Study on comparison adsorption of calcium and sulfate on scheelite and fluorite surfaces

This study investigated the adsorption of calcium and gypsum on scheelite and fluorite using micro-flotation, X-ray photoelectron spectroscopy, scanning electron microscope with energy-dispersive spectrometer, and zeta potential measurements. Micro-flotation showed scheelite recovery is more sensitive to calcium, and gypsum shows stronger inhibition than calcium. Stick-shape precipitates as sulfate-bearing are only found on fluorite surface in gypsum solution. Change law of the zeta potentials of scheelite and fluorite in gypsum solution is obviously different from that in calcium solution. Therefore, we concluded that gypsum would make the separation of scheelite from fluorite more difficult than calcium.     

Adhesion of air bubbles to a fluorite surface in the presence of oleate species

Measurements of the detachment force of air bubbles from a surface of fluorite covered with an oleate film immersed in an aqueous sodium oleate solution or water were carried out. The contact angles for the systems fluorite/oleate film-drop of aqueous sodium oleate solution-air, fluorite/oleate film-air bubble-aqueous sodium oleate solution, and fluorite/oleate film-air bubble-water were also measured. The detachment forces were also calculated from the measured contact angles. It was found that the adhesion of air bubbles to the fluorite surface increased considerably in the presence of an oleate film on the fluorite surface, but decreased if the oleate film was at the water-air interface. Good agreement between the theoretically calculated and the measured values of the detachment force for the system fluorite/oleate film-air bubble-sodium oleate aqueous solution when the concentration of this latter solution was in the range 0 to 87.1 mg/dm³ was also found, but for concentrations over 87.1 mg/dm³ the calculated values of the detachment force were higher than the measured values. The calculations and measurements indicate that the most favourable condition for the adhesion of air bubbles to fluorite grains is the presence of a chemisorbed film of oleate without surface precipitation of calcium oleate salt at low concentrations of oleate species in water.     

Effect of calcium ions on scheelite flotation using mixed collectors

The flotation results show that Ca²⁺ significantly reduces the flotation recovery of scheelite using single dodecylamine (DDA) or single sodium oleate (NaOL), whereas Ca²⁺ hardly affects scheelite recovery using mixed collectors DDA/NaOL. Zeta potential measurements and solution chemistry confirm that the zeta potential of scheelite shows a significant positive shift after conditioning of Ca²⁺, which hinders the adsorption of same positively charged DDA on the mineral surface. Simultaneously, the addition of Ca²⁺ consumes single NaOL and generates Ca(OL)₂. As for DDA/NaOL, the predominant components are RNH₃⁺ and RCOO^? at pH 7; they form new highly active complexes through electrostatic attraction, reducing adverse effect of Ca²⁺. Fourier transform infrared spectroscopy measurements and adsorption measurements further confirm that the pre-adsorption of Ca²⁺ does not interfere with the adsorption of mixed collectors.     

Utilization of sodium humate as selective depressants for calcite on the flotation of scheelite

The flotation separation of scheelite from calcite using sodium humate (SH) as a potential depressant has been studied through micro-flotation experiments, zeta potential and Fourier transform infrared (FT-IR) spectra measurements. The flotation results indicate SH exhibited selective depression effect on calcite in the presence of sodium oleate, achieving the flotation separation of scheelite from calcite. Zeta potential results indicate that SH strongly absorbed on calcite surface but negligibly on scheelite surface, which prevents the adsorption of sodium oleate on calcite surface. The FT-IR results also show that SH can be adsorb on the surface of calcite. Results shown a higher Ca density on the calcite than on scheelite surface, and that calcite can accommodate the interaction of SH.     

Interactions Between Sodium Oleate and Polyoxyethylene Ether and the Application in the Low-Temperature Flotation of Scheelite at 283 K

The poor collecting performance of fatty acids at low temperatures is a problem in mineral flotation. In this study, the floatability of scheelite at 283 K was studied using sodium oleate and binary mixtures of sodium oleate and lauryl alcohol polyoxyethylene ether (MOA-9) as the collector, and interactions between the two surfactants at 283 K were investigated by the means of surface tension and steady state fluorescence measurements. The flotation experiment results show that the collecting performance of the mixed anonic/nonionic collector is stronger than that of single surfactant, and the best molar ratio of sodium oleate to MOA-9 is 10:1 at pH 10. The surface tension results show that the critical micelle concentration value of sodium oleate, MOA-9 and the binary solution is about 2 × 10^?4, 2.5 × 10^?4, and 1.2 × 10^?4 mol/l, respectively. Compared with single surfactants, the mixture exhibits better surface activities since it is more efficient at decreasing the air–water surface tension. The steady state fluorescence results indicate that the hydrophobic parts of MOA-9 molecules insert into the hydrophobic region of sodium oleate micelles to form larger and less compact mixed micelles. The decrease in zeta potential of scheelite treated with the mixed collector indicates the presence of MOA-9 can enhance the chemical adsorption of sodium oleate on the scheelite surface. Therefore, the mixed anonic/nonionic collector can enhance the flotation behavior of scheelite at 283 K.     

柠檬酸对白云母可浮性的抑制机理

为研究油酸钠体系中柠檬酸对白云母可浮性的影响规律及其与白云母的作用机理，利用红外光谱(FT-IR)、光电子能谱(XPS)、ζ电位和浮选溶液化学等方法对不同白云母样品进行了表征。结果表明，柠檬酸可明显抑制白云母的可浮性，在矿浆pH值为6、油酸钠浓度为9.20×10–4 mol/L的条件下，使用4.76×10–5 mol/L柠檬酸，白云母的回收率仅为0.40%。柠檬酸抑制白云母的可浮性主要是柠檬酸在溶液中生成的C6H7O7–和C6H6O72–等离子吸附在白云母表面，阻碍了油酸根等离子的吸附，且这些离子的吸附导致白云母表面ζ电位负向增大，削弱了油酸根等离子在白云母表面的静电吸附及化学吸附作用。此外，C6H7O7–和C6H6O72–等离子含羟基等强烈亲水基团，吸附在白云母表面会使白云母表面强烈亲水，白云母的可浮性大大降低。     

硫酸钙处理含磷废水特性研究

研究工业石膏的主要成分硫酸钙对含磷废水的处理特性.讨论了废水pH、磷的初始含量、处理时间、投加量等参数对处理的影响,并对吸附等温特性进行了探讨.结果表明,硫酸钙对含磷废水具有良好的吸附作用,等温吸附特征与Langmuir方程和Temkin方程比较吻合,其吸附性能在碱性条件下较佳,初始含量对吸附影响明显,吸附规律为随着含量的增加,磷去除率逐渐减小,在磷的初始质量浓度低于20mg·L-1时,去除效果较好,可达到95%以上;随着吸附剂投加量的增加,磷去除率逐渐增大,而吸附容量逐渐减小.     

Mechanism of the Adsorption of Ammonium Ions from Aqueous Solution by a Chinese Natural Zeolite

Abstract

The adsorption of ammonium ions onto a Chinese natural zeolite in an agitated batch adsorber was studied. A trial‐and‐error non‐linear method was developed to examine two widely used isotherms, the Langmuir and Freundlich. The data gained from the adsorption system fitted the Freundlich isotherm better. An ion exchange model, describing the relationship among the total metal ions in the solution, NH₄ ⁺ removed from the solution, and ions initially released from the zeolite, was developed for the adsorption system. In addition, a parameter of the ion exchange potential was defined to describe the adsorption mechanism. Ion exchange was the main mechanism that accounted for the adsorption of ammonium ions onto the Chinese natural zeolite.     

混合脂肪酸钠辅助制备硫酸钙晶须

硫酸钙晶须应用范围广、综合性能优异、性价比高,具有良好的应用前景。以氯化钙为主要原料,添加油酸钠、硬脂酸钠以及油酸钠与硬脂酸钠的混合物作为改性剂,采用常压酸化法制备了长径比高、疏水性能好的硫酸钙晶须。探究了氯化钙浓度、反应时间、反应温度、油酸钠和硬脂酸钠及其混合物的用量等因素对制备的硫酸钙晶须长径比及疏水性的影响,确定了最佳制备条件。采用扫描电镜（SEM）、接触角测量仪、X射线衍射仪（XRD）、红外光谱（FT-IR）及Zeta电位分析等对产品进行了表征。通过实验得到制备硫酸钙晶须的最佳工艺条件：氯化钙溶液质量浓度为0.11 g/mL时,添加与氯化钙等物质的量的浓硫酸4.8 mL,加入4%油酸钠和6%硬脂酸钠混合物（以质量分数计）作为改性剂,在140 ℃油浴锅中加热搅拌1 h。在此工艺条件下,制备的硫酸钙晶须长径比为32~106,接触角可达120.2°。XRD结果表明,所得硫酸钙晶须为半水硫酸钙晶须和二水硫酸钙晶须的混合物。红外光谱和Zeta电位分析表明,油酸钠和硬脂酸钠以化学吸附的形式吸附在晶须表面。当加入油酸钠和硬脂酸钠混合物时,油酸钠和硬脂酸钠共吸附于晶须表面,使得晶须表面吸附的脂肪酸更多,晶须疏水性更强。     

The combined effect of lead ion and sodium silicate in the flotation separation of scheelite from calcite

Flotation separation of scheelite from calcite is difficult because of the existence of the same cation in the minerals and similar physicochemical characteristics. Many studies have been performed to determine the selective depressants for calcite, but the separation of scheelite from calcite is still a big problem. In this article, the flotation separation of scheelite from calcite has been studied by flotation tests. The results show that benzohydroxamic acid has weak collecting ability to both scheelite and calcite. Lead ions can activate the flotation of scheelite and calcite, but the flotation separation of scheelite from calcite can’t be realized. The depressant saline sodium silicate (mixture of sodium silicate and lead ions) has selective depression effect on calcite and the optimum ratio of sodium silicate to lead ions is 3:1. The use of saline sodium silicate as a depressant can achieve the flotation separation of scheelite from calcite. The zeta potential results and adsorption studies showed that the pre-adsorption of saline sodium silicate only interferes with the adsorption of benzohydroxamic acid on calcite surface; this is the main reason for the selective depression effect of saline sodium silicate on calcite.     

Study on flotation performances and adsorption mechanism of 2-carboxyethylphenylphosphinic acid to cassiterite

A novel collector, 2-carboxyethylphenylphosphinic acid (CEPPA), was first used in the flotation of cassiterite. The flotation performances and the adsorption mechanism of CEPPA on cassiterite were investigated by flotation tests, adsorption experiments, zeta potential measurements, Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses. The results indicated that CEPPA had strong collecting power for cassiterite and fluorite over a wide pH range but little on quartz. In the separation of the cassiterite–quartz mixture, a concentrate containing 90.9% SnO₂ was obtained with a recovery of 95.7% at pH 7.0. The cassiterite in the cassiterite–fluorite mixture could be effectively separated using 300 mg/L sodium silicate in conjunction with 60 mg/L CEPPA, and a concentrate with a grade of 90.3% SnO₂ and a recovery of 92.6% was achieved at neutral pH. Zeta potential analysis demonstrated that the adsorption process involved both physical and specific forces. The results of FTIR and XPS further suggested that the four O atoms of CEPPA reacted with the Sn atoms on cassiterite surface, forming a complex which was similar to the Sn–CEPPA precipitate, and hydrogen bonding adsorption could have taken place between the terminal hydroxyl groups and CEPPA anions.     

油酸钠体系下Mg2+对白云母的活化机理研究

针对油酸钠体系下Mg2+对白云母浮选行为的影响进行了研究,结合浮选溶液化学、Zeta电位、XPS等手段探讨了Mg2+与白云母的作用机理。结果表明,Mg2+在碱性条件下可以明显提高白云母的可浮性,并且pH值越大Mg2+对白云母的活化效果越好。当pH=12,油酸钠用量为9.20×10-4 mol/L时,3.44×10-4 mol/L的Mg2+可使白云母的回收率提高到82.20%。 Mg2+活化白云母的根本原因在于：Mg2+可强化油酸根离子在白云母表面的局部正电区域的静电吸附作用,同时可以提高白云母表面铝和硅离子与油酸根离子的反应的机率。此外,白云母表面覆盖的Mg2+可与油酸根离子反应生成疏水的油酸镁。在这三者共同作用下,白云母的可浮性得到了显著的提高。     

Ion‐exchange adsorption of calcium ions from water and geothermal water with modified zeolite A

The modified zeolite A was prepared by a two‐step crystallization method to remove scale‐forming cations from water and geothermal water. The adsorption kinetics, mechanism and thermodynamics were studied. The calcium ion adsorption capacity of the modified zeolite A was 129.3 mg/g (1 mg/g = 10^?3 kg/kg) at 298 K. The adsorption rate was fitted well with pseudo‐second‐order rate model. The adsorption process was controlled by film diffusion at the calcium ion concentration less than 250 mg/L (1 mg/L = 10^?3 kg/m³), and it was controlled by intraparticle diffusion at the concentration larger than 250 mg/L. The calculated mass‐transfer coefficient ranged from 2.23 × 10^?5 to 2.80 × 10^?4cm/s (1 cm/s = 10^?2m/s). Dubinin–Astakhov isotherm model could appropriately describe the adsorption thermodynamic properties when combined with Langmuir model. The adsorption process included not only ion exchange but also complexation between calcium and hydroxyl ions. The adsorption was spontaneous and endothermal. The high adsorption capacity indicates that the modified zeolite A is a suitable adsorption material for scale removal from aqueous solution. © 2014 American Institute of Chemical Engineers AIChE J, 61: 640–654, 2015     

Factors Affecting on the Sorption/Desorption of Eu (III) using Activated Carbon

Abstract

The sorption and desorption of Eu (III) on H‐APC activated carbon using a batch technique has been studied as a function of carbon type, shaking time, initial pH solution, temperature, particle size of carbon, and concentration of the adsorbent and the adsorbate. The influence of different anions and cations on adsorption has been examined. The experimental data have been analyzed by Langmuir, Freundlich, and Temkin sorption isotherm models and the adsorption data for Eu (III) onto activated carbon were better correlated to the Temkin isotherm and the maximum absorption capacities obtained was 46.5 mg g^?1. Anions of phosphate, carbonate, oxalate, and acetate were found to increase the adsorption of Eu (III), whereas nitrate, chloride and all studied cations, potassium, sodium, calcium, magnesium, and aluminum have a negative effect on the adsorption capacity. More than 99% europium adsorbed on H‐APC eluted with 0.5 M HCl solution. The activated carbon prepared from apricot stone using 70% H₃PO₄ could be considered as an adsorbent that has a commercial potential for Eu (III) treatment.     

F-在方解石表面的吸附及其对方解石表面性质的影响

氟元素主要存在于磷矿和萤石等矿物中,这些矿物中都伴生有方解石脉石矿物,在浮选分离的弱酸条件下,矿物表面的F^-会部分溶出并吸附到矿物表面,从而影响矿物表面性质。本文研究了F^-在方解石表面的吸附及其对方解石表面性质的影响机理。结果表明,在矿浆pH 值为5.5时,F^-以化学吸附的方式吸附在方解石表面,随着吸附时间的增加吸附量逐渐增加,90 min时方解石对F^-的吸附达到平衡。在油酸钠(NaOL)为捕收剂时,F^-的存在会降低方解石表面的疏水性。通过Zeta电位测试、溶液化学计算和X射线光电子能谱仪(XPS)分析表明,F^-会和方解石表面的Ca²⁺反应生成CaF₂沉淀,占据方解石表面的Ca位点,降低NaOL在方解石表面的吸附量。     

Synthesis of crosslinked oxidized starch and its adsorption behavior for calcium ion

Cornstarch, after crosslinking with epichlorohydrin (4%, v/w, dry basis of the starch), was oxidized with hydrogen peroxide over the catalyst Cu(II). The newly synthesized products were applied to examine the calcium ion removal activity from water, under various conditions. Removal efficiency of calcium ion from aqueous solution increased proportionally with carboxyl content and the dose of crosslinked oxidized starch in the solution. Ionization of carboxyl groups in starch was necessary for the effective calcium removal. When the pH of the solution was adjusted below 4.0, the starch was no longer an effective calcium‐sequestering agent. Adsorption isotherm models were developed, wherein the best fit was obtained in the Langmuir model. Thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy change (ΔH^θ), the entropy change (ΔS^θ), and free energy change (ΔG^θ) of the adsorption process were calculated with adsorption isotherm data and basic thermodynamic relations. It was assessed that adsorption occurred by strong electrostatic interactions with the negative adsorption enthalpy (ΔH^θ). The regeneration and reusability of oxidized starch were also assessed and were found to retain the adsorption capacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1539–1546, 2006     

Process Intensification: Extraction of Chromium(VI) by Emulsion Liquid Membrane

Abstract

Electroplating is one of the important processes involved in surface finishing and metal deposition for better life of articles and for decoration. Chromium(VI) is the most commonly used metal for electroplating. Thus, the waste water of such industries contains Chromium(VI) ions. Emulsion Liquid Membrane (ELM) separation technique provides a potentially powerful technique for the removal of Chromium(VI) ions from the waste water. In the present study, the effect of different parameters such as pH, different carriers concentration, synergistic effect caused by a mixture of two appropriate carriers concentration, effect of electrostatic surface potential and effects of composition of a dilute polymer solution; which will intensify the extraction efficiency of Chromium(VI); are systematically investigated using Aliquat 336 and tri‐n‐octyl amine as extractant, sorbitan mono‐oleate (span 80) as surfactant, kerosene as membrane phase and sodium hydroxide as stripping solution.     

Study of the retarding mechanism of linear sodium polyphosphates on α-calcium sulfate hemihydrate

Linear sodium polyphosphates possessing different average chain lengths were characterized and studied as retarder for α-calcium sulfate hemihydrate. Their effect on the hydration kinetics of aqueous α-CaSO₄·0.5H₂O pastes was quantified by heat flow calorimetry, mini slump test and determination of time-dependent degree of hydration. Already at very low dosages (0.025% bwob) polyphosphates strongly retard hydration of hemihydrate. The retarding effect decreases with increasing chain length. Interaction between polyphosphates and calcium ions and Ca^2 + concentration dependent formation of insoluble precipitates were studied via pH and turbidity measurements. Additionally, the influence of polyphosphates on individual hydration steps (binder dissolution and gypsum precipitation) was determined. It was found that the working mechanism of polyphosphates mainly relies on a strong decrease of binder dissolution rate while delayed gypsum precipitation from the solution and inhibition of dihydrate crystal growth by adsorption of polyphosphate play a minor role.     

钙芒硝石膏深度提纯工艺的研究

钙芒硝石膏是工业上采用溶浸法生产元明粉的副产尾矿,与脱硫石膏和磷石膏等工业副产石膏相比其杂质含量高、纯度低、利用价值低。采用酸浸-重结晶工艺对钙芒硝石膏进行提纯,通过酸浸去除钙芒硝石膏中的酸溶性杂质,并将二水硫酸钙（DH）脱水转化为无水硫酸钙（AH）,然后控制水化条件,使AH水化为大尺寸的DH晶体,并与小尺寸的酸不溶性杂质分离开来,得到高纯度的二水石膏。研究了硫酸浓度、水化激发剂、液固质量比、反应时间等对石膏提纯的影响。研究结果表明：常压下,在硫酸酸洗液质量分数为35%、反应温度为80 ℃、石膏与硫酸溶液固液质量比为1∶5、酸洗时间为2 h时能有效去除钙芒硝石膏中的酸溶性杂质;在水化硫酸质量分数为5%、硫酸钾质量分数为1.74%、反应温度为25 ℃、固液质量比为1∶6、陈化时间为18 h时能有效去除钙芒硝石膏中酸不溶性杂质,提纯后的石膏纯度可达97%以上。     

Removal of methylene blue from aqueous solution by sorption on lignocellulose-g-poly(acrylic acid)/montmorillonite three-dimensional cross-linked polymeric network hydrogels

Batch lignocellulose-g-poly(acrylic acid)/montmorillonite (LNC-g-PAA/MMT) hydrogel nanocomposites were applied as adsorbents. The nanocomposites were characterized by FTIR, XRD, SEM, and TEM. The results showed that montmorillonite (MMT) could react with the monomers and change the structure of polymeric network of the traditional superabsorbent materials, an exfoliated structure was formed in the nanocomposites. The effect of process parameters such as MMT content (wt%), contact time (t), initial concentration of dye solution (C ₀), adsorption temperature (T), and pH value (pH) of the dye solution for the removal of methylene blue (MB) from aqueous solution were also studied. The results showed that the adsorption capacity for MB increased with increasing contact time, initial dye concentration, and pH value, but decreased with increasing MMT content and temperature. The adsorption kinetics were better described by the pseudo-second-order equation, and their adsorption isotherms were better fitted for the langmuir equation. By introducing 20 wt% MMT into LNC-g-PAA polymeric network, the obtaining hydrogel composite showed the high adsorption capacity 1994.38 mg/g and economic advantage for MB. The desorption studies revealed that the composite provided the potential for regeneration and reuse after MB dye adsorption, which implied that the composite could be regarded as a potential adsorbent for cationic dye MB removal in a wastewater treatment process.