Adsorption of surfactants from water onto raw and HCl-activated clays in fixed beds

The removal of surfactants from water by adsorption onto raw and HCl-activated montmorillonite in fixed beds was studied. Three surfactants hexadecylpyridinium chloride (cationic), sodium dodecyl sulfate (anionic), and Triton X-102 (non-ionic) were selected in the concentration ranges lower than their critical micelle concentrations in fixed bed experiments. It was shown that the adsorption of anionic surfactant onto Ca-montmorillonite (SAz-1) decreased with increasing pH but that of cationic surfactant increased. The adsorption capacity of non-ionic surfactant was maximized at pH 7.0. For given clay, the adsorption capacities of surfactants were strongly pH-dependent. The adsorption capacity and adsorption rate of non-ionic surfactant onto SAz-1 could be largely improved after acid activation of the clay. Such an improvement was due to the fact that the dissolution of Al³⁺ or Fe²⁺ of montmorillonite occurs in acid solution. The calculated breakthrough curves in fixed bed agreed with the measured ones (standard deviation < 6%). The 50% C/C₀ breakthrough time (τ) decreased with increasing liquid flow rate. The effects of flow rate on the adsorption constant and adsorption capacity were also discussed.     

Acid treatment of south Tunisian palygorskite: Removal of Cd(II) from aqueous and phosphoric acid solutions

The object of this work is to study the modifications of Tunisian palygorskite upon HCl treatment and to investigate the ability of natural and acid treated palygorskite to adsorb heavy metal ions. Chemical analysis, X ray diffraction, infrared spectra, MAS-NMR methods, BET surface and surface charge of HCl treated palygorskite have been reported. It was established that acid leaching at reflux temperature resulted in an increase in the amount of Mg, Fe and Al extracted and in surface area from 59.7 to 437 m² g^− 1 for 2 M HCl samples and from 59.7 to 360 m² g^− 1 for 4 M HCl samples, due to a dissolution of the octahedral sheet and the creation of mesoporosity. ²⁹Si-MAS-NMR studies yield information on changes occurring in the structure of the mineral. During acid treatment the clay structure is progressively transformed into amorphous silica (essentially for samples treated by HCl 4 M for 10 h and HCl 2 M for 35 h).Natural palygorskite and the activated samples were applied as adsorbents for the removal of Cd(II) from aqueous solutions. The effects of various experimental parameters were investigated. The adsorption isotherms of activated palygorskites for Cd(II) could be described by the Freundlich model. The acid activated sample showed a higher adsorption capacity for Cd(II) than the natural palygorskite. The retention of Cd(II) ions by palygorskite occurs dominantly by specific adsorption. A different behaviour was observed in the phosphoric acid medium. Despite increases in the surface areas upon acid activation, improvements in the adsorption were not observed, as a result of the decreasing number of negative surface sites, as main centers for specific adsorption.     

Synthesis,characterization and application of acid and alkaline activated volcanic ash-based geopolymers for adsorptive remotion of cationic and anionic dyes from water

In this work, two geopolymers were prepared by acid activation (GPAc) and alkaline activation (GPAl) approaches using volcanic ash (VA) as the precursor material. The geosorbents were characterized by X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier-transform infrared and Brunauer-Emmett-Teller (BET) surface area analyses and their comparative adsorptive potential for anionic (Eriochrome Black T/EBT) and cationic (methylene blue/MB) dyes from water is herein reported for the first time. GPAl and GPAc had 74.47 and 42.75 m²/g BET surface areas, respectively. Equilibrium adsorption data were described by the isotherm models in the order Freundlich > Sips > Langmuir model. Relative to acid activation (GPAc), alkaline activated geopolymer (GPAl) had the highest adsorption capacity for both MB and EBT, estimated at 952 mg/g and 251 mg/g, respectively, consistent with the BET surface areas. The adsorption rates were best described by the pseudo-second order (PSO) kinetic model. GPAl exhibited faster adsorption kinetics than GPAc as denoted by the adsorption half-life, t_1/2. The thermodynamic functions indicated that the adsorption of both MB and EBT onto the geopolymers was spontaneous, exothermic and feasible. The adsorption was pH-dependent implying electrostatic interactions is the dominant driving mechanism of adsorption. The results show that alkaline activated geopolymers are better sorbents for dye removal than acid activated geopolymers under the examined conditions.     

Preparation of granular activated carbon from oil palm shell by microwave-induced chemical activation: Optimisation using surface response methodology

In this study, waste palm shell was used to produce activated carbon (AC) using microwave radiation and zinc chloride as a chemical agent. The operating parameters of the preparation process were optimised by a combination of response surface methodology (RSM) and central composite design (CCD). The influence of the four major parameters, namely, microwave power, activation time, chemical impregnation ratio and particle size, on methylene blue (MB) adsorption capacity and AC yield were investigated. Based on the analysis of variance, microwave power and microwave radiation time were identified as the most influential factors for AC yield and MB adsorption capacity, respectively. The optimum preparation conditions are a microwave power of 1200 W, an activation time of 15 min, a ZnCl₂ impregnation ratio of 1.65 (g Zn/g precursor) and a particle size of 2 mm. The prepared AC under the optimised condition had a BET surface area (S_BET) of 1253.5 m²/g with a total pore volume (V_tot) of 0.83 cm³/g, which 56% of it was contributed to the micropore volume (V_mic).     

Acid modified local clay beads as effective low-cost adsorbent for dynamic adsorption of methylene blue

Locally sourced clay was harnessed to study its adsorptive potential of methylene blue (MB) in wastewater streams. The clay was modified with sulfuric acid and aluminum hydroxide. The raw and modified freeze dried clay bead RHC and MHC were subjected to batch and batch/fixed-bed adsorption studies, respectively. Elemental analysis, morphological structures were determined, and surface area of 19.3 (RHC) and 101.2 (MHC) m²/g were obtained. Langmuir, Freundlich and Redlich–Peterson isotherms models were analyzed and the modification increased adsorption capacity from 58.02 to 223.19 mg/g at 30 °C. The MB adsorption on RHC/MHC was spontaneous, exothermic and obeyed pseudo-second-order model.     

In situ co-adsorption of arsenic and iron/manganese ions on raw clays

The use of clays as effective arsenic sorbents has been strongly limited due to their low pH_ZPC and cation active behaviour in aqueous systems at pH > 3.5. A simple Fe/Al/Mn pre-treatment can significantly improve their sorption affinity to oxyanions, including arsenites and arsenates. The dynamics of arsenic adsorption from groundwater is also controlled by dissolved Fe/Mn ions, which behave as promoters of As adsorption, or competitors to adsorption sites. Low grade calcinated kaolin (MT) and bentonite (BT) were used as clay sorbents. Arsenic adsorption on raw clays without presence of Fe/Mn ions is very slow and limited. During co-adsorption the Fe/Mn ions and As oxyanions were adsorbed together onto a sorbent surface. Both Mn and Fe particles demonstrated a good sorption affinity to the clay surface, but only Fe particles supported As adsorption considerably (80% of As were removed in Fe/As system, while < 30% only in the Mn/As system). The kinetics of co-adsorption compared to the use of Fe/Mn pre-modified sorbents indicated a more dynamic process, while all mechanisms corresponded to the first order run (k ≈ 9.10^− 6- 1.10^− 4 s^− 1). Arsenic was strongly stabilized in pre-modified sorbents.     

Removal of basic dyes from aqueous solutions using natural clay

Adsorption properties of natural clay (from Eski?ehir of Turkey) were investigated by depending on different adsorption conditions such as different initial dye concentrations and contact times. The chemical composition of the natural clay was analyzed by X-ray fluorescence spectrometry (XRF). The removal of basic dyes such as Nile Blue (NB) and Brilliant Cresyl Blue (BCB) from aqueous solutions using natural clay in this study was described. After the equilibrium adsorption time of 8 h, the adsorption capacities for NB and BCB reach about 25 mg/g and 42 mg/g, respectively. Lagergren kinetic equation was used to test the experimental data to examine the controlling mechanism of adsorption processes. Adsorption data of the BCB and NB onto natural clay were fitted well by the pseudo-first-order model. The adsorption isotherms data were correlated with the Freundlich equation and the Freundlich constants K_f (mg/g) and n (intensity of adsorption) were calculated. The r² (regression coefficients) values were 0.9835 and 0.9849 for NB and BCB, respectively. The adsorption capacities of natural clay for NB and BCB have the following order: BCB > NB.     

Kinetic and analytical comparison of horseradish peroxidase on bare- and redox-modified single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) were coated first with methylene blue (MB) by noncovalent adsorption and then by horseradish peroxidase (HRP) by cross-linking with glutaraldehyde. The MB-SWNT/HRP composites formed stable films on glassy carbon electrodes. MB was probably present with a coverage of a monolayer or less. The MB voltammetry was consistent with fast electron transfer to a surface-confined species. The presence of HRP did not significantly affect the MB electrochemistry. MB could mediate electron transfer from HRP in the presence of H₂O₂. Cyclic voltammograms of this process were used to determine the rate constants for the reactions of the native ferriperoxidase with H₂O₂ and of the oxyferryl Compound II with the reduced form of MB. For comparison purposes, the rate constant for the direct electrode reduction of the HRP oxyferryl π-cation radical Compound I was determined in MB-free SWNTs. The results indicate a considerably faster regeneration rate for native ferriperoxidase by the mediated reaction than by direct electrochemistry. Using the MB-SWNT/HRP composites, H₂O₂ could be calibrated by amperometry at −0.3 V vs. SCE. The optimized response (at pH 7.0) had a sensitivity of 661.0 μA mM⁻¹ cm⁻² and a limit of detection (3 × S/N) of 0.1 μM.     

Removal of plant poisoning dyes by adsorption on Tomato Plant Root and green carbon from aqueous solution and its recovery

The organic dyes directly pollute the soil, water, plants and all living systems in the environment. The dyes like cationic Methylene blue (MB) and Crystal violet (CV) adsorption has been studied on Tomato Plant Root powder (TPR) and green carbon from aqueous solution for identifying the plant poisoning nature of cationic dyes. TPR powder is a cellulose material and green carbon is prepared from TPR powder by an ecofriendly method. The dyes adsorption mechanism on basic surface of cellulose and neutral surface of green carbon are correlated to evaluate the plant poisoning nature of organic dyes. The adsorption parameters were optimized to maximum adsorption. The maximum uptake of both dyes on TPR was 97% at 15 min and on carbon is 18% (CV) & 20% (MB) at 30 min. The adsorptions of MB and CV on TPR powder followed Freundlich and Langmuir adsorption isotherms and pseudo second order kinetics. The ?S^o, ?H^o and ?G^o of adsorption on TPR are calculated. The dyes recovery has been studied from dyes adsorbed TPR and green carbon. The adsorption mechanism and dye recovery studies proved the plant poisoning nature of MB and CV.     

Regeneration of spent catalyst from vinyl acetate synthesis as porous carbon: Process optimization using RSM

Optimization of the process of regeneration of spent catalyst from vinyl acetate synthesis was attempted using response surface methodology (RSM) based on the central composite design (CCD). The optimization was performed to maximize the response variables of methylene blue (MB) adsorption capacity as well as the yield of the porous carbon, with the process variables being regeneration temperature, regeneration duration and steam flow rate. The two factor interaction model and quadratic model were developed to correlate the process variables with the response variables. Based on the analysis of variance (ANOVA), all the three process parameters were found to be significant. The optimized process conditions were identified to be activation temperature of 946 °C, activation time of 30 min and steam flow rate of 2.4 g min⁻¹ with MB adsorption capacity of 420 mg/g and a yield of 50.7%. The MB adsorption capacity as compared with the majority of the literature reported values, along with high yield of the regenerated carbon, certify the economic feasibility of the process, with potential application in variety of liquid phase adsorption processes.     

不同黏土矿物种类和含量的泥粉对亚甲蓝值的影响

研究了石粉中含不同黏土矿物种类和含量的泥粉与亚甲蓝值的相互关系,探究不同黏土矿物吸附性能对亚甲蓝(MB)值的影响.结果表明:随着纯石粉含量的增加,MB值逐渐增大,但也远小于1.00,增幅较小、变化不大.纯泥粉和混合泥粉对MB值影响较大,呈现出线性关系;蒙脱土和以蒙脱土为主的混合泥粉对MB值影响最大,分别高达8.00、4...     

Cocoa (Theobroma cacao) shell-based activated carbon by CO2 activation in removing of Cationic dye from aqueous solution: Kinetics and equilibrium studies

Cocoa shell (CS) was used as a low-cost precursor for production of activated carbon (AC) and evaluated for its ability to adsorb Methylene Blue (MB) dye. Cocoa shell-based pellets were carbonized at 800 °C and subjected to 850 °C under a flow of CO₂ in different activation times. The cocoa (Theobroma cacao) shell-based activated carbon (CSAC) showed moderate surface area with the average pore size 2.7 nm. CSAC also displays the presence of aliphatic, aromatic hydrocarbons and near absence of C–O, carboxylic acid, and the –COOH functional group. Only the presence of O–H groups was detected. The influences of adsorption time and initial dye concentration on adsorption performance have been measured in a batch system. The results are well described by the Freundlich and Langmuir isotherms. The results from the kinetic study show that MB adsorption follows pseudo-second-order and Boyd models, which indicated the MB adsorption on the CSAC was controlled by film diffusion.     

Temperature effects on iodine adsorption on organo-clay minerals: I. Influence of pretreatment and adsorption temperature

The sorptive capability of clay minerals for anionic radionuclides can be improved substantially by exchanging the natural inorganic interlayer cations with certain organic cations. After screening a variety of possible candidates, four organic cations were selected and combined with three clay minerals, providing 12 organo-cation/clay mineral combinations. The samples were tested for anion adsorption in batch experiments with radioiodide in a concentration range of 10⁻² to 10⁻⁹ mol l⁻¹ and exhibited high adsorption in bidistilled water as well as in synthetic groundwater. Results for two clay minerals—a smectite and a vermiculite—and four organic cations are given in this paper.Tests were also performed with temperature pretreated material. An increase of the pretreatment temperature from 20 to 40, 60, 80 and 100 °C did not result in a remarkable effect on iodide adsorption, except for the 1,12-dipyridiniododecan/vermiculite combination.In batch experiments with equilibrium temperatures of 20–60 °C, iodide adsorption decreased slightly with increasing temperature. Only 1,12-dipyridiniododecan in combination with smectite and vermiculite showed a somewhat lower iodide adsorption at higher temperatures.     

Preparation and characteristics of rice-straw-based porous carbons with high adsorption capacity

To prepare porous carbons with high adsorption capacity from rice straws, two different kinds of precursors, i.e. one as the raw rice straws (one-stage process) and the other as pre-carbonized rice straws (two-stage process), were activated with KOH of various impregnation ratios. The two-stage process was found very effective for manufacturing porous carbons with high surface area and adsorption capacities for MB and I₂. For example, the porous carbon that was carbonized at 700°C and subsequently activated at 900°C exhibited the surface area of 2410 m²/g, the adsorption capacities of 800 and 1720 mg/g for MB and I₂, respectively, and the total pore volume of 1.4 ml/g. In the two-stage method, there was a preferential optimum impregnation ratio of KOH to a precursor carbon, i.e. 4:1, with which high surface area of porous carbons could be achieved. The formation of uni- and bidentate carboxylic salt structure, induced by reaction between KOH and oxygen containing carbon, that facilitates the formation of azo group (-NN-) on a subsequent heat treatment was considered as one of the key factors for the presence of optimum impregnation ratio of KOH. In contrast, the porous carbons of only moderate adsorption capacity could be obtained from the one-stage method. The original morphology of rice straw was sustained during the two-stage process, yet not during the one-stage process.     

Thermodynamics,kinetics, and isotherms studies for gold(III) adsorption using silica functionalized by diethylenetriaminemethylenephosphonic acid

A novel hybrid material silica gel chemically modified by diethylenetriaminemethylenephosphonic acid GH-D-P has been developed and characterized. The results of the adsorption thermodynamics and kinetics of the as-synthesized GH-D-P for Au(III) showed that this high efficient inorganic–organic hybrid adsorbent had good adsorption capacity for Au(III), and the best interpretation for the experimental data was given by the Langmuir isotherm equation, the maximum adsorption capacity for Au(III) is 357.14 mg/g at 35 °C. Moreover, the study indicated the adsorption kinetics of GH-D-P could be modeled by the pseudo-second-order rate equation wonderfully, and the adsorption thermodynamic parameters ΔG, ΔH and ΔS were −20.43 kJ mol⁻¹, 9.17 kJ mol⁻¹, and 96.24 J K⁻¹ mol⁻¹, respectively. Therefore, the high adsorption capacity make this hybrid material have significant potential for Au(III) uptake from aqueous solutions using adsorption method.     

Highly mesoporous carbonaceous material of activated carbon beads for electric double layer capacitor

The activated carbon beads (ACB) are prepared by a new preparation method, which is proposed by mixing the coal tar pitch and fumed silica powder at a certain weight ratio and activation by KOH at different weight ratios and different temperatures. The BET surface area, pore volume and average pore size are obtained based on the nitrogen adsorption isotherms at 77 K by using ASAP 2010 apparatus. The results show that our samples have much high specific surface area (SSA) of 3537 m² g⁻¹and high pore volume value of 3.05 cm³ g⁻¹. The percentage of mesopore volume increases with the weight ratio of KOH/ACB ranging from 4% to 72%. The electrochemical double layer capacitors (EDLCs) are assembled with resultant carbon electrode and electrolyte of 1 mol L⁻¹ Et₄NBF₄/PC. The specific capacitance of the ACB sample could be as high as 191.7 F g⁻¹ by constant current charge/discharge technique, indicating that the ACB presents good characteristics prepared by the method proposed in this work. The investigation of influence of carbon porosity structure on capacitance indicates that the SSA plays an important role on the capacitance and all the pore sizes of less than 1 nm, from 1 to 2 nm and larger than 2 nm contribute to the capacitance. Mesopore structure is beneficial for the performance at high current density.     

Enhancement of H2 and CH4 adsorptivities of single wall carbon nanotubes produced by mixed acid treatment

Single wall carbon nanotubes (SWCNTs) were treated with a HNO₃/H₂SO₄ mixed solution to increase the number of narrow micropores. The mixed acid treatment increased the micropore volume from 0.13 to 0.35 mL g⁻¹ as measured by N₂ adsorption at 77 K. The micropore volume evaluated with CO₂ adsorption at 273 K increased from 0.06 to 0.27 mL g⁻¹. This remarkable micropore volume increase was ascribed to the formation of a highly packed and ordered SWCNT assembly with the acid treatment, which was confirmed by field emission scanning electron microscopy. The adsorption amount of supercritical H₂ at 77 K under 5 MPa pressure increased twofold as a result of the acid treatment, while the supercritical CH₄ adsorption amount at 303 K and 5 MPa pressure increased by 40%. These remarkable increases were caused by increased amount of narrow micropores as a result of the acid treatment.     

Adsorption of bromo-phenol blue from an aqueous solution onto thermally modified granular charcoal

The adsorption phenomenon of bromo-phenol blue onto pristine and thermally evacuated granular charcoal (GC) was studied via a batch technique at 25 °C. The effect of evacuation temperature on the GC surface and pore structure (e.g. pore volume and diameter) was studied by Fourier transform infrared spectroscopy (FT-IR), point of zero charge (PZC), proximate analysis, Brunauer, Emmett and Teller (BET) method and field emission scanning electron microscopy (FE-SEM). The FT-IR spectra of the samples after evacuation showed considerable decrease in the acidic functional groups. PZC showed that the surface of the evacuated charcoal became basic as the evacuation temperature was increased from 300 to 800 °C. Volatile matter decreased while ash and fixed carbon contents increased during evacuation, which led to an increase in the micro-pore volume from 0.25 to 0.42 cm³ g⁻¹, meso-pore volume from 0.04 to 0.13 cm³ g⁻¹, pore diameter from 5.01 to 6.21 nm, and specific surface from 150.32 to 254.70 m² g⁻¹. Adsorption of the bromo-phenol blue onto charcoal, increased as the evacuation temperature was increased from 300 to 800 °C. The interaction of bromo-phenol blue with charcoal was proposed to have occurred via hydrogen bonding. The adsorption data fitted well with the Langmuir equation, which indicated that the monolayer adsorption has occurred at specific sites within the adsorbent.     

Enhanced mechanical strength of chitosan hydrogel beads by impregnation with carbon nanotubes

Chitosan (CS) hydrogel beads were impregnated with carbon nanotubes (CNTs), and their mechanical strength, acid stability and adsorption capacity to the anionic dye, Congo red (CR), were investigated by comparing with a conventional reinforcing method of cross-linking with epichlorohydrin (ECH). CS/CNT hydrogel beads were manufactured by dispersing CNTs (0.01 wt.%) with cetyltrimethylammonium bromide (CTAB) (0.05 wt.%) into CS solution (1 wt.%). Maximum endurable force at complete breakdown of CS hydrogel beads increased from 1.87 to 7.62 N with incorporation of CNTs and its adsorption capacity increased from 178.32 to 423.34 mg g⁻¹ for adsorption of CR.     

Adsorption of pigments and free fatty acids from shea butter on activated Cameroonian clays

Adsorption of pigments and free fatty acids from shea butter on acid‐activated Cameroonian local clays was investigated. The adsorption of the pigments was followed by the reduction of the absorbance of the shea butter at 295 nm. The kinetic study revealed that both the temperature at which the experiment was performed and the degree of activation of the clays influence the time of contact required to reach adsorption equilibrium of the pigments and the amount of pigments adsorbed. Thus, at 90 °C, the time required was 30 min for the clays activated with 0.5 M (A0.5M) and 1.0 M solutions (A1M) of sulphuric acid, and 45 min for the clay activated with a 2.0 M solution (A2M) of sulphuric acid. At 80 °C, the adsorption equilibrium was reached after 45 min for clays A0.5M and A1M, and 60 min for clay A2M. At 65 °C, the contact time to reach adsorption equilibrium was longer than 75 min for all the adsorbents used. At 90 °C, the amount of pigments adsorbed at equilibrium by clay A2M was about two thirds of that adsorbed by clay A0.5M, and one half of the amount adsorbed by clay A1M. For each adsorbent, the amount of pigment adsorbed decreased with temperature. A1M was the most efficient local clay for the adsorption of shea butter pigments and compared favourably with the industrial clay used as reference. The same evolution was observed with the adsorption of free fatty acids on different clays. The contact time needed for the elimination of peroxides was 40 min for all the clays used. The most efficient adsorbents for the adsorption of the pigments and free fatty acids were also the ones that gave the best results in the elimination of peroxides. The energy of activation for the adsorption of the pigments, as determined by the adsorption kinetic model of Brimberg, were 61 ± 9 kJ/mol, 73 ± 11 kJ/mol, 67 ± 10 kJ/mol, and 47 ± 7 kJ/mol for the industrial adsorbent (EN) and clays A0.5M, A1M and A2M, respectively. These values of activation energies indicate that the shea butter pigments are chemisorbed on acid‐activated clays. It was found that the adsorption isotherms follow the Freundlich equation.