Removal of 2.4-dichloro phenoxyacetic acid from aqueous solution by adsorption on activated carbon. A kinetic study

The sorption of 2.4-dichloro phenoxyacetic acid (2.4-D) on two different activated carbons was determined using the batch equilibration technique. The calculated slopes of the Freundlich sorption isotherms were significantly less than 1. The (K) values were higher for the activated carbon which has the higher specific surface, and increased with NaCl concentration. The rate of attaining equilibrium of 2.4-D increased with a decrease in absorbent concentration. Dynamic modelling of the adsorption showed that a first order reversible kinetic model was followed for the adsorption process. The overall rate constant K′, the adsorption rate K₁, the desorption rate constant K₂, and the equilibrium constant K_c for the adsorption process were calculated.     

Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds: Kinetics,isotherms, mass transfer,thermodynamics and process design

The adsorption of Basic Magenta II onto H₂SO₄ activated immature Gossypium hirsutum seeds was analysed using Ho, modified Freundlich, Sobkowsk–Czerwi, Blanchard, Elovich, Avrami, and modified Ritchie kinetic models by nonlinear regression-sum of normalized errors analysis. The goodness of fit was evaluated with coefficient of determination and root mean square error. The good agreement of experimental data to Avrami second-order model indicated that the mechanism of adsorption followed multiple kinetic orders. The Avrami second-order mechanism was applied to predict the rate constant of sorption and the equilibrium capacity and subsequently the obtained equilibrium adsorption capacities were utilized to find the equilibrium concentrations. Langmuir, Freundlich, Temkin, Sips and Hill isotherms were investigated to understand the nature of adsorption with the help of nonlinear regression analysis. Both Sips and Hill isotherms were best fit to the adsorption equilibrium data showing the homogeneous adsorption on the heterogeneous surface of carbon and the positive co-operative manifestations of the Basic Magenta II molecules. The mass transfer study depicted the details such as mass transfer coefficient, intra-particle diffusion rate, pore diffusion coefficient, and film diffusion coefficient. The adsorption process was found to be controlled by film diffusion. The thermodynamic parameters like, Gibbs free energy change, enthalpy change, entropy change and isosteric heat of adsorption confirmed the endothermic, feasible and spontaneous nature of adsorption. A single stage batch adsorber was designed using Sips isotherm constants to estimate the amount of carbon required for desired purification.     

Synthesis, characterization and study of arsenate adsorption from aqueous solution by α- and δ-phase manganese dioxide nanoadsorbents

Single-phase α-MnO₂ nanorods and δ-MnO₂ nano-fiber clumps were synthesized using manganese pentahydrate in an aqueous solution. These nanomaterials were characterized using the Transmission Electron Microscope (TEM), Field Emission Scanning Electron Microscope (FE-SEM), Powder X-ray diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N₂ adsorption). The structural analysis shows that α-MnO₂ (2×2 tunnel structure) has the form of needle-shaped nanorods and δ-MnO₂ (2D-layered structure) consists of fine needle-like fibers arranged in ball-like aggregates. Batch adsorption experiments were carried out to determine the effect of pH on adsorption kinetics and adsorption capacity for the removal of As(V) from aqueous solution onto these two types of nanoadsorbents. The adsorption capacity of As(V) was found to be highly pH dependent. The adsorption of As(V) onto α-MnO₂ reached equilibrium more rapidly with higher adsorption capacity compared to δ-MnO₂.     

Isotherm, kinetic and thermodynamic studies of lead and copper uptake by H2SO4 modified chitosan

The kinetic and thermodynamic adsorption and adsorption isotherms of Pb(II) and Cu(II) ions onto H₂SO₄ modified chitosan were studied in a batch adsorption system. The experimental results were fitted using Freundlich, Langmuir and Dubinin–Radushkevich isotherms; the Langmuir isotherm showed the best conformity to the equilibrium data. The pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were employed to analyze the kinetic data. The adsorption behavior of Pb(II) and Cu(II) was best described by the pseudo-second order model. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined; the adsorption process was found to be both spontaneous and exothermic. No physical damage to the adsorbents was observed after three cycles of adsorption/desorption using EDTA and HCl as eluents. The mechanistic pathway of the Pb(II) and Cu(II) uptake was examined by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The equilibrium parameter (R_L) indicated that chitosan–H₂SO₄ was favorable for Pb(II) and Cu(II) adsorption.     

Enhanced adsorption of radioactive strontium ions from aqueous solution by H2O2-modified attapulgite

Effective adsorption of Sr(II) onto H₂O₂-modified attapulgite in aqueous solution was investigated about kinetics and isothermal equilibrium adsorption. The adsorption equilibrium process of Sr(II) on adsorbents reached about 8 h at 40 °C. The adsorption kinetics followed the pseudo-second order equation and the isothermal adsorption data were fit well with the Langmuir isotherm model. The enhanced adsorption mechanism of H₂O₂-modified attapulgite for Sr(II) in aqueous solution was expatiated in detail. The H₂O₂ treatment for attapulgite is effective and as-made adsorbents can be applied for removal of Sr(II) in radioactive waste water.

     

A dynamic column breakthrough apparatus for adsorption capacity measurements with quantitative uncertainties

A dynamic column breakthrough (DCB) apparatus was used to study the separation of CH₄+N₂ gas mixtures using two zeolites, H⁺-mordenite and 13X, at temperatures of (229.2 and 301.9)?K and pressures to 792.9?kPa. The apparatus is not limited to the study of dilute adsorbates within inert carrier gases because the instrumentation allows the effluent flow rate to be measured accurately: a method for correcting apparent effluent mass flow readings for large changes in effluent composition is described. The mathematical framework used to determine equilibrium adsorption capacities from the dynamic adsorption experiments is presented and includes a method for estimating quantitatively the uncertainties of the measured capacities. Dynamic adsorption experiments were conducted with pure CH₄, pure N₂ and equimolar CH₄+N₂ mixtures, and the results were compared with similar static adsorption experiments reported in the literature. The 13X zeolite had the greater adsorption capacity for both CH₄ and N₂. At 792?kPa the equilibrium capacities of the 13X zeolite increased from 2.13±0.14?mmol?g^?1 for CH₄ and 1.36±0.10?mmol?g^?1 for N₂ at 301.9?K to 3.97±0.19?mmol?g^?1 for CH₄ and 3.33±0.12?mmol?g^?1 for N₂ at 229.2?K. Both zeolites preferentially adsorbed CH₄; however, the mordenite had a greater equilibrium selectivity of 3.5±0.4 at 301.9?K. Equilibrium selectivities inferred from pure fluid capacities using the Ideal Adsorbed Solution theory were limited by the accuracy of the literature pure fluid Toth models. Equilibrium capacities with quantitative uncertainties derived directly from DCB measurements without reference to a dynamic model should help increase the accuracy of mass transfer parameters extracted by the regression of such models to time dependent data.     

Carboxymethyl Chitosan-Fe3O4 Nanoparticles: Preparation and Adsorption Behavior toward Zn2+ Ions

A novel magnetic nanoadsorbent was prepared by the covalent binding of carboxymethyl chitosan (CMC) onto the surface of Fe₃O₄ magnetic nanoparticles, which was developed using a coprecipitating method. This nanoadsorbent was characterized by transmission electron microscopy (TEM) and X-ray diffraction patterns (XRD), etc. Moreover, the adsorption performance of the nanoadsorbent toward Zn²⁺ ions was investigated. The results showed that the mean diameter of the magnetic nanoadsorbent was 18 nm and the amount of CMC was about 5%. The nanoadsorbent showed high efficiency for the removal of Zn²⁺ ions. The adsorption rate was so rapid that the equilibrium was achieved within 2 min. The isotherm adsorption data obeyed the Langmuir model, with a maximum adsorption capacity of 20.4 mg·g^?1 and an adsorption equilibrium constant of 0.0314 L·mg^?1. The thermodynamic calculations indicated that the adsorption process was exothermic and that the enthalpy change was ?5.68 kJ·mol^?1.     

源自密胺基多孔聚合物的富氮微孔炭及选择性吸附CO_2

以间苯二甲醛和三聚氰胺为原料,通过Schiff碱缩合反应合成了密胺基多孔聚合物(POP),经高温炭化后得到富氮微孔炭(NMC).利用N2吸脱附和傅里叶变换红外(FTIR)光谱表征了POP和炭化后产物NMC的结构和组成,与POP相比,NMC的官能团数量减少,比表面积和微孔孔容大幅增加.元素分析表明NMC含氮量高达12.5%(w).采用体积法测定了CO2、CH4和N2在NMC上的单组分吸附平衡等温线,NMC展示出良好的CO2吸附性能,298 K、100 kPa下CO2平衡吸附量可达2.34 mmol·g-1.双位Langmuir(DSL)模型和单位Langmuir(SSL)模型分别较好地描述了CO2、CH4和N2在NMC上的吸附平衡数据,在此基础上,应用理想吸附溶液理论(IAST)预测了双组分混合气在NMC上的吸附等温线,结果表明NMC对CO2-N2和CO2-CH4有非常高的CO2吸附选择性,分别为144.9和12.8.     

Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite

Adsorptive removal of dichloromethane, chloroform, and carbon tetrachloride from aqueous solutions at 25 °C by activated carbon (AC) that was loaded with cerium oxide nanoparticles (CeO₂-NP/AC) was investigated. The developed adsorbent was characterized by scanning electron microscope (SEM), FTIR spectrophotometer, X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The effect of contact time, initial concentration, and the adsorbent dosage were also studied. The equilibrium and kinetics of adsorption were studied in a batch-type adsorption system, and the equilibrium experimental data were analyzed using Langmuir, Freundlich, and Temkin isotherm models. Freundlich adsorption isotherm showed the best fit for the equilibrium adsorption data. Three adsorption kinetic models, pseudo first- and second-order, and intraparticle diffusion models were applied to test the kinetic data. Kinetic characterization of the adsorption process onto CeO₂-NP/AC is well-described by the pseudo second-order model, and the adsorption best-fit by the intraparticle diffusion model. Our study shows that at optimum conditions, 82.72%, 99.40% and 89.42% of dichloromethane, chloroform, and tetrachloride, respectively, were removed by CeO₂-NP/AC, at concentration between 0.25 and 5.00 g/L.     

Polymeric Adsorption of Methylene Blue in TiO2 Colloids—Highly Sensitive Thermochromism and Selective Photocatalysis

The polymeric adsorption of methylene blue (MB) on a TiO₂ surface is reported. The MB molecule on the TiO₂ surface mainly exists as the H‐trimeric adsorption state, which results in the MB@TiO₂ polymeric sol. The trimeric adsorption leads to a remarkable “blueshift” of visible‐light adsorption of MB. Electrostatic attraction is important for trimeric adsorption of MB on TiO₂ surfaces. The trimer–monomer equilibrium is highly sensitive on temperature changes, showing an interesting reversible thermochromism. The MB@TiO₂ polymeric sol can be photodegraded under UV illumination without destroying the equilibrium of trimer–monomer. Compared with anionic methyl orange, the TiO₂ colloid hydrosol shows highly selective photocatalysis of MB and other cationic dyes, including crystal violet, methylene green, and victoria blue B. The MB@TiO₂ polymeric sol is stable under visible‐light illumination because interfacial transfer of electrons does not exist between MB and TiO₂.     

Hierarchically structured β-Ni(OH)2 clusters: a uniquely efficient aqueous phase pollutant adsorbent for multiple anionic dyes and heavy metal ions

Herein, for the first time mesostructured 3D self-assembled β-Ni(OH)₂ clusters with high surface area, large pore size, and uniform flower-like morphology have been synthesized by implementing a novel microwave heating method, using glycine as the cappant. The β-Ni(OH)₂ clusters are subjected to aqueous phase pollutant adsorption for multiple anionic dyes [congo red (CR), acid fuchsin (AF) and acid red 27 (AR-27)], and heavy metal ions [divalent lead ion, Pb(II) and divalent cadmium ion, Cd(II)]. The comprehensive kinetic analyses show that the adsorption of dyes and metal ions on the β-Ni(OH)₂ cluster surface occurs by chemisorption (pseudo-second order kinetics) and intraparticle diffusion (film and pore diffusion) processes. Further, the β-Ni(OH)₂ clusters show excellent equilibrium adsorption capacity for all the anionic dyes and metal ions. The equilibrium isotherm data show homogenous distribution of CR and AF dyes, and heterogeneous distribution of AR-27 dye on the β-Ni(OH)₂ surface. The excellent adsorption efficiency is attributed to the microwave-induced highly hydroxylated rippled 2D surface, open pore architecture, and suitable pore distribution of the β-Ni(OH)₂ clusters, which collectively cause strong hydrogen bonding between the cluster surface and anionic dyes as well as metal ions.     

2-chlorophenol sorption from aqueous solution using granular activated carbon and polymeric adsorbents

Adsorption equilibrium and kinetics of 2-chlorophenol (2-CP) one of the chlorophenols (CPs) onto bituminous coal based Filtrasorb-400 grade granular activated carbon and three different types of polymeric adsorbents were studied in aqueous solution in a batch system. Langmuir isotherm models were applied to experimental equilibrium data of 2-CP adsorption. Equilibrium data fitted very well to the Langmuir equilibrium models of 2-CP. Adsorbent monolayer capacity Q Langmuir constant b and adsorption rate constants k _a were evaluated. 2-CP adsorption using GAC is very rapid in the first hour of contact where 70–80% of the adsorbate is removed by GAC followed by a slow approach to equilibrium. Whereas in case of polymeric adsorbents 60–65% of the adsorbate is removed in the first 30 min which is then followed by a slow approach to equilibrium. The order of adsorption of 2-CP on different adsorbents used in the study is found to be in following order: F-400 > XAD-1180 > XAD-4 > XAD-7HP.     

Adsorption and separation of carbon dioxide and methane in new zeolites using the Grand Canonical Monte Carlo method

The adsorption and separation behaviors of CO₂ and CH₄ in new siliceous zeolites (IFO, JSR, OKO, SEW) were simulated using the Grand Canonical Monte Carlo method in the paper. The adsorption isotherms for pure components and binary mixtures of CO₂ and CH₄ in four siliceous zeolites were obtained. The adsorption thermodynamic properties including Gibb’s free energy change, enthalpy change and entropy change were investigated. The results demonstrate that the adsorbed amount of pure components increases with an increase in pressure, and larger pore volume and surface area are beneficial to improve the adsorption capacity. The adsorption amount of CO₂ and CH₄ in the JSR zeolite is 7.08 and 2.27 mmol g^?1 at 1000 kPa, respectively. In view of the thermodynamic results, the new siliceous zeolites show a higher affinity for CO₂. The adsorption capacities of CO₂ in all zeolites were five times more than those of CH₄ in binary mixtures based on the ratios of equilibrium adsorption capacity. Considering the adsorption uptake and selectivity for CO₂/CH₄, the JSR zeolite is a good candidate for the separation of CO₂/CH₄ at low pressure.     

In situ synthesis of MnO<Subscript>2</Subscript>-loaded biocomposite based on microcrystalline cellulose for Pb<Superscript>2+</Superscript> removal from wastewater

We fabricated a new MnO₂-loaded biocomposite based on microcrystalline cellulose (MCC–MnO₂) by an in situ synthesis method and investigated its adsorption behavior and mechanism for Pb²⁺ removal from aqueous medium. As-prepared MCC–MnO₂ was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) analyses. The effects of pH value, initial Pb²⁺ concentration, contact time, and solution temperature on the uptake of Pb²⁺ onto MCC–MnO₂ were investigated using a batch system. Adsorption equilibrium could be achieved in 3 h for various studied initial concentrations, and a pseudo-second-order model could fit the adsorption behavior well. The equilibrium data could be well described by the Langmuir isotherm model, and the maximum monolayer adsorption capacity of MCC–MnO₂ (with 7.98% MnO₂ loading) for Pb²⁺ was estimated to be 247.5 mg/g at 313 K. Thermodynamic studies indicated a spontaneous and endothermic adsorption process. X-ray photoelectron spectroscopy (XPS) was used to analyze the adsorption mechanism, revealing that the chemical speciation of Pb²⁺ on MCC–MnO₂ was similar to the compound PbO. Moreover, no variations in the valence of Mn were observed after adsorbing Pb²⁺. The regeneration study showed that the adsorption capacity retained about 89.6% of its initial value at the fifth sequential regeneration cycle, indicating that this material is an efficient and renewable hybrid adsorbent for Pb²⁺ removal.     

Amin-functionalized magnetic-silica core-shell nanoparticles for removal of Hg2+ from aqueous solution

Magnetic nanoparticles with monodisperse shape and size were prepared by a simple method and covered by silica. The prepared core-shell Fe₃O₄@silica nanoparticles were functionalized by amino groups and characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. The synthesized nanoparticles were employed as an adsorbent for removal of Hg²⁺ from aqueous solutions, and the adsorption phenomena were studied from both equilibrium and kinetic point of views. The adsorption equilibriums were analyzed using different isotherm models and correlation coefficients were determined for each isotherm. The experimental data were fitted to the Langmuir–Freundlich isotherm better than other isotherms. The adsorption kinetics was tested for the pseudo-first-order, pseudo-second-order and Elovich kinetic models at different initial concentrations of the adsorbate. The pseudo-second-order kinetic model describes the kinetics of the adsorption process for amino functionalized adsorbents. The maximum adsorption occurred at pH 5.7 and the adsorption capacity for Fe₃O₄@silica-NH₂ toward Hg²⁺ was as high as 126.7 mg/g which was near four times more than unmodified silica adsorbent.     

Adsorption equilibria of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> in cation-exchanged zeolites 13X

Ion-exchange with different cations (Na⁺, NH₄ ⁺, Li⁺, Ba²⁺ and Fe³⁺) was performed in binderless 13X zeolite pellets. Original and cation-exchanged samples were characterized by thermogravimetric analysis coupled with mass spectrometry (inert atmosphere), X-ray powder diffraction and N₂ adsorption/desorption isotherms at 77 K. Despite the presence of other cations than Na (as revealed in TG-MS), crystalline structure and textural properties were not significantly altered upon ion-exchange. Single component equilibrium adsorption isotherms of carbon dioxide (CO₂) and methane (CH₄) were measured for all samples up to 10 bar at 298 and 348 K using a magnetic suspension balance. All of these isotherms are type Ia and maximum adsorption capacities decrease in the order Li > Na > NH₄–Ba > Fe for CO₂ and NH₄–Na > Li > Ba for CH₄. In addition to that, equilibrium adsorption data were measured for CO₂/CH₄ mixtures for representative compositions of biogas (50 % each gas, in vol.) and natural gas (30 %/70 %, in vol.) in order to assess CO₂ selectivity in such scenarios. The application of the Extended Sips Model for samples BaX and NaX led to an overall better agreement with experimental data of binary gas adsorption as compared to the Extended Langmuir Model. Fresh sample LiX show promise to be a better adsorption than NaX for pressure swing separation (CO₂/CH₄), due to its higher working capacity, selectivity and lower adsorption enthalpy. Nevertheless, cation stability for both this samples and NH₄X should be further investigated.     

铁脂质体/水分配系数测定及影响因素考察

基于PAF-301分子模型通过Li 掺杂或B取代等模式设计了几种新型多孔芳香骨架(PAFs)材料, 采用量子力学和分子力学方法对新材料的储氢性能进行研究. 由量子力学计算得到了不同分子片段与H₂之间的结合能, 并结合DDEC方法计算了各分子片段的原子电荷分布. 利用巨正则蒙特卡洛(GCMC)模拟方法计算了77和298 K下H₂在不同PAFs材料中的吸附平衡性质. 结果表明, H₂直接与苯环的结合能较低, 但掺杂Li 原子能够提高H₂与六元环的结合能, 同时Li 原子体现出较高的正电性质, B原子取代苯环中的两个C原子后, 使得原有C原子电负性增强; 77 K下PAF-301Li 具有最高的储氢性能, 而PAF-C₄B₂H₄-Li₂-Si 和PAF-C₄B₂H₄-Li₂-Ge体现出较好的常温储氢性能, 各种材料的常温储氢性能远低于其低温储氢性能. 通过77 K下H₂在PAFs材料中的等位能面分布和吸附平衡质心密度分布对H₂在PAFs 材料中的优先吸附位置进行分析, 发现在PAF-301 和PAF-301Li 骨架中, 由于中心能量较低的等位能区域范围较宽, H₂在其中存在四个明显的吸附高密度分布区域, 而其它三种PAFs晶胞中心能量较低的等位能区域范围较窄, 使得H₂在其中只存在两个明显的吸附高密度分布区域.     

Synthesis,characterization and CO2 adsorption of NaA,NaX and NaZSM-5 from rice husk ash

NaA, NaX and NaZSM-5 zeolites were prepared by using silica extracted from rice hull ash as a raw material, and they were investigated for CO₂ adsorption performance as an adsorbent in order to solve the problem of suppressing the global warming. Three zeolites were synthesized by hydrothermal methods with seed technology, and a series of characterization methods, including XRD, FTIR, nitrogen adsorption-desorption and SEM, were used to demonstrate their advantages compared to traditional hydrothermal methods. The maximum equilibrium adsorption capacity of NaA-RS, NaX-RS and NaZSM-5-RS was 1.46, 3.12 and 2.20 mmol/g at 0 °C and 101.3 kPa, respectively. The CO₂ and N₂ adsorption isotherms recorded at different temperatures were perfectly fitted by the Dual-site Langmuir model. The CO₂/N₂ selectivity and Henry's law constants were calculated to demonstrate that the samples have a stronger affinity for CO₂, especially at low pressures. The isosteric heat of CO₂ and N₂ adsorption of the three zeolites was calculated, which was indicated that they were in an excellent potential for adsorption and separation of CO₂ in industrial flue gas.     

Enhanced adsorption of atrazine from aqueous solution by molecularly imprinted TiO2 film

TiO₂ film imprinted by atrazine molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted TiO₂ film was characterized by scanning electron microscopy and cyclic voltammetry, and the atrazine adsorption was investigated by quartz crystal microbalance (QCM) technique. In comparison with non-imprinted TiO₂ film, the molecularly imprinted TiO₂ film exhibits high selectivity for atrazine, better reversibility and a much higher adsorption capacity for the target molecule, the adsorption equilibrium constant estimated from the in situ frequency measurement is about 6.7 × 10⁴ M⁻¹, which is thirteen times higher than that obtained on non-imprinted TiO₂ film.     

Synthesis and application studies of chitosan acryloylthiourea derivative for the separation of rare earth elements

The adsorption behaviors of lanthanum (III) from an aqueous chloride medium, using Chitosan acryloylthiourea (CATU) derivative, were studied using an equilibrium batch technique. Here, the chemical modification of chitosan is of interest because the modification would not change the fundamental skeleton of chitosan, would keep the original physicochemical and biochemical properties, and finally would bring new or improved properties. The optimum pH value was defined to be 5.0 at a temperature of 298?K. Kinetic and isotherm experiments were carried out at the optimum pH. It was enough to reach the adsorption equilibrium at 4 hours and the maximum uptake capacity was 2.1?mmol?g^?1 at 25°C. Complexion, ion exchange, and electrostatic interaction were all believed to play a role in lanthanum adsorption on CATU derivative. The equilibrium adsorption data were fitted to a second-order kinetic equation. The Langmuir adsorption isotherm models were used to describe the adsorption process. The proposed method was validated and successfully applied for the determination of lanthanum in certified reference samples and ore sample with satisfactory results. The elution experiment was carried out by 0.05?mol/L CaCl₂ as an eluent.