the mechanisms of how oily bubbles help improve bitumen recovery and to justify the use of oily bubbles while processing poor oil sand ores. Oily bubbles showed a marginal effect on the contact angle values compared to air bubbles. However, the spreading of oily bubbles on a bitumen surface was found to be much faster than that of air bubbles. The induction time for bubble–bitumen attachment in the process water from poor processing ores was found to be much shorter for oily bubbles than for air bubbles. The reduced induction time for kerosene-coated air bubble–bitumen attachment correlates well with the improved bitumen recovery from poor processing ores using kerosene-coated oily bubble flotation technology.     

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...     

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.     

低阶煤颗粒-气/油泡间的疏水力常数研究

浮选实验表明油泡对低阶煤颗粒的捕收能力要远强于传统浮选过程的起泡。这主要是由于油泡表面被捕收剂覆盖,其表面疏水性要远高于气泡表面的疏水性。因此,在油泡浮选矿化过程中,低阶煤颗粒-油泡间水化膜的薄化速度要远快于煤颗粒-气泡间的薄化速度。诱导时间测试发现,随着DAH溶液浓度从10~(-7) mol/L增加到5×10~(-5) mol/L时,低阶煤颗粒-气泡间的诱导时间从93 ms下降到12 ms。随着DAH溶液浓度从5×10~(-5) mol/L增加到10~(-3) mol/L时,低阶煤颗粒-气泡间的诱导时间从12 ms增加到35 ms。当DAH浓度由10~(-7) mol/L(纯去离子水溶液)增加到5×10~(-5) mol/L,低阶煤颗粒-油泡间的诱导时间由35 ms降低到10 ms。随着DAH浓度的进一步增加到10~(-3) mol/L时,低阶煤颗粒-油泡间的诱导时间由10 ms增加到25 ms。为了从微观尺度下去表征油泡表面较气泡表面所具有的强疏水性,本文通过低阶煤颗粒-油/气泡间的诱导时间,利用non-DLVO理论及Stefan-Reynolds水化膜薄化模型,拟合出初始水化膜厚度h与疏水性常数K_(132)之间的关系,进而得到了低阶煤颗粒-油/气泡间的疏水力常数K_(132)与十二烷胺盐酸盐DAH溶液浓度的关系。疏水力常数K_(132)拟合结果表明,当DAH溶液的浓度为5×10~(-5) mol/L时,低阶煤颗粒-油泡间的疏水力常数K_(132)约为低阶煤颗粒-气泡间的疏水力常数K_(132)的3倍;当DAH溶液的浓度为10~(-6) mol/L时,前者是后者的15倍。因此,油泡表面较气泡具有更强的疏水性质。从而解释了低阶煤-油泡浮选矿化过程优于传统浮选过程的本质特征。     

Detachment of coarse composite sphalerite particles from bubbles in flotation: Influence of xanthate collector type and concentration

The force required to detach sphalerite ore particles from air bubbles has been measured in flotation concentrates, for particles in the size range of 150–300 μm and 300–600 μm with different degrees of liberation. An electro-acoustic vibrating apparatus, that produces typical force conditions experienced in a flotation cell, was used to measure particle–bubble detachment as a function of the vibrational acceleration. Sodium isopropyl xanthate (SIPX) and potassium amyl xanthate (PAX) collectors were used in flotation, at different concentrations. At a fixed frequency of 50 Hz, the maximum vibrational amplitude at which a particle detaches from bubble was used to calculate the particle detachment force. It was shown that changes in surface hydrophobicity (contact angle), due to variations in reagent conditions have significant impact on particles detaching from bubbles. On average, detachment of particles from oscillating bubble correlated well with xanthate concentration and hydrocarbon chain length of xanthate ions. Particles (300–600 μm) with high contact angle obviously required higher force to detach from bubbles than similar particles with lower contact angle. This correlated well with the flotation response at the different reagent conditions. SEM analysis of particles after detachment showed that fully liberated particles attached to bubbles more readily and also gave higher detachment force than composite particles. Moreover larger detachment forces were observed, on average, for particles with irregular shape compared to particles with rounded shape of the same size range.     

低阶煤煤泥油泡浮选技术研究

采用烃类油蒸发制造油气,将油气通入浮选柱气泡发生器的吸气口,生成油泡.对低阶煤煤泥进行油泡柱浮选试验,试验结果表明:油泡对低阶煤煤泥具有强捕收能力与高选择性,分选指标较好.将油泡浮选技术用于工业浮选柱分选,可有效降低浮选捕收剂用量,浮选泡沫层稳定,分选指标好.油泡浮选技术在低阶煤煤泥浮选提质中的应用,为低阶煤煤泥的资源...     

On the role of cavitation in particle collection in flotation – A critical review. II

Research in applying hydrodynamic cavitation to recovery of natural resources during the last decade is reviewed. The existence and formation of tiny bubbles or gas nuclei (with diameter from microns down to nano sizes) in natural water were verified from both direct and in-direct measurements, thus providing a foundation for applying hydrodynamic cavitation to flotation systems. The interactions between tiny bubbles and fine particles in aqueous slurry were analysed based on particle surface properties and types of gas nuclei present in water. Tiny bubbles generated by hydrodynamic cavitation were found to increase contact angle of solids and hence attachment force, bridge fine particles to form aggregates, minimize slime coating, remove oxidation layers on particle surfaces, and in consequence reduce reagents consumption. Experiments on generating tiny bubbles by hydrodynamic cavitation revealed that the energy dissipation levels for cavity formation in a flowing liquid could be much lower than predicted, depending on the content of dissolved gases, presence of free gas nuclei and design of cavitation tubes. Application of hydrodynamic cavitation to fine and coarse particle flotation, high intensity conditioning, oil agglomeration of fine coal, and oil sands processing has confirmed the role of tiny bubbles formed by cavitation in improving recovery efficiency. Based on the characteristics of vapor cavity bubbles, increased flotation kinetics by hydrodynamic cavitation could be attributed to a dual role: some collapsing cavity bubbles serving to break interfacial layers on particle surfaces, while other cavity bubbles attaching to those freshly exposed mineral surfaces. The role of water vapor and other gases within cavity bubbles in particle–bubble attachment remains to be explored, as does the action of frothers. Incorporating hydrodynamic cavitation into flotation systems to take advantage of its unique features is expected to develop the next generation of flotation machines.     

The role of colloidal precipitates in the interfacial behavior of alkyl amines at gas–liquid and gas–liquid–solid interfaces

Alkyl amines are widely used as cationic collectors in froth flotation. They are generally referred to as weak electrolyte collectors and frequently form solid insoluble precipitates. Much work has been done to measure the interfacial tension and contact angle regarding alkyl amine collectors. However, the role of these colloidal precipitates in adsorption phenomena and the kinetics involved in the adsorption have not been systematically studied and decoupled from those of soluble species in flotation. Using dodecyl amine (DDA) as the model surfactant, four sets of intimately linked measurements were made on the dynamic surface tension of amine true solutions and solutions containing precipitates to demonstrate the difference in the surface activity kinetics of colloidal precipitates and soluble species. The effects of the interfacial kinetics on the bubble size in a two-phase system and on the contact angle in a three-phase system were also studied to understand the migration of precipitates between different interfaces. The experimental data showed that kinetic effects existed whenever precipitates were involved, but were absent from true amine solutions. A three-stage mechanism (migration–adsorption–aggregation) was proposed and tested to explain the kinetic behavior associated with precipitates. The size of air bubbles generated in the true solutions was not affected by the surface age of bubbles, while bubble size was affected by the surface age in the presence of precipitates. The observed kinetics of contact angle evolution suggested that the migration of DDA species between air–water–interfaces occurred.     

Poly (N-isopropylacrylamide) (PNIPAM) as a flotation collector: Effect of temperature and molecular weight

Poly (N-isopropylacrylamide) (PNIPAM), a temperature responsive polymer, was tested for its potential use as a collector in a quartz flotation system. The effect of PNIPAM on the surface characteristics of quartz particles were studied using induction time, contact angle and zeta potential measurement and analysed in terms of the probability of bubble/particle attachment and the probability of formation of stable bubble/particle aggregates. It was found that probability of bubble/particle attachment of quartz significantly increases in the presence of PNIPAM, particularly at temperatures above the lower critical solution temperature (LCST) of 32 °C. Furthermore, the probability of bubble/particle attachment increases with increasing PNIPAM molecular weight. This was attributed to the increased hydrophobicity of the quartz surface as well as the decrease in the double layer repulsion between bubbles and particles. This leads to the conclusion that PNIPAM could act as an effective collector in a flotation system.     

Adsorption of collectors on model surface of Wiser bituminous coal: A molecular dynamics simulation study

Coal flotation makes use of the hydrophobicity of coal surface. To enhance the hydrophobicity of coal particles, oily collectors are usually added. Although collectors have been widely applied in coal processing, the microscopic collection mechanism remains a formidable task due to the complexity of coal surface structure. In this work, different combined systems formed by collectors, water and a model surface of Wiser bituminous coal have been studied using molecular dynamics calculations. We modeled the interaction of each collector oil droplet with the coal surface in aqueous phase. In addition, water/collector model systems were also considered in order to reproduce the interaction of the different collectors with water molecules in the collector adsorption process. The results indicate that all three collectors, i.e. dodecane, nonylbenzene and nonylphenol, form spherical insoluble oil droplet in aqueous phase. After the addition of collector droplet over coal surface, all these collectors could thermodynamically repel the interfacial water molecules and spread over the coal surface, thereby reducing roughness of coal surface. The adsorption of nonylphenol on coal surface via both π–π stacking and hydrogen bonds is most favorable, followed by that of nonylbenzene and dodecane. The presence of collector on the coal surface could improve the hydrophobicity. The number of hydrogen bond between water and modified coal surface decreases and the mobility of water molecules increases compared to the original coal surface. However, the extent of hydrophobicity of modified coal surface by these collectors is inconsistent with their adsorption capabilities. Nonylphenol is the worst collector to improve the surface hydrophobicity of coal as part of nonylphenol molecules orient away from coal surface to form hydrogen bonds via their hydroxyl groups with water molecules. Dodecane should be the most effective collector as the hydration energy of the modified surface and the number of formed hydrogen bond between this surface and water molecules are the lowest, whereas the mobility of water molecules on this modified surface is the highest.     

巯基捕收剂浮选细粒的某些特性

阐明了浮选不同粒级硫化物巯基捕收剂作用的研究。结果表明,当浮选细粒硫化物时,由于黑药的结构特点（有两个非极性基）,它比黄药优越。按矿粒在气泡上沿环固着的假说,探讨了使用黄药和黑药时存在不同的矿物－气泡集合体的作用机理。研究结果可用于修正选厂的药剂制度。     

高质量浓度曲拉通X-100对煤泥浮选的抑制效应及机理

表面活性剂在煤泥浮选领域中应用广泛,且表面活性剂常被用于煤泥浮选促进剂,本文从另一个方面探究了表面活性剂在过量的情况下对煤泥浮选的抑制效应及其机理。以低灰煤粒和表面活性剂曲拉通X-100为研究对象,采用X射线光电子能谱(XPS)表征曲拉通X-100在煤表面的吸附状态,静态接触角测定仪测定曲拉通X-100对煤表面疏水性的影响,并探究了不同质量浓度曲拉通X-100液滴在煤粒表面的润湿与铺展情况,采用诱导时间测量仪分析不同质量浓度曲拉通X-100水溶液中的气泡与煤粒的黏附情况,最后通过紫外分光光度计定量表征浮选槽中残留曲拉通X-100质量浓度与不同浮选时间下浮选结果的对应关系。结果表明:高质量浓度曲拉通X-100会抑制煤粒上浮,随着浮选试验的进行,曲拉通X-100质量浓度逐渐降低,低质量浓度曲拉通X-100会促进煤粒被上浮气泡黏附而浮出;高质量浓度曲拉通X-100能够在煤粒表面发生有效吸附,该吸附属于物理吸附,且在一定程度上提高了煤表面的疏水性;高质量浓度曲拉通X-100水溶液更容易润湿煤表面,从而减缓了气泡-煤粒黏附过程中的液膜薄化与破裂速率;在高质量浓度曲拉通X-100水溶液中,气泡表面...     

浮选中颗粒-气泡间相对运动研究进展

颗粒-气泡间相对运动的研究对浮选机理的认知至关重要,对新型浮选机的开发和提高浮选效率均具有指导意义,本文系统综述了颗粒-气泡间相对运动的研究进展。早期研究过程中,研究者忽略了颗粒和气泡性质的影响,将颗粒视为随流线运动的点,气泡视为刚性球体,利用流线方程对颗粒-气泡间的相对运动展开研究;随着认知过程的不断深入,颗粒和气泡物理化学性质的影响逐步得到了关注,研究者分别从颗粒惯性力、重力、形状和粗糙度以及气泡表面流动性等方面并展开了大量研究;颗粒-气泡间相对运动的试验研究多通过颗粒沉降法进行,研究对象由单个玻璃微珠发展为大量矿物颗粒,且出现了关于运动玻璃球与上升气泡之间相对运动的研究。研究表明,当颗粒粒度较细、密度较小时,利用流线方程对颗粒-气泡间相对运动的研究具有一定的适用性;当颗粒粒度较粗、密度较大时,需考虑正负惯性力、重力等因素对颗粒-气泡间相对运动的影响。此外,颗粒形状的不规则性会影响颗粒周围液体对颗粒的作用力,导致临界碰撞半径减小,且颗粒表面不规则的凸起会促进颗粒-气泡间水化膜的破裂,减少诱导时间,增大颗粒表面粗糙度有助于增强颗粒-气泡间的黏附强度。气泡表面的流动性可采用"滞留帽"模型进行分析,具有较好的适用性。对于颗粒-气泡间相对运动的试验研究主要采用颗粒沉降法,亲水玻璃微珠只能在气泡上半球滑行,到达气泡赤道位置附近后便离开气泡,疏水玻璃微珠会刺破颗粒-气泡间的水化膜,越过气泡赤道后会继续沿气泡表面滑行并最终黏附在气泡底部,煤颗粒与气泡的黏附效率随碰撞角和密度的增大而减小。然而目前的试验研究多集中于静水领域,对于浮选流场中颗粒-气泡间相对运动的试验研究尚需进一步探索。     

The limits of fine particle flotation

Understanding the limits of fine particle flotation is the key to the selective separation of fine mineral particles. Fine particles have low collision efficiencies with gas bubbles and float slowly. There has been a great deal of work aimed at overcoming the inefficient collision of small particles with rising air bubbles. This review deals with the influence of bubble size, particle aggregation, different flow conditions, particle induction time, as well as the action of surface and capillary forces on fine particle–bubble capture. Recommendations for practice are given.     

不同捕收剂对氧化煤表面性质影响的实验研究

为了提高氧化煤泥浮选效果,改善氧化煤浮选效率低下、药剂消耗较大的问题,选择了极性油酸和煤油的复配捕收剂,并加入了无机盐CaCl2,探究了在浮选过程中,单一及复配捕收剂,以及无机盐的加入对氧化煤浮选的作用机理和作用效果。结果表明:捕收剂的加入可以覆盖煤泥表面的亲水基团,增强煤泥与气泡的粘附几率;油酸煤油的复配捕收剂可以明显降低煤泥表面的亲水性,无机盐的加入更加促进了煤油在氧化煤表面的附着,煤泥表面因疏水性油膜的形成疏水性增强,利于浮选。     

由地沟油制备羧酸捕收剂强化低阶煤浮选的研究

由于低阶煤表面含氧官能团的存在,用传统的非极性油捕收剂无法实现低阶煤泥的有效回收。与使用传统柴油捕收剂对比,本文在地沟油醇解为生物柴油的基础上进一步合成含有羧酸官能团的捕收剂来强化低阶煤浮选。通过红外光谱分析、核磁氢谱分析、X射线光电子能谱分析和接触角测定进一步分析了捕收剂促进浮选的机理。分别使用羧酸捕收剂、0^#柴油与生物柴油对某低阶极难浮选煤样进行浮选实验,结果表明,羧酸捕收剂获得的浮选精煤效果最好,比柴油捕收剂,精煤产率提升了14.63%,灰分下降了12.06%。     

电解质对低阶煤油泡浮选矿化过程的影响

浮选矿浆中离子的种类与浓度直接影响着矿物颗粒和气泡的表面电位,进而支配着浮选矿化过程。从热力学和动力学两个方面入手,通过DLVO理论探究了不同电解质对煤粒和油泡间的相互作用势能的影响,结合其在不同电解质条件下诱导时间的差异,最终通过相应条件下的油泡浮选试验来证实电解质对低阶煤-油泡浮选矿化黏附过程的影响。结果表明:对于NaCl和CaCl_2两种电解质,随其浓度的增大,煤粒和油泡表面电位的负值均不断减小,煤粒和油泡间的能垒也不断降低,当CaCl_2浓度为100 mmol/L时,煤粒和油泡间的相互作用不存在能垒;并且随这两种电解质浓度的增大,黏附过程的诱导时间逐渐减小,相应地可燃体回收率不断提高,且相同的电解质浓度下,CaCl_2电解质对其相互作用能垒和诱导时间的降低程度更大,可燃体回收率更高。而对于AlCl_3电解质,当其浓度大于20 mmol/L时且随浓度的增大,煤粒和油泡间的相互作用能垒和诱导时间不断增大,相应地可燃体回收率则不断降低。     

浮选体系中气泡运动特性研究进展

在浮选体系中,气泡的运动特性直接影响着矿物浮选的选别效果,因此,研究气泡的运动特性,对于优化浮选工艺与改善浮选效果有着重要意义。本文首先简述了浮选中常见的气泡生成方式,主要有机械搅拌发泡、气泡发生器发泡、电解发泡及超声波发泡四种方式;气泡参数中介绍了气泡形态特征参数、运动特征参数和分布特征参数的含义和计算公式;然后重点阐述了浮选中起泡剂、捕收剂、抑制剂、浮选机叶轮参数、浮选柱气泡发生器及充气量对气泡参数的影响;归纳了纳米气泡在微细粒矿物浮选中的应用;最后指出,完善气泡测量方法、侧重于气泡在实际浮选环境中的运动特性研究以及研发新型纳米气泡生成设备将是未来的发展方向。