Effects of Particle Size and Chain Length on Flotation and Adsorption of Quaternary Ammonium Salts onto Kaolinite

Effects of particle size and chain length on flotation of quaternary ammonium salts (QAS) onto kaolinite have been investigated by mico-flotation tests. The two kinds of quaternary ammonium salts [RN(CH3)3] with different chain lengths, dodecyltrimethylammonium chloride (DTAC) and cetyltrimethylammonium chloride (CTAC) were used as collectors for kaolinite in different particle size fractions (0.075–0.01 mm, 0.045–0.075 mm, 0–0.045 mm). The anomalous flotation behavior of kaolinite have been further explained based on crystal structure considerations by adsorption tests and molecular dynamics (MD) simulation. The results show that the flotation recovery of kaolinite in all different particle size fractions decreases with an increase in pH when DTAC and CTAC are used as collectors. As the concentration of collectors increases, the flotation recovery increases. The longer the carbon chain of QAS is, the higher the recoveries of coarse kaolinite (0.075–0.01 mm and 0.045–0.075 mm) are. But the flotation recovery of the finest kaolinite (0–0.045 mm) decreases with chain lengths of QAS collectors increasing, which is consistent with the flotation results of unsifted kaolinite (0–0.075 mm). It is explained by the froth stability related to the residual concentration of QAS collector. In lower residual concentration, the froth stability becomes worse. Within the range of flotation collector concentration, it's easy of CTAC to be completely adsorbed by kaolinite in the particle size fraction (0–0.045 mm), which led to lower flotation recovery. Moreover, it is interesting that the particle size of kaolinite is coarser, the flotation recovery is higher. The anomalous flotation behavior of kaolinite is rationalized based on crystal structure considerations. The results of MD simulations show that the (001) kaolinite surface has the strongest interaction with DTAC, compared with the (001), (010) and (110) surfaces. On the other hand, when particle size of kaolinite is altered, the number of basal planes and edge planes is changed. It is observed that the finer kaolinite particles size become, the greater relative surface area of edges is, and the more the number of edges is. It means that fine kaolinite particles have more edges to adsorb less cationic colletors than that of coarse kaolinite particles, which is responsible for the poorer floatability of fine kaolinite.     

The anomalous behavior of kaolinite flotation with dodecyl amine collector as explained from crystal structure considerations

The electrokinetics and flotation behavior of kaolinite have been investigated through flotation experiments, zeta potential measurements, and FTIR spectral analysis. These results have been explained based on crystal structure considerations and quantum mechanical calculations. It has been shown that the PZC of kaolinite is at pH 4.2. Kaolinite exhibits good floatability in weakly acidic solution with dodecyl amine (DDA) collector. The negative zeta potential of kaolinite increases with an increase in pH, and hence the adsorption of DDA on kaolinite increases. However, the flotation of kaolinite decreases with an increase in pH and an increase in DDA adsorption. This anomalous flotation behavior is rationalized based on crystal structure considerations and particle aggregation phenomena. It is considered that the silica (001) and the alumina (001¯) basal planes of kaolinite are negatively charged. From quantum chemistry calculations, the interaction between DDA and the (001) plane was found to be stronger than at the (001¯) alumina plane due to the difference in the structure at the (001) and (001¯) planes. The self-aggregation between (001¯) faces and the edge planes and the adsorption of DDA at the silica (001) plane make the kaolinite aggregates hydrophobic, and good floatability is achieved in acidic solution. In alkaline solution, the kaolinite particles are dispersed. In the presence of DDA, hydrophobic aggregation appears to occur in alkaline solution between the (001) planes due to adsorbed DDA, and thus the hydrophilic (001¯) faces are exposed and flotation is not achieved.     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

Flotation of fluorite with n-alkylammonium chlorides

Experimental study on the electrokinetic and flotation behaviour of fluorite in solutions of n-alkylammonium chlorides (with 10, 12 and 14 carbon atoms) is given. The zero point of charge (ZPC) of luorite was determined by measuring zeta potential (streaming potential method) as a function of pH. Two conditioning times of the mineral with the solution were used (10 minutes and 48 hours) and the respective ZPC were located at pH 2.2 and 8.4. Decyl-, dodecyl- and tetradecylammonium ions seem to be strongly adsorbed on the interface because they made the zeta potential more positive as the concentration increases. Hallimond tube flotation of fluorite was studied and shown to be influenced by the chain length of the collector and both collector and hydrogen ion concentrations. Flotation recovery for a given concentration of collector increases with the number of carbon atoms of the chain. The results have been discussed in the light of the electrical double-layer theory.     

Hallimond tube flotation of scheelite and calcite with amines

Hallimond tube flotation experiments have been carried out on the two calcium minerals scheelite and calcite using dodecylammonium chloride as collector. The main variables studied were the calcium ion concentration and the pH.In the case of scheelite, addition of calcium chloride markedly lowered the flotation recovery. Recovery was also lowered when the pH was reduced below about 10. Since it is known that the zeta potential of scheelite is almost independent of pH this confirms that co-adsorption of un-ionized amine is necessary for good flotation. Other un-ionized long-chain molecules can replace the amine; thus it was shown that excellent flotation can be obtained event at about pH 7 by adding dodecanol together with dodecylammonium chloride. With the completely ionic trimethyldodecylammonium chloride recoveries were poor and were independent of pH.In the case of calcite, calcium chloride had no immediate effect on flotation recovery, but at low collector concentrations marked depression occurred after many hours standing in the presence of calcium ions. The effect of pH on flotation of calcite was anomalous and there appear to be two pH regions in which recoveries are high.The results are discussed and attention is drawn to the need for more thorough studies of the calcium carbonate/water interface.     

新型捕收剂RA-92在低品位碳酸锰矿选矿中的应用

微细粒低品位锰矿由于颗粒间的非选择性聚集、浮选药剂用量大、浮选效率低等技术难题而致使其利用困难,造成大量浪费。在品位低于13%的锰矿浮选技术研究中,捕收剂最受关注,前人已研究了多种类型的捕收剂,所得精矿品位在16.9%~18.3%之间,回收率为56%~97%,回收率比较理想,但精矿品位总体不高。本文将新型捕收剂RA-92应用于湖南凤凰-花垣地区低品位碳酸锰矿(锰品位为10.7%)的选矿工艺中,实验研究了磨矿细度、pH值、抑制剂和捕收剂用量对浮选效果的影响,在最佳工艺条件下,精矿品位由原矿的10.7%提升至17.4%,回收率达到80.2%。研究表明RA-92对碳酸锰矿具有良好的捕收性能,浮选工艺相对简单且捕收剂用量少,浮选成本较低,可为此种捕获剂在微细粒低品位碳酸盐锰矿选矿中的应用得到推广。     

Infrared study of the adsorption on silica of a collector with an oxyethylene chain

Positive results obtained for the flotation of quartz at low pH by a molecule containing a polyoxyethylene chain ($\text{OPEG}\text{=}\text{Triton}\text{× 100}$) led us to examine the nature of the interactions between this collector and the quartz surface, using infrared spectroscopy and considering a porous silica as a model adsorbent.The infrared spectra obtained after adsorption of increasing amounts of OPEG show the disappearance of the free OH groups of silica surface and the development of a band due to bridged hydroxyls. This indicates the formation of hydrogen bonds between ether groups of the collector and silica surface hydroxyls.     

A study of factors affecting on the zeta potential of kaolinite and quartz powder

The purpose of this study was to determine the effects of pH, ion type (salt and metal cations), ionic strength, cation valence, hydrated ionic radius, and solid concentration on the zeta potential of kaolinite and quartz powder in the presence of NaCl, KCl, CaCl₂, CuCl₂, BaCl₂, and AlCl₃ solutions. The kaolinite and quartz powder have no isoelectric point (iep) within the entire pH range (3 < pH < 11). In the presence of hydrolysable metal ions, kaolinite and quartz powder have two ieps. As the cationic valence increases, the zeta potential of kaolinite and quartz powder becomes less negative. Monovalent cation, K⁺, yields more negative zeta potential values than the divalent cation Ba²⁺. As concentration of solid increases, the zeta potential of the minerals becomes more positive under acidic conditions; however, under alkaline conditions as solid concentration increases the zeta potential becomes more negative. Hydrated ionic radius also affects the zeta potential; the larger the ion, the thicker the layer and the more negative zeta potential for both kaolinite and quartz powder.     

Interaction of thionocarbamate and thiourea collectors with sulphide minerals: a flotation and adsorption study

The ability of O-isopropyl-N-ethyl thionocarbamate (IPETC), O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC) and butyl ethoxycarbonyl thiourea (BECTU) collectors to increase the flotation of the sulphide minerals, chalcopyrite, galena and pyrite, has been studied. For each collector, the flotation characteristics of these minerals, flotation rate constant and flotation recovery maximum, have been calculated from the flotation data and compared as a function of pH and collector concentration. Overall, the flotation performance of these collectors is stronger for chalcopyrite than for galena and pyrite. Flotation increases with collector concentration and decreasing pH values. For chalcopyrite, the collector performances of BECTU are slightly better than those of IPETC but far superior to those of IBECTC, especially at high pH values or at low collector concentrations. The flotation performance of these collectors has been shown to be in good agreement with the amount of collector adsorbed at the mineral surface. The affinity of BECTU for the various minerals has been calculated using a multilayer adsorption model.     

The influence of humic materials on the flotation of coal

The effect of humic material on the flotation response of coal has been examined. The results show that while hydrogen ions do not adversely affect the flotation of coal particles, they interact with humic material adsorbed on the surface of the clay particles and render their surfaces oleophilic. This behaviour enables the clay particles to adsorb collector in preference to the coal particles and thus inhibit coal flotation.     

The Role of Flotation Reagents in the Reverse Flotation of Carbonate-Containing Iron Ores

The Influence of pulp pH, dispersants and auxiliary collectors on reverse flotation of carbonate-containing iron ores were explored. Interactions between iron ores and quartz were theoretically analyzed by flotation solution chemistry and DLVO theory. The results indicated that the iron concentrate grade improved sharply when pH increased from 11.0 to 12.0, but changed unobviously when pH was larger than 12.0, which was related to solution chemistry of siderite and interactions among particles. Sodium tripolyphosphate was an effective dispersant and sodium dodecyl sulfate was an effective auxiliary collector of KS-III. Both recovery and grade enhanced by the action of sodium dodecyl sulfate or sodium tripolyphosphate when pH was 12.0.     

Sorptive removal of ibuprofen from water using selected soil minerals and activated carbon

Pharmaceuticals have gained significant attention in recent years due to the environmental risks posed by their versatile application and occurrence in the natural aquatic environment. The transportation and distribution of pharmaceuticals in the environmental media mainly depends on their sorption behavior in soils, sediment?Cwater systems and waste water treatment plants, which varies widely across pharmaceuticals. Sorption of ibuprofen, a non-steroidal anti-inflammatory drug, onto various soil minerals, viz., kaolinite, montmorillonite, goethite, and activated carbon, as a function of pH (3?C11), ionic strength (NaCl concentration: 0.001?C0.5?M), and the humic acid concentration (0?C1,000?mg/L) was investigated through batch experiments. Experimental results showed that the sorption of ibuprofen onto all sorbents was highest at pH 3, with highest sorption capacity for activated carbon (28.5?mg/g). Among the minerals, montmorillonite sorbed more ibuprofen than kaolinite and goethite, with sorption capacity increasing in the order goethite (2.2?mg/g)?<?kaolinite (3.1?mg/g)?<?montmorillonite (6.1?mg/g). The sorption capacity of the selected minerals increased with increase in ionic strength of the solution in acidic pH condition indicating that the effect of pH was predominant compared to that of ionic strength. An increase in humic acid concentration from low to high values made the sorption phenomena very complex in the soil minerals. Based on the experimental observations, montmorillonite, among the selected soil minerals, could serve as a good candidate to remove high concentrations of ibuprofen from aqueous solution.     

Solution chemistry studies and flotation behaviour of apatite,calcite and fluorite minerals with sodium oleate collector

The maximum flotation response for three naturally occurring calcium minerals, apatite, calcite and fluorite with sodium oleate collector correlated directly with the minimum interfacial tension of the air/solution interface. For fluorite and apatite the minimum surface tension occurred about the mid-pH region and was attributed to the formation of pre-micellar associated species in solution. In the case of calcite the minimum was observed at high pH since the presence of high concentrations of calcium ions in solution appeared to reduce the concentration of amphililic species in the low and mid-pH regions.Microelectrophoresis data demonstrated that the three minerals acquired a negative charge in sodium oleate solution, resulting from adsorption of oleate species on the mineral surfaces.The flotation behaviour of the systems were shown to be related to the species distribution diagrams suggesting that the role of the acid soap dimer, soap dimer, molecular and lattice species could make a significant contribution to the character and composition of the interfacial films.High flotation response was explained by strong adhesion between the hydrophobic particle and bubble. It was suggested that the reduction in surface tension may not be the major factor contributing to the flotation efficiency but indicated the presence of associated surfactant species in solution which could also synergistically adsorb at the solid/liquid interface, increasing the hydrophobic character of the mineral surface. This would maximize the magnitude of the contact angle and hence the strength of the adhesion between particle and bubble. This adsorption behaviour is not in general agreement with conventionally non-hydrolyzable collector theory which is usually based on electrostatic models.     

不同形态洛美沙星在高岭土上的吸附特性

本研究采用批实验方法探究了不同形态洛美沙星(LOM)在高岭土上的吸附特性。LOM吸附动力学结果符合准二级反应动力学方程,吸附等温数据可用Langmuir方程很好地拟合。随着溶液pH值增大,洛美沙星吸附量先增大后减小,且pH值在洛美沙星pKa1与pKa2间吸附量达到最大。不同形态LOM在高岭土上的吸附量排序为LOM^±>LOM^+>LOM^-。溶液离子强度和无机阳离子种类对LOM^+在高岭土上的吸附影响十分微弱,但均明显抑制了LOM^±的吸附,且离子强度越大,抑制作用越明显。不同无机阳离子抑制程度排序为Mg^2+>Ca^2+>K^+>Na^+。LOM^+在高岭土上的吸附机理主要是内层络合和阳离子交换;LOM^±在高岭土上的吸附机理主要是阳离子交换、氢键作用和静电引力作用;LOM^-与高岭土表面存在较大静电斥力,导致吸附量很小,可能是外层表面络合引起少量的吸附。     

Deposition and mobilization of functionalized multiwall carbon nanotubes in saturated porous media: effect of grain size,flow velocity and solution chemistry

Carbon nanotubes (CNTs) are widely manufactured nanoparticles which are utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is, therefore, essential to improve the current understanding of environmental fate and transport of CNTs. The current study systematically investigated the effect of solution chemistry (pH and ionic strength) and physical conditions (collector grain size and flow rate) on the deposition and mobilization of functionalized multiwall carbon nanotubes (MWCNTs) using a series of column experiments under fully saturated conditions. A one-dimensional convection–dispersion model including collector efficiency for cylindrical nanoparticles was used to simulate the transport of MWCNTs in porous media. It was observed that an increase in pH resulted in increased mobility of MWCNTs. However, the transport of MWCNTs was strongly dependent on ionic strength of the background solution and a critical deposition concentration was observed between 3 and 4 mM NaCl concentration, with more than 99 % filtration of MWCNTs at 4 mM. The finer sand grains were able to filter a significant amount of MWCNTs (15 % more than coarse sand) from the inflow solution; this was likely caused by grain-to-grain straining mechanisms in the finer sand. A decrease in pore water velocity also led to more deposition of MWCNTs due to lowering of the kinetic energy of the particles. The results from this study indicated that a weak secondary minimum existed under unfavorable conditions for deposition, but the particles were trapped at both primary and secondary minimum.     

Oxidation-Reduction effects in the flotation of chalcocite and cuprite

A laboratory study of the batch flotation of chalcocite from chalcocite-quartz mixtures and of cuprite from cuprite-quartz mixtures with potassium ethyl xanthate as collector has shown that the oxidation-reduction state of the flotation pulp can have a pronounced influence on mineral floatabilities. At pH 11 chalcocite floated over a relatively narrow Eh range of about 300 mV; pH had no influence on the potential of the lower flotation boundary in reducing conditions but had a significant effect on the potential of the upper boundary in oxidizing conditions. Below this upper limit, the floatability was reversible with respect to Eh. Provided the Eh was in correct region chalcocite could be floated in the absence of measurable concentrations of dissolved oxygen.Cuprite displayed a high level of floatability with ethyl xanthate for which, by contrast with chalcocite, no flotation limit in reducing conditions was found; over a small range of potentials close to zero, its behaviour was strongly pH dependent.An attempt to account for the floatabilities of chalcocite and cuprite in terms of the formation of cuprous ethyl xanthate on their surfaces did not lead to correlations with the observed behaviour in reducing conditions but provided a rough correlation with the upper flotation potential limit. It is believed that more detailed and properly controlled comparative flotation studies of the chalcocite-xanthate and cuprite-xanthate systems could help to resolve some of the uncertainties associated with the effects of Eh, pH and oxygen concentration in sulphide mineral flotation.     

Interpretation of interaction effects and optimization of reagent dosages for fine coal flotation

The effect of three most important reagents for coal flotation namely sodium meta silicate, collector (kerosene) and frother (MIBC) was studied using 2³ full factorial design. The regression models were developed using factorial experiment data to quantify the effect of sodium meta silicate, collector and frother and to predict grade and recovery of combustible material for different reagent conditions. The addition of sodium meta silicate increased the recovery without affecting the grade significantly. The MIBC addition reduce the surface tension at the liquid–vapor interface, which results in the production of finer bubble size distribution and thus improves flotation rates and recovery values. However, a finer bubble size distribution also increases water recovery, which results in a greater recovery of entrainable ash bearing particles and thus degradation of the product grade. The interaction between OH group of MIBC and hydrated mineral matter improves flotability of high ash coal particles and degrades the product grade further. The negative effect of kerosene and MIBC interaction on both grade and recovery could be due to the recovery of high ash coal particles in preference to low ash coal particles. The highest possible grade of product is 94.19% combustibles with 25.33% recovery. A product with 91.11% combustibles grade at 95.58% recovery was obtained at 0.1 g/kg sodium silicate, 0.4 g/kg collector and 0.075 g/kg frother from the coal fines tested.     

石英与钠长石浮选分离的研究

用十八胺(阳离子捕收剂)和十二烷基磺酸钠(阴离子捕收剂,SDS)作浮选为捕收剂分离石英与钠长石,研究了浮选条件对分离效果的影响以及捕收剂在矿物表面的吸附行为.结果表明,最佳浮选条件是浮选液的pH=2,阴、阳离子捕收剂的浓度分别为3.0×10-6 mol/L和4.0×10-6 mol/L;阴阳离子捕收剂在石英与钠长石两种矿物上表现出相同的吸附行为.在最佳浮选条件下,对不同配比的石英和钠长石混合物进行浮选,石英回收率为14%,钠长石回收率达80%,分离效果显著;对含微量长石的石英矿粉进行浮选,分离效果与石英与钠长石混合物相近.     

Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25°C

Rate laws reported for the oligomerization of silica in natural environments are often contradictory, and the kinetics of monosilicic acid condensation are poorly understood. Here we present rate expressions that systematically describe the initial oligomerization of silica in terms of concentration of initial silica, ionic strength, and pH for a natural brine solution. The oligomerization of silica in dilute aqueous solutions was examined in solutions with ionic strengths of 0.01 and 0.24 molal, from pH 3 to 11, and with initial silica concentrations of 4.2, 12.5, and 20.8 millimolal (250, 750, and 1250 ppm SiO₂ respectively). The decrease in concentration of molybdate-reactive silica was monitored over time to determine the extent of oligomerization. This decrease in concentration of molybdate-reactive silica is accompanied by the appearance of a transient population of nanocolloidal particles with diameter ∼3 nm, as determined by atomic force microscopy (AFM). The oligomerization rate increases as pH approaches near neutral and as ionic strength increases. Early in the reaction where the concentration of molybdate-reactive silica, [SiO₂]_n≤3, is assumed to equal the concentration of monosilicic acid, [H₄SiO₄], the rate of change of monosilicic acid as a function of time, R, shows a fourth-order dependence:

R=k₄⁴[H₄SiO₄]     

Modeling the kinetics of silica nanocolloid formation and precipitation in geologically relevant aqueous solutions

The kinetics of the formation and precipitation of nanocolloidal silica from geologically relevant aqueous solutions is investigated. Changes in monomeric (SiO_2(mono)), nanocolloidal (SiO_2(nano)) and precipitated silica (SiO_2(ppt)) concentrations in aqueous solutions from pH 3 to 7, ionic strengths (IS) of 0.01 and 0.24 molal, and initial SiO₂ concentrations of 20.8, 12.5 and 4.2 mmolal (reported in [Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25 °C. Geochim. Cosmochim. Acta69(2), 293-303.]) were fit using two kinetic models. The first model, termed the concentration model, is taken from Icopini et al. (2005) and assumes that the rate of change of SiO_2(mono) as a function of time has a fourth-order dependence on the concentration of SiO_2(mono) in solution. The second model, termed the supersaturation model, incorporates the equilibrium concentration of amorphous silica and predicts that polymerization will be a function of the degree of silica supersaturation in solution with respect to amorphous silica. While both models generally predicted similar rate constants for a given set of experimental conditions, the supersaturation model described the long-term equilibrium behavior of the SiO_2(mono) fraction more accurately, resulting in significantly better fits of the monomeric data. No difference was seen between the model fits of the nanocolloidal silica fraction. At lower pH values (3-4), a metastable equilibrium was observed between SiO_2(mono) and SiO_2(nano). This equilibrium SiO_2(mono) concentration was found to be 6 mmolal, or three times the reported solubility of bulk amorphous silica under the experimental conditions studied and corresponds to the predicted solubility of amorphous silica colloids approximately 3 nm in diameter. Atomic force microscopy was used to determine the average size of the primary nanocolloidal particles to be ∼3 nm, which is in direct agreement with the solubility calculations. Larger aggregates of the primary nanocolloids were also observed to range in size from 30 to 40 nm. This work provides the first kinetic models describing the formation and evolution of nanocolloidal silica in environmentally relevant aqueous solutions. Results indicate that nanocolloidal silica is an important species at low pH and neutral pH at low ionic strengths and may play a more important role in geochemical cycles in natural aqueous systems than previously considered.