水溶液中氟的吸附平衡模型研究进展

氟是人体必需的微量元素,但高浓度含氟废水对人体和环境会造成很大危害。吸附法是目前最常用的除氟方法,新型吸附材料也成为世界研究热点。吸附平衡模型广泛地应用于水中氟的吸附过程表征,研究这些模型对揭示吸附机理、设计除氟工艺和选择合适的吸附材料具有重要意义。对国内外水中氟吸附的平衡模型及其应用实例综述,其中最常用的是Langmuir和Freundlich平衡模型。由于各种模型都有其各自的优缺点和适用范围,单独使用某一种吸附模型不能精确地表征吸附剂对溶液中氟的吸附作用。今后应从具体的吸附作用机理角度改进氟的吸附平衡模型,或综合采用多种模型来分阶段表征氟的吸附过程,并且建立模型参数之间的联系,提高模型在实际应用中对选择合适吸附材料和最佳吸附工艺条件的指导作用。

矿物浮选吸附平衡模型构建与应用:精准解析矿物表面离子/药剂特征吸附

矿物浮选吸附平衡模型是准确描述矿物浮选过程中所涉及的矿物表面离子/药剂吸附平衡的数学模型,首次实现了矿物表面位点与浮选药剂吸附作用亲和性的量化解析。传统浮选理论对矿物表面作用位点缺乏科学描述,难以阐明浮选药剂的吸附作用能力及平衡状态,新浮选药剂体系开发多以“试错法”“复配法”等经验性方法为主。药剂选择性吸附作为浮选作业的核心机制,若不能准确预测其在各矿物表面的吸附行为,将严重限制浮选工艺智能化控制的发展。本文详细论述了矿物浮选吸附平衡模型的构建原理,以赤铁矿-石英和一水硬铝石-高岭石两个浮选体系为例,通过对少量实验数据的拟合计算,解析出矿物表面活性位点密度Ns、加/去质子反应常数K_(t1)/K_(t2)、药剂吸附常数Kf等矿物浮选特征常数。将解析的矿物浮选特征常数代入到平衡模型中,预测出各条件下矿物表面电性、离子及浮选药剂的吸附量,通过零电点、实验及测试等方法验证了可靠性,形成了矿物浮选过程预测系统的内核算法。该算法对各条件下每种矿物药剂吸附的初步准确预测,可在一定程度上反映其可浮性趋势,有助于缩短浮选工艺开发周期,对矿物表面药剂吸附机理研究、浮选药剂分子设计、浮选工艺流程优化及智能控制等具有重要意义。

稻壳基活性炭对亚甲基蓝吸附平衡与动力学研究

以粮食副产物——稻壳为原料,采用化学活化法制成了微介孔共存的孔隙发达的稻壳基活性炭,此稻壳基活性炭对亚甲基蓝的吸附量可以达到464.8 mg·g-1。通过大量亚甲基蓝吸附实验结果拟合,发现其吸附平衡过程符合Freundlich吸附模型,动力学模型符合准二级吸附动力学模型。通过吸附平衡模型与动力学模型的建立,为此活性炭的实际应用提供理论预测模板。

B．subtilis吸附Cu2+、Zn2+和Cd2+的等温吸附平衡性能研究

从吸附动力学过程着手分析了生物体对重金属离子吸附过程的等温吸附平衡，在一系列简化条件基础上，建立了用于描述这一过程的等温吸附平衡模型。当n=1时，该模型与经典等温吸附平衡模型Langmuir方程具有一致的表达形式。采用最小二乘法求得理论模型中的参数值，针对含Cu^2＋、Zn^2＋和Cd^2＋3种重金属离子的废水，将枯草芽孢杆菌活菌体（Bacillus subtilis）作为吸附剂，进行等温吸附平衡实验．将已知参数的理论模型与实验数据曲线进行比较。理论曲线能够很好的吻合实验数据曲线的走向趋势，证明了该模型的合理性及可用性。

两种大型真菌子实体对Cd^(2+)的生物吸附特性

对两种多孔菌科大型真菌槐栓菌(Trametes robiniophila)和木蹄层孔菌(Fomes fomentarius)子实体生物吸附Cd2+的影响因素(包括吸附剂用量、初始pH、吸附时间、初始Cd2+浓度)和吸附特性进行分析。结果表明,槐栓菌和木蹄层孔菌对低浓度的Cd2+(10 mg/L)吸附的最适pH为6;Cd2+的去除率随吸附剂用量和吸附时间的增加而增大,槐栓菌和木蹄层孔菌均在吸附剂用量为2g/L时达到吸附平衡,槐栓菌在吸附时间为30 min时达到吸附平衡,而木蹄层孔菌在吸附时间为60 min时达到吸附平衡;槐栓菌和木蹄层孔菌对10 mg/L Cd2+的最大去除率分别为98%和94%。Langmuir等温吸附平衡模型比Freundlich等温吸附平衡模型能更好的拟合两种大型真菌对Cd2+的吸附过程;槐栓菌和木蹄层孔菌对10 mg/L Cd2+的最大吸附量分别为17.40mg/g和8.91 mg/g。对实验数据进行动力学模型拟合可知,两种大型真菌对Cd2+的生物吸附过程均符合准二阶动力学模型。槐栓菌和木蹄层孔菌生物吸附低浓度Cd2+的化学反应机理可能为离子交换。

硫酸铝浸渍活性氧化铝球吸附饮水中的高浓度氟

硫酸铝浸渍活性氧化铝球(AIAA)是饮水除氟领域常用的吸附剂,它对氟的吸附性能受各种因素的影响。静态吸附通过改变AIAA质量与氟溶液体积比(m(AIAA):V)(2～40 g.L-1)、氟的质量浓度(ρ(F))(2～100 mg.L-1)、pH值(4～10)、温度(11～33℃)和时间等实验参数,研究这些因素对AIAA吸附除氟的影响。在11～33℃的温度范围内、pH值变化为4～10之间时,当m(AIAA):V为20 g.L-1,3 h内处理ρ(F)为10 mg.L-1水溶液其氟的去除率可达90%以上,足以保证其满足饮用水的含氟标准。利用Langmuir和Freundlich模型对吸附数据进行了拟合研究,结果表明:在ρ(F)为2～100 mg.L-1、pH=5～10、温度11～33℃范围内,Langmuir线性拟合模型是最优拟合方式;而当溶液氟质量浓度为2～1 000 mg.L-1或2～100 mg.L-1且pH为4时,Freundlich非线性拟合模型是最优拟合方式。AIAA吸附容量随溶液氟质量浓度升高、pH降低及温度升高逐渐增加。

孔雀石绿在煤质活性炭和桃核活性炭上吸附行为的理论分析

选取由无烟煤和桃核制备的商用活性炭,考察了25~45℃,初始浓度60~200 mg/L下,它们对水溶液中孔雀石绿的吸附时间和平衡吸附量.通过准一级动力学模型、准二级动力学模型和粒子内扩散动力学模型,分析了吸附动力学;通过Langmuir模型和Freundlich模型对吸附平衡进行了研究.结果表明,虽然煤质炭和桃核炭对孔雀石绿的吸附行为不同,但是准二级动力学模型和Langmuir模型均可以拟合实验数据,这说明它们对孔雀石绿的吸附机理是相同的.通过关联孔结构参数,发现活性炭的比表面积是影响吸附性能的关键因素.

Equilibrium Modeling for Hydrogen Isotope Separation by Cryogenic Adsorption

The separation of hydrogen and deuterium by cryogenic adsorption was conducted, using the molecular sieve 5A as adsorbent, helium as the carder gas in a fixed column. The breakthrough curves of hydrogen, deuterium and the mixture of two components in helium carder gas were measured, a separation factor, approximately 2, for the hydrogen-deuterium binary mixture was obtained. The equilibrium model was built for simulation of the concentration distribution for single hydrogen, deuterium and their mixture with helium carder in the fixed column, and the simulation compared well with the experimental results.

Adsorption Equilibrium of Volatile in Condensed Mode Polyethylene Process

In this paper n-hexane is chosen as typical volatile in condensed mode polymerization process, and the adsorption equilibrium of volatile in polyethylene particles is studied through experiments at different temperatures, pressures and particle diameters. It is found that more adsorbed quantity of volatile at equilibrium can be obtained with lower temperature, higher pressure and smaller particle diameter. Under polymerization conditions, the adsorbed quantity at equilibrium is more strongly affected by temperature than by pressure, and if the diameter distribution of particles is very wide the effect of diameter on the adsorbed quantity must be taken into consideration. With theoretical analyses a model is proposed for calculating the adsorbed quantity of volatile at equilibrium.

Development of a first-order kinetics-based model for the adsorption of nickel onto peat

The use of peat for the removal of nickel from aqueous solutions has been investigated at various pH values by means of static conditions. The present research shows that the ability of Ni to bind to peat increases as the pH value increases. The solutions reach adsorption equilibrium rapidly. A reasonable kinetic model, first-order in nickel concentration, has been developed and fitted to the adsorption of nickel （Ⅱ） onto peat. The first-order model provides a good correlation to the experimental data. The characteristic parameters of the Langmuir isotherm were determined at various temperatures. The relationship between kinetics and equilibrium isotherms was established through the forward- and backward-rate-constants, k~ and k2, and the equilibrium constant, K.

Removal of aqueous Ni(Ⅱ) with carbonized leaf powder: Kinetics and equilibrium

Nickel is a heavy metal which has the potential threaten to human＇s health and attracts public concern recently. The carbonized leaf powder is expected as suitable adsorbent for Ni（II） removal became of the composition of some beneficial groups. In this work, carbonized leaf powder was evaluated for its adsorption performance towards Ni（II）. According to the results, adsorbent component, dosage, initial solute concentration, solution pH, temperature and contact time can significantly affect the efficiency of Ni（II） removal. Sips model fits the test results best, and the adsorption capacity towards Ni（II） is determined around 37.62 mg/g. The thermodynamic behaviors reveal the endothermic and spontaneous nature of the adsorption. The free adsorption energy （fluctuate around 8 kJ/mol） predicted by D-R model indicates that the adsorption capacity originated from both physical and chemical adsorption. Room temperature （15-25 ℃） is suitable for Ni（II） removal as well as low energy consumption for temperature enhancement. Further conclusions about the mechanism of chemical adsorption are obtained through analysis of the FT-IR test and XRD spectra, which indicates that the adsorption process occurs predominantly between amine, carbonate, phosphate and nickel ions.

Adsorption equilibrium for Z-ligustilide on C18-bonded silica from supercritical carbon dioxide

Adsorption equilibrium is of great importance for the preparative supercritical fluid chromatography(pre-SFC) in defining supercritical adsorption behavior and the industrial amplification.This paper presents adsorption isotherms of Z-ligustilide from supercritical carbon dioxide(SC-CO_2) on C18-bonded silica.Adsorption behavior was studied at 305.15 K,313.15 K and 323.15 K with SC-CO_2 density varying from 0.687 g·cm^(-3) to0.863 g·cm^(-3) with the elution by characteristic points(ECP) method.The adsorption amount of Z-ligustilide from SC-CO_2 on C18-bonded silica decreased with the increasing density of the mobile phase as well as the increasing temperature.Adsorption equilibrium data were fitted by Langmuir and Freundlich isotherm models,and the Langmuir isotherm model performed better for describing the whole adsorption process on the column.The monolayer saturation adsorption capacity of Z-ligustilide is in the range of 3.0 × 10^(-4) mg·cm^(-3) to5.5 × 10^(-4) mg·cm^(-3) with an average value of 4.0 × 10^(-4) mg·cm^(-3).

Error Analysis of Adsorption Isotherm Models for Acid Dyes onto Bamboo Derived Activated Carbon

High surface area activated carbons were produced by thermal activation of waste bamboo scaffolding with phosphoric acid.Single component equilibrium dye adsorption was conducted on the carbons produced and compared with a commercially available carbon.Two acid dyes with different molecular sizes,namely Acid Yellow 117(AY117) and Acid Blue 25(AB25),were used to evaluate the adsorption capacity of the produced carbons.It was found that the dye with smaller molecular size,AB 25,was readily adsorbed onto the produced carbon,nearly three times higher than a commercially available carbon,while the larger size dye,AY117,showed little adsorption.The experimental data were analyzed using isotherm equations including Langmuir,Freundlich,Tempkin,Toth,Redlich-Peterson and Sips equations.The equilibrium data were then analyzed using five different non-linear error analysis methods.

Heavy metals adsorption by banana peels micro-powder: Equilibrium modeling by non-linear models

In this study the copper and lead adsorption efficiency onto banana peels powder was investigated. The agroindustrial waste recovery represents one of the Circular Economy pillars. In the view of the synthesis of an environmentally friendly adsorbent material, the powder was used without any preliminary chemical or thermal activation, but only after simple washing, drying and grinding. The bio-adsorbent was characterized by the FTIR technique and tested in batch mode on synthetic aqueous solutions containing Pb and Cu in the range 10–90 mg·L^(-1). A selection of two(Langmuir, Freundlich) and three(Sips, Redlich–Peterson, Koble–Corrigan) parameter isotherm models was chosen to fit adsorption equilibrium data by non-linear regression procedure. The best fit isotherm model was selected relying on the error function with the lowest average percentage error(APE) value, among those characterized by the highest R^2 values. As expected, the three-parameter models are found to better represent both metals bio-adsorption, with APE and R^2 values always lower and higher, respectively, than the corresponding values obtained for the two-parameter models.

Two-state energy model and experimental study of coal adsorb methane

There are two states of methane existing in coal, free methane and adsorptive methane. The two states of methane exchanged with each other which need the energy exchange with outside. It is released heat when methane adsorption on coal, instead of absorbed heat. According to the gas molecules Boltzmann energy distribution, is obtained the equilibrium equations of the two states of methane in coal, as well as the heat of adsorption equation when exchanged into each other. At the same time, high temperature experiments of methane adsorption on coal have been certificated to the theoretical model. At last the experimental results presented that： the two-state energy model could be accurately described the distribution of the two states of methane in the coal; the adsorption heat is related to the initial equilibrium state of methane adsorption; the adsorption heats are different with different coal ranks.

Adsorption of 2-naphthalenesulfonic acid/sulfuric acid/sulfurous acid from aqueous solution by iron-impregnated weakly basic resin：Equilibrium and model

Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid(NSA), sulfuric acid and sulfurous acid from their solution at 298 K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorption models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute competitive adsorption behavior.

Adsorption of Naphthol Green B on unburned carbon：2-and3-parameter linear and non-linear equilibrium modelling

The study deals with adsorption of Naphthol Green B on two unburned carbons and the parent coal,from which the UCs have been created in a fluidised-bed power station.Particular attention has been paid to the adsorption equilibrium modelling:experimental data has been analysed using 2-parameter(Langmuir,Freundlich) and3-parameter(Redlich-Peterson) isotherms — both linear and non-linear regressions have been used for the estimation of the isotherm parameters.In the case of both UCs,the Langmuir isotherm model provides the worst fit,whereas 2-parameter Freundlich and 3-parameter Redlich-Peterson models are both good,from which 3-parameter Redlich-Peterson isotherm provides slightly better results(despite the penalty used for the higher number of parameters).In the case of both UCs,the linear regression of Freundlich and Redlich-Peterson models provides good results(comparable with non-linear regressions).Unlike both UCs,the best fit of the experimental data from the adsorption on the coal has been achieved by the Langmuir isotherm model.The results based on the Freundlich or Redlich-Peterson model were(in this case) somewhat worse.

Comparative Study of the Adsorption Thermodynamic Parameters Estimated through Different Approaches

The equilibrium constant （K0）, change in free energy （△G）, enthalpy （△H） and entropy （△S） of ammonium adsorption by a Cuban natural zeolite were estimated at the temperatures of 25, 35, 45 and 55℃ using extensively used approaches. Equilibrium data were obtained in the concentration range 50-1,200 mg·L-1 of ammonium and used in the estimation of thermodynamic parameters. Freundlich＇s isotherm model was found as with the best adjustment to equilibrium data at 25, 45 and 55℃, whereas, Redlich-Peterson＇s model had a better performance at 35 ℃. A discontinuous and unusual behavior was observed on adsorption capacity of the zeolite, with an increase from 25 ℃ to 35 ℃ followed by a decrease from 35℃ to 55 ℃. K0 values presented differences that reached up to 105 from one methodology to other. Depending on the method considered, AS results indicated both increase or decrease in system degree of disorder and △G indicated both physisorption or chemisorption process, proving the poor correlation between the estimation proceedings of such important data. The results from Gaines and Thomas method were recognized as the most correlated to calorimetric studies, as well as to equilibrium data and observations related to system entropy.

Removal of Pb(Ⅱ) ions from aqueous solutions by litchi pericarp and its leachate

The adsorption capacity of Pb(Ⅱ) on litchi pericarps was investigated as a function of temperature,pH,and adsorbent dose using batch experiments.The experimental data obtained were evaluated using adsorption equilibrium isotherms and a kinetic model.Additionally,the removal of Pb(Ⅱ) in leachate of litchi pericarps was also evaluated.The results show that litchi pericarps exhibit a high adsorption capacity to Pb(Ⅱ),with the maximum removal efficiency occurring at a temperature of 25 ℃,a pH of 6.0-7.0 and an adsorbent dosage of 10 g/L.Langmuir and Freundlich isotherms and the pseudo-second-order kinetic model can all fit the equilibrium adsorption satisfactorily,with correlation coefficients(R^2) of 0.9935,0.9918 and 1.0,respectively.An average removal efficiency of 66.65% is found for Pb(Ⅱ) in leachate of litchi pericarps.