An evaluation of coal fly ash as an adsorbent for the removal of methylene blue from aqueous solutions: kinetic and thermodynamic studies

Abstract

In this study the effect of the dose and particle size of the adsorbent, initial dye concentration, initial pH, contact time and temperature were investigated for the removal of by means of fly ash (FA) methylene blue (MB) from an aqueous solution. The FA dose was found to be 2.0?g and the under 270 mesh sized particles were found to be effective particles for adsorption. The adsorption process reached its maximum value at 0.5?mg/L dye concentration and attained equilibrium within 10?minutes. The adsorption isotherm was found to follow the Langmuir model. The estimated adsorption free energy (ΔG^o), enthalpy change (ΔH^o), and entropy change (ΔS^o) for the adsorption process were ?37.77?kJ mol^?1, ?13.44?kJ mol^?1 and 122 J mol^?1 K^?1 respectively at 298 K. The maximum adsorption capacity is 0,12?mg g^?1 at 298 K and 0,07?mg g^?1 at 398 K. The adsorption process was exothermic, feasible and spontaneous. The positive value of ΔS^o shows the affinity of FA for MB while the low value of ΔG^o suggests a physical adsorption process.     

MCM-41, MOF and UiO-67/MCM-41 adsorbents for pre-combustion CO2 capture by PSA: adsorption equilibria

Three different adsorbent materials, which are promising for pre-combustion CO₂ capture by a PSA (Pressure Swing Adsorption) process, are synthesized, pelletized and characterized. These materials are USO-2-Ni metal organic framework (MOF), mesoporous silica MCM-41 and a mixed material consisting of UiO-67 MOF bound with MCM-41. On these materials, equilibrium adsorption isotherms of CO₂ and H₂ are measured at different temperatures (25–140?°C) in a wide pressure range (up to 15?MPa). From the experimental data the parameters of different isotherm equations (Langmuir, Sips and Quadratic) are determined, together with the isosteric heats of adsorption. Binary adsorption of CO₂/H₂ mixtures on USO-2-Ni MOF is additionally measured and compared to predicted values using IAST (Ideal Adsorbed Solution Theory) showing a good agreement. The potential of the materials for the application of interest is evaluated by looking at their cyclic working capacity and compared to those of a commercial activated carbon. From this evaluation especially the USO-2-Ni MOF adsorbent looks promising compared to the commercial activated carbon. For the other two materials a smaller improvement, which is limited to lower temperatures, is expected.     

Gas adsorption in mesoporous micelle-templated silicas: MCM-41, MCM-48, and SBA-15

This paper reports a molecular simulation and experimental study on the adsorption and condensation of simple fluids in mesoporous micelle-templated silicas MCM-41, MCM-48, and SBA-15. MCM-41 is described as a regular cylindrical silica nanopore, while SBA-15 is assumed to be made up of cylindrical nanopores that are connected through lateral channels. The 3D-connected topology of MCM-48 is described using a gyroid periodic minimal surface. Argon adsorption at 77 K is calculated for the three materials using Grand Canonical Monte Carlo simulations. Qualitative comparison with experiments for nitrogen adsorption in mesoporous micelle-templated silicas is made. The adsorption isotherm for SBA-15 resembles that for MCM-41. In particular, capillary condensation and evaporation are not affected by the presence of the connecting lateral channels. In contrast, the argon adsorption isotherm for MCM-48 departs from that for MCM-41 having the same pore size. While condensation in MCM-41 is a one-step process, filling of MCM-48 involves two successive jumps in the adsorbed amounts which correspond to condensation in different domains of the porosity. The condensation pressure for MCM-48 is larger than that for MCM-41. We attribute this result to the morphology of the MCM-48 surface (made up of both concave and convex regions) that differs from that for MCM-41 (concave only). Our results suggest that the pore connectivity affects pore filling when the size of the connections is comparable to that of the nanopores.     

Preparation of MnCo/MCM-41 catalysts with high performance for chlorobenzene combustion

MCM-41 was synthesized by a soft template technique. The specific surface area and pore volume of the MCM-41 were 805.9 m²/g and 0.795 cm³/g, respectively. MCM-41-supported manganese and cobalt oxide catalysts were prepared by an impregnation method. The energy dispersive X-ray spectroscopy clearly confirmed the existence of Mn, Co, and O, which indicated the successful loading of the active components on the surface of MCM-41. The structure and function of the catalysts were changed by modulating the molar ratio of manganese to cobalt. The 10%MnCo(6:1)/MCM-41 (Mn/Co molar ratio is 6:1) catalyst displayed the best catalytic activity according to the activity evaluation experiments, and chlorobenzene (1000 ppm) was totally decomposed at 270 °C. The high activity correlated with a high dispersion of the oxides and was attributed to the exposure of more active sites, which was demonstrated by X-ray diffraction and high-resolution transmission electron microscopy. The strong interactions between MnO₂, Co₃O₄, MnCoO_x, and MCM-41 indicated that cobalt promoted the redox cycles of the manganese system. The bimetal-oxide-based catalyst showed better catalytic activity than that of the single metal oxide catalysts, which was further confirmed by H₂ temperature-programmed reduction. Chlorobenzene temperature-programmed desorption results showed that 10%MnCo(6:1)/MCM-41 had higher adsorption strength for chlorobenzene than that of single metal catalysts. And stronger adsorption was beneficial for combustion of chlorobenzene. Furthermore, 10%MnCo(6:1)/MCM-41 was not deactivated during a continuous reaction for 1000 h at 260 °C and displayed good resistance to water and benzene, which indicated that the catalyst could be used in a wide range of applications.     

Modified Calcium Alginate Beads with Sodium Dodecyl Sulfate and Clay as Adsorbent for Removal of Methylene Blue

In present study, we have investigated the effect of an anionic surfactant sodium dodecyl sulfate (SDS) and clay on calcium alginate beads was studied to remove methylene blue (MB) and to improve the adsorption capacity. The effects of various experimental parameters, such as shaking rate, initial dye concentration, temperature, and pH on the adsorption rate, have been studied. Equilibrium studies showed that the sorption of the dye was enhanced in presence of SDS. Scanning electron microscope (SEM) analysis showed that SDS entrapped beads have more pores and cavities which could be responsible for improved adsorption of MB. The kinetics of cationic dye adsorption nicely followed pseudo-second-order process. The evaluated thermodynamic parameters (ΔG ^o, ΔH ^o, ΔS ^o) suggest endothermic adsorption of MB. The results revealed that the surfactant entrapped alginate could be considered as potential adsorbents for MB removal from aqueous solutions.     

氮气在MCM－41分子筛中的吸附：实验和分子模拟

用美国Micromeritics公司生产的ASAP2010物理吸附仪测定了低温（77 K） N_2在MCM-41分子筛中的吸附等温线，获得了表征MCM-41特征的BET比表面、BJH孔 容和平均孔径。同时用巨正则Monte Carlo（GCMC）模拟方法考究了N_2在MCM-41中 的吸附，得到了N_2在MCM-41中的模拟吸附等温线，分析了流体在MCM-41分子筛中 的微观结构。GCMC模拟中MCM-41介孔材料模型化为圆柱孔，N_2模型化为Lennard- Jones（LJ）球。N_2和MCM-41介孔墙壁间的相互作用采用Tjatjopoulos-Feke- Mann（TFM）势能模型进行表征。通过使模拟和实验结果有一个好的吻合，确定了 一组有效的MCM-41分子筛的势能参数（σ_(ww) = 0.265 nm，∈_(ww)/k = 190 K ）。这为以后其他吸附质在MCM-41中吸附的预测奠定了基础、提供了依据。     

Removal of Cr(VI) from aqueous solutions using EDCC-MCM-41: Isotherm,kinetics and thermodynamic evaluation

Abstract

EDCC-MCM-41, a novel ethylenediamine derivative of MCM-41 was synthesized from a sugar industry waste, bagasse fly ash. Studies were carried out on its ability to remove Cr(VI) from aqueous solution. Its performance was also compared with that of unmodified MCM-41 and an already known derivative NH₂-MCM-41 (both also synthesized from bagasse fly ash) at the same experimental conditions. Results show that the novel adsorbent produced a better sorption performance (adsorption capacity of 49.04?mg g^?1) than MCM-41 and NH₂-MCM-41 which produced adsorption capacities of 13.78?mg g^?1 and 25.29?mg g^?1 respectively. Thermodynamics, kinetics and isotherm studies confirm that the sorption process involving the novel adsorbent is favorable for Cr(VI) and can best be represented by pseudo-second-order kinetics model. The sorption process was also found to be multistep, involving both film diffusion and intraparticle diffusion into the pores on the adsorbent’s surface.

Abbreviations: BFA: Bagasse Fly Ash; MCM-41: Mobil Composition of matter no. 41; NH2-MCM-41: mine functionalized MCM-41; EDCC-MCM-41: Ethylenediamine grafted MCM-41; qe: Mass of material adsorbed at equilibrium per mass of adsorbent; qt: Mass of material adsorbed at any time t per mass of adsorbent; C0: The initial concentration; Ce: The residual concentration at equilibrium; Ct: Residual concentration at any time t; W: The weight of adsorbents; rRMSD: Root mean square deviation; R: Gas constant     

Surface activity and thermodynamic properties of water‐soluble polyester surfactants based on 1,3‐dicarboxymethoxybenzene used for enhanced oil recovery

The surface activity and thermodynamic properties for eight low molecular weight nonionic co‐polyester (PE) surfactants have been investigated. Surface and interfacial tensions (IFT) of surfactants in aqueous solutions were measured using the spinning drop technique. From these measurements, the critical micelle concentration (CMC), the surface pressure at CMC (Y_CMC), the maximum surface concentration (Γ_max), the minimum area/molecule at the aqueous solution/air interface (A_min), the effectiveness of surface tension reduction (Π_CMC), the alkane carbon number (n_min) and the IFT at n_min (Y_min) were determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic and ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad and ΔS_ad) for these polymeric surfactants were also calculated. Structural effects on micellization and adsorption are discussed in terms of these parameters. The results show that the ΔG_ad values were more negative than ΔG_mic values for these compounds, so that they favored adsorption before the micellization process. They exhibited IFT in the order of 10⁻³ to 10⁻⁴ mN/m against the thin alkane carbon number range 6–9. This range seemed to be prefered for enhanced oil recovery. Copyright © 2000 John Wiley & Sons, Ltd.     

Adsorption of Methylene Blue from Aqueous Solution on High Lime Fly Ash: Kinetic,Equilibrium, and Thermodynamic Studies

Kinetic, equilibrium, and thermodynamic studies were performed for the batch adsorption of methylene blue (MB) on the high lime fly ash as a low cost adsorbent material. The studied operating variables were adsorbent amount, contact time, dye concentration, and temperature. The kinetic data were analyzed using the pseudo-first order and pseudo-second order kinetic models and the adsorption kinetic was followed well by the pseudo-second order kinetic model. The equilibrium data were fitted with the Freundlich, Langmuir, and Dubinin Radushkevich (D–R) isotherms and the equilibrium data were found to be well represented by the Freundlich and D–R isotherms. Based on these two isotherms MB is taken by chemical ion exchange and active sites on the high lime fly ash have different affinities to MB molecules. Various thermodynamic parameters such as enthalpy of adsorption (ΔH°), free energy change (ΔG°), and entropy change (ΔS°) were investigated. The positive value of ΔH° and negative value of ΔG° indicate that the adsorption is endothermic and spontaneous. The positive value of ΔS° shows the increased randomness at the solid–liquid interface during the adsorption. A single-stage batch adsorber was also designed based on the Freundlich isotherm for the removal of MB by the high lime fly ash.     

MCM-41分子筛的合成及129Xe核磁共振的研究

Purely siliceous MCM-41 with a narrow pore-size distribution, different pore size, high surface area was synthesized . As prepared, calcined and catalytically tested MCM-41 materials have been comprehensively characterized by N₂ adsorption/desorption at 77K and ¹²⁹Xe NMR. By adding mesitylene during the synthesis, the pore size of MCM-41 was enlarged to 5.2nm. The chemical shift in ¹²⁹Xe NMR spectroscopy of adsorbed xenon indicates that the MCM-41 is one dimensional pore channels .     

Kinetic,equilibrium and thermodynamic study of 2-chlorophenol adsorption onto Ricinus communis pericarp activated carbon from aqueous solutions

ABSTRACT

This study reports on the adsorption of 2-chlorophenol from an aqueous solution using activated carbon prepared by H₂SO₄ activation of the pericarp of Ricinus communis (RCAC). The pericarp was carbonized and activated by treating with H₂SO₄ solution followed by heating in an oven at 105°C for 12 hrs. Batch adsorption experiments were carried out as a function of pH, contact time, initial concentration of the adsorbate, adsorbent dosage and temperature of the solution. Kinetic data were best fit to a pseudo-first-order rate equation for the adsorption of 2-chlorophenol on RCAC. Thermodynamic parameters ΔH^o, ΔS^o and ΔG^o for the adsorption were also determined which shows that adsorption on the surface of RCAC was spontaneous in nature, and exothermic between temperatures of 20°C and 80°C. The equilibrium data better fit the Langmuir isotherm model for 2-chlorophenol adsorption on RCAC. IR spectrum for loaded and unloaded RCAC was obtained and found to be in good agreement.     

MCM-41表面新戊基锆和氧化锆的制备

首次在高真空系统中利用Ｚr[CH2C(CH3)3]4与表面羟基的反应把－Ｚr[CH2C(CH3)3]2基团接枝在介孔硅胶ＭＣＭ－４１的表面上,经进一步氧化和水解得到了表面富锆ＭＣＭ－４１材料,采用元素分析、ＦＴＩＲ、固态ＮＭＲ、Ｘ射线粉末射及吡啶化学吸附等分别表征了材料的组成及性质,初步研究表明接枝法制备的ＺrMCM-41比水热法合成的样品有更好的吸附和催化性能。     

Physisorption of alcohols and water vapour by MCM-41, a model mesoporous adsorbent

Adsorption isotherms of methanol, ethanol, propan-1-ol, butan-1-ol and water vapour have been determined on MCM-41, a model mesoporous adsorbent. The isotherms of the alcohols are all of Type IV, whereas the water isotherm is of Type V in the IUPAC classification. Each adsorption isotherm exhibits a sharp step, indicative of capillary condensation within a narrow distribution of mesopores. The isotherms are reversible in the monolayer-multilayer region, but distinctive hysteresis loops are associated with the condensation-evaporation cycle. The area within the loop is dependent on the adsorptive, increasing in scale from methanol to butan-1-ol and water. It is evident that the large internal surface of MCM-41 is somewhat hydrophobic and that its mesopore structure is remarkably uniform and stable.Nomenclature d _p Pore Diameter/nm - P/P ₀ Pressure/Saturation vapour pressure at the temperature of the isotherm run - T Temperature of isotherm run/K - n _m BET monolayer capacity/mmol g^–1 - n(0.1) Amount adsorbed at relative pressureP/P ₀=0.1/µ mol g^–1 - a _m Cross sectional area of an adsorbed molecule/nm² - V _p Effective pore volume/cm³ g^–1     

Adsorption of diazinon and fenitothion on MCM-41 and MCM-48 mesoporous silicas from non-polar solvent

The adsorption of two common organophosphorus pesticides, diethoxy-[(2-isopropyl-6-methyl-4-pyrimidinyl)oxy]-thioxophosphorane (diazinon) and dimethoxy-(3-methyl-4-nitrophenoxy)-thioxophosphorane (fenitrothion), by MCM-41 and MCM-48 mesoporous silicas at room temperature was investigated. UVvis and IR spectroscopy, small-angle X-ray diffraction, and the specific surface area analysis (S _BET) were used to study the adsorption behavior of diazinon and fenitrothion. The results show that the MCM-41 and MCM-48 mesoporous silicas adsorb diazinon more efficiently than fenitrothion. The extraction of adsorbed materials from the adsorbents with polar solvents and subsequent analysis by ³¹P NMR showed that the adsorption of diazinon and fenitrothion on mesoporous silicas is destructive and non-destructive, respectively. Nitrogen adsorption measurements showed that the specific surface area of both silicas decreases after the adsorption of pesticides, and the larger effect is observed for diazinon. The article is published in the original.     

Sol–gel derived ion imprinted thiocyanato-functionalized silica gel as selective adsorbent of cadmium(II)

A Cd(II)-imprinted thiocyanato-functionalized silica gel adsorbent with high adsorption capacity was prepared by surface imprinting technique combined with sol–gel process for the selective adsorption of Cd(II) ion in aqueous solution, and was characterized by Fourier-transform infrared spectroscopy, nitrogen gas sorption and thermogravimetric analysis. The influences of different conditions (such as the pH of solutions, the contact time and the initial concentrations of Cd(II) ions) on the adsorption capacity of Cd(II) were investigated. The optimum pH of adsorption was in the range of 4–8.5. The adsorption equilibrium could be reached in 20 min. The relatively selectivity coefficients of the imprinted silica were higher than those of the non-imprinted adsorbents. Ho’s pseudo-second-order model well described the kinetics of the adsorption reaction. The adsorption process of metals followed Redlich–Peterson isotherm model, and the experimental value of maximum adsorption capacity for Cd(II) was 72.8 mg·g^?1. The positive value of ΔH ^o suggested endothermic nature of Cd(II) adsorption on the imprinted silica adsorbent. Increase in entropy of adsorption reaction was shown by the positive value of ΔS ^o and the negative value of ΔG ^o indicating that the adsorption was spontaneous in nature.     

Phase Transformation of MCM-41 in the Mother Liquid at Moderate Temperature

A new crystalline phase (via amorphous intermediate), NCUZ-1, was obtained when MCM-41 (Si/Al=9) was under prolonged heating in the mother liquid (which contains NaAlO₂, [N(CH₃)₄]₂SiO₃, SiO₂, and surfactant C₁₆H₃₃N(CH₃)₃OH(aq) at 105°C for more than two weeks. The largest d spacing of NCUZ-1 calculated from X-ray diffraction data is approx. 6 Å, indicating that the long-range order of the mesopores in MCM-41 was not present in NCUZ-1. Nitrogen absorption studies showed that NCUZ-1 contains both mesopores and micropores. The volume ratio of the mesopore to micropore is approx. 10 to 1 and the BET surface area is 400 m²/g. The TEM micrograph of NCUZ-1 revealed a homogenous phase with distorted mesopores. The ¹³C NMR spectrum of NCUZ-1 before calcination is similar to that of uncalcined MCM-41, indicating that the organic templates in both phases have a similar structure. In the phase transformation process, the counteranion (OH⁻) of the surfactant template played an important role. It increased the solubility of the aluminosilicate wall; the breaking and reforming the Si–O and Al–O bonds make the phase transformation possible, although the process is very slow. When C₁₆H₃₃N(CH₃)₃Cl, instead of C₁₆H₃₃N(CH₃)₃OH, was used as a template, no NCUZ-1 phase was obtained under the same reaction conditions. TEM micrograph, nitrogen absorption isothermal, and ¹³C NMR spectra of NCUZ-1 suggested that the mesopores were present in the NCUZ-1 phase, although there is no long-range order of these mesopores.     

Adsorption of crystal violet dye from aqueous solution using mesoporous materials synthesized at room temperature

In this work, batch adsorption experiments are carried out for crystal violet dye using mesoporous MCM-41 synthesized at room temperature and sulfate modified MCM-41 prepared by impregnation method using H₂SO₄ as sulfatising agent. The surface characteristics, pore structure, bonding behavior and thermal degradation of both the MCM-41 samples are characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction (XRD) patterns, Fourier transform infrared (FT-IR) spectroscopy and thermo gravimetric analysis (TGA). The adsorption isotherm, kinetics and thermodynamic parameters are investigated for crystal violet (CV) dye using the calcined and sulfated MCM-41. Results are analysed using Langmuir, Freundlich and Redlich-Peterson isotherm models. It is found that the Freundlich model is an appropriate model to explain the adsorption isotherm. The highest adsorption capacity achieved is found to be 3.4×10⁻⁴ mol g⁻¹ for the sulfated MCM-41. The percentage removal of crystal violet dye increases with increase in the pH for both the MCM-41 adsorbents. Kinetics of adsorption is found to follow the second-order rate equation. From the thermodynamic investigation, it is evident that the adsorption is exothermic in nature.     

Thermodynamics of Dissociation and Metal Complexation of 3-Nitro-1,5-Diphenylformazan

Thermodynamic parameters for dissociation of 3-nitro-1,5-diphenylformazan and its complexation by some divalent metal ions were determined in a 50%(v/v) dioxane–water mixture at constant ionic strength (0.1 M KCl) using an automatic potentiometric technique. The changes in the standard Gibbs energy ΔG^o and enthalpy ΔH^o accompanying the complexation were found to decrease with increasing metal ionic radius and to increase with the electronegativity, the ionization enthalpy, and the enthalpy of hydration. The order of ?ΔG^o and ?ΔH^o values were found to be Mn²⁺ < Fe²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺, in accordance with the Irving–Williams order. The complexes were stabilized by both enthalpy and entropy changes and the results suggest that the complexation is an enthalpy-driven process. The transition-series contraction energy E_r(Mn–Zn) and the ligand field stabilization energy δ H were calculated from the enthalpy changes.     

Kinetic study of degradation of heavy oil over MCM-41

Thermogravimetry was applied in order to investigate the catalytic degradation of heavy oil (15.4^oAPI) over silica-based MCM-41 mesoporous molecular sieve. This material was synthesised by the hydrothermal method, using cetyltrimethylammonium bromide as organic template. The physicochemical characterization by nitrogen adsorption, X-ray diffraction, and thermogravimetry, showed that the obtained material presents well-defined structure, with a uniform hexagonal arrangement. The thermal and catalytic degradation of heavy oil was performed by thermogravimetric measurements, in the temperature range from 30 to 900 °C, at heating rates of 5, 10, and 20 °C min⁻¹. By using the model-free kinetics, proposed by Vyazovkin, it was determined that the activation energy to degrade the heavy oil was ca. 128 kJ mol⁻¹, and for degradation of oil in presence of MCM-41, this value decreased to 69 kJ mol⁻¹, indicating the performance of the mesoporores catalyst for the degradation process.     

Effect of temperature on the adsorption of phosphatidylcholine by silicon-containing materials with various degrees of order

Features of the adsorption of phosphatidylcholine (PCh) by inorganic silicon-containing materials with various degrees of order (MCM-41, MMC-1, and silica gel) from solutions in hexane under equilibrium conditions in the temperature range of 283–323 K are considered. It is found that the adsorption of the phospholipid within the C _e = (0.6–4.0) × 10^–4 mmol/dm³ range of concentrations on the investigated materials is characterized by monomolecular absorption. Differential thermodynamic characteristics (ΔG, ΔH, and ΔS) of the sorption of PCh by silicon-containing materials with various degrees of order in the temperature range of 283–323 K are considered. An increase in the affinity of silicon-containing materials toward the phospholipid upon an increase in the temperature of the sorption process is observed.