Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic,equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (ΔH°), Gibbs free energy (ΔG°) and entropy (ΔS°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.     

Preparation of activated carbons from unburnt coal in bottom ash with KOH activation for liquid-phase adsorption

In this work, unburnt coal (UC) in bottom ash from coal-fired power plants was soaked in KOH solution and activated for 1 h at 780 °C. The yield of activated carbons varied from 47.8 to 54.8% when the KOH/UC weight ratio changed from 2 to 4. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were characterized based on N₂ adsorption isotherms. It was shown that the isotherms for the adsorption of methylene blue, acid blue 74, and 4-chlorophenol from aqueous solutions on these activated carbons at 30 °C were well fitted by the Langmuir equation (correlation coefficient r² > 0.9968). The adsorption capacities of methylene blue, acid blue 74, and 4-chlorophenol were obtained to be 2.40–2.88, 0.57–1.29, and 2.34–5.62 mmol/g, respectively. Moreover, the adsorption kinetics could be suitably described by the Elovich equation.     

Phenol removal from aqueous environments by natural & chemically modified kaolin clay

Natural, acid and base modified kaolin clays were studied for the sake of phenol and 4-chlorophenol removal from aqueous environments and their application to real ground and industrial wastewater samples. Scanning electron microscope (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), Thermo Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), and Surface area analysis were employed for characterization of the adsorbents microstructure. Operating factors such as adsorbent dose, solution pH, initial phenol concentration, and contact time were studied. The experimental data displayed that the increase of the adsorbent dose, contact time, and pH value from 2 to 7 increases the efficiency of the removal process. Optimal conditions for phenolic removal were; contact time of 300 min, primary phenol solution of 25 mg/L, pH 7 and 2.5 g/L as an appropriate adsorbent dose using crude (natural), acid modified and base modified kaolin clays. The higher phenolic removal efficiencies were obtained at 5 mg/L as 90, 97, 96.2%, respectively, for the adsorbents in the previously mentioned order. The adsorption capacity in the removal of phenol and 4-chlorophenol were 7.481 and 4.195, 8.2942 and 3.211, and 8.05185 and 18.565 mg/g, respectively, for the adsorbents in the same mentioned order. The adsorption equilibrium data were fitted and analyzed with four isotherm models, namely, Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm equations. The adsorption process of phenol on studied adsorbents was exothermic, spontaneous and thermodynamically favorable proved by the negative values of their thermodynamic parameters ΔH° and ΔG°. The correlation coefficient (R²) for all concentrations was higher than 0.94, which indicates that in the studied system, the data suitably fit the first-order kinetics. The % desorption capacity was amounted to 96%, 91.11%, and 87.06% of adsorbed phenol, respectively, for the adsorbents in the previous order using 0.1N NaOH and 10% V/V ethanol solutions as eluents at 25°C, indicating the reusability of the adsorbents. Kaolin and its modified forms can be introduced as eco-friendly and low-cost adsorbents in water remediation implementation.     

Biosorption of lead by maize (Zea mays) stalk sponge

This study investigated the removal of Pb(II) from aqueous solutions by a maize (Zea mays) stalk sponge. Equilibrium and kinetic models for Pb(II) sorption were developed by considering the effect of the contact time and concentration at the optimum pH of 6 ± 0.2. The Freundlich model was found to describe the sorption energetics of Pb(II) by Z. mays stalk sponge, and a maximum Pb(II) loading capacity of 80 mg g^?1 was determined. The kinetic parameters were obtained by fitting data from experiments measuring the effect of contact time on adsorption capacity into pseudo-first and second-order equations. The kinetics of Pb(II) sorption onto Z. mays biosorbent were well defined using linearity coefficients (R²) by the pseudo-second-order equation (0.9998). The results obtained showed that Zea may stalk sponge was a useful biomaterial for Pb(II) sorption and that pH has an important effect on metal biosorption capacity.     

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH > ACPAH > ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl solution.     

Loofa egyptiaca as a novel adsorbent for removal of direct blue dye from aqueous solution

In this paper, Loofa egyptiaca (LE), an agricultural plant cultivated in Egypt, was used to prepare low-cost activated carbon (LE_C1 and LE_C2) adsorbents. The adsorbents (LE, LE_C1 and LE_C2) were evaluated for their ability to remove direct blue 106 dye from aqueous solutions. Batch mode experiments were conducted using various parameters such as pH, contact time, dye concentration and adsorbent concentration. The surface chemistry of LE, LE_C1 and LE_C2 was analyzed by scanning electron microscopy (SEM). The experimental data were examined using Langmuir, Freundlich, Temkin and Harkins–Jura isotherms. The results showed that the adsorption of direct blue 106 was maximal at the lowest value of pH (pH = 2). Removal efficiency was increased with an increase in dye concentration and a decrease in amount of adsorbent. Maximum adsorption capacity was found to be 57.14, 63.3 and 73.53 mg/g for LE, LE_C1 and LE_C2 respectively. Kinetics were also investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The experimental data fitted very well with the pseudo-first-order and pseudo-second-order kinetic models. The results indicate that LE, LE_C1 and LE_C2 could be employed as adsorbents for the removal of direct blue dye from aqueous solutions.     

Biosorption of copper(II) and lead(II) onto potassium hydroxide treated pine cone powder

Pine cone powder surface was treated with potassium hydroxide and applied for copper(II) and lead(II) removal from solution. Isotherm experiments and desorption tests were conducted and kinetic analysis was performed with increasing temperatures.As solution pH increased, the biosorption capacity and the change in hydrogen ion concentration in solution increased. The change in hydrogen ion concentration for lead(II) biosorption was slightly higher than for copper(II) biosorption. The results revealed that ion-exchange is the main mechanism for biosorption for both metal ions. The pseudo-first order kinetic model was unable to describe the biosorption process throughout the effective biosorption period while the modified pseudo-first order kinetics gave a better fit but could not predict the experimentally observed equilibrium capacities. The pseudo-second order kinetics gave a better fit to the experimental data over the temperature range from 291 to 347 K and the equilibrium capacity increased from 15.73 to 19.22 mg g^?1 for copper(II) and from 23.74 to 26.27 for lead(II).Activation energy was higher for lead(II) (22.40 kJ mol^?1) than for copper(II) (20.36 kJ mol^?1). The free energy of activation was higher for lead(II) than for copper(II) and the values of ΔH* and ΔS* indicate that the contribution of reorientation to the activation stage is higher for lead(II) than copper(II). This implies that lead(II) biosorption is more spontaneous than copper(II) biosorption.Equilibrium studies showed that the Langmuir isotherm gave a better fit for the equilibrium data indicating monolayer coverage of the biosorbent surface. There was only a small interaction between metal ions when simultaneously biosorbed and cation competition was higher for the Cu-Pb system than for the Pb-Cu system. Desorption studies and the Dubinin–Radushkevich isotherm and energy parameter, E, also support the ion-exchange mechanism.     

Cellulose-based anion exchanger with tertiary amine functionality for the extraction of arsenic(V) from aqueous media

A novel cellulose-based anion exchanger (Cell-AE) with tertiary amine functionality was synthesized by graft polymerization reaction of cellulose and glycidyl methacrylate using N,N′-methylene-bis-acrylamide as a crosslinker and benzoyl peroxide as an initiator, followed by dimethylamine (amination) and acid (HCl) treatment. The chemical modification was confirmed by infrared spectroscopy and CHN analysis. The anion exchanger was used in batch processes to study AS(V) adsorption in solutions. The operating variables studied were pH, contact time, initial As(V) concentration, sorbent mass, and ionic strength. The process was affected by solution pH with an optimum adsorption occurring at pH 6.0. Adsorption equilibrium was achieved within 1 h. Increasing ionic strength of solution negatively affected the arsenic uptake. The adsorption process performed more than 99.0% of As(V) removal from an initial concentration of 25.0 mg/L. The process of adsorption followed pseudo-second-order kinetics. The adsorption equilibrium isotherm data were analyzed using the Langmuir, Freundlich, Redlich–Peterson and Langmuir–Freundlich equations. The Langmuir–Freundlich isotherm described the adsorption data over the concentration range 25–400 mg/L. The adsorption mechanism appears to be a ligand-exchange process. A simulated groundwater sample was treated with Cell-AE to demonstrate its efficiency in removing As(V). The adsorbed As(V) ions were desorbed effectively by a 0.1 M NaOH solution.     

Calcium oxide for CO2 capture: Operational window and efficiency penalty in sorption-enhanced steam methane reforming

Calcium oxide (CaO) is a material that is being widely investigated in the context of CO₂ capture. One such application is as a CO₂ sorbent in the sorption-enhanced steam methane reforming processes (SERP). CO₂ is captured in an adsorption mode, where the conversion of CH₄ to H₂ is also enhanced, and released later in a separate desorption mode. This work presents an analysis of the relation between different process conditions and parameters during both adsorption and desorption modes. The interrelation between these conditions and the sorbent properties as well as the targeted carbon capture ratio is analysed. Conditions relevant for capturing 85% of carbon in the feed on CaO are determined and interlinked. A steam-to-carbon ratio of 4.2 has been determined to be relevant under 600 °C and 17 bar adsorption conditions. Similarly, process conditions relevant for regenerating the sorbent are determined and interlinked. For purge steam-to-CO₂ ratio of 1.8 at a desorption pressure of 1 bar, relevant desorption temperature has been calculated to be 820 °C. System simulations under these adsorption and desorption conditions resulted in a system efficiency of 50.8%. Effect of tuning process operating conditions on system efficiency as well as the efficiency penalty associated with the regeneration of the sorbent are investigated by process simulations using Aspen Plus^®. Possible system heat integration routes to reduce the efficiency penalty are proposed and the results of the process simulations are presented.     

Biosorption of Cu and Zn from aqueous solutions by dried marine green macroalga Chaetomorpha linum

The biosorption of the heavy metals Cu²⁺ and Zn²⁺ by dried marine green macroalga (Chaetomorpha linum) was investigated. The biosorption capacities of the dried alga for copper and zinc were studied at different solution pH values (2–6), different algal particle sizes (100–800 μm) and different initial metal solution concentrations (0.5–10 mM). An optimum pH value of 5 was found suitable for both metal ions biosorption for both metal ions. At the optimum particle size (100–315 μm), biosorbent dosage (20 g/l) and initial solution pH (pH 5), the dried alga produced maximum copper and zinc uptakes values (q_max) of 1.46 and 1.97 mmol/g respectively (according to the Langmuir model). The kinetic data obtained at different initial metal concentrations indicated that the biosorption rate was fast and most of the process was completed within 120 min. This study illustrated an alternative technique for the management of unwanted biological materials using processed algal material. C. linum is one of the fast-growing marine algae in the lake of Tunis and could be utilized as a biosorbent for the treatment of Cu²⁺ and Zn²⁺ contaminated wastewater streams.     

Adsorption of carbon dioxide using impregnated activated carbon promoted by Zinc

The effect of impregnation of activated carbon with Cr₂O and Fe₂O₃ and promotion by Zn²⁺ on its adsorptive properties of carbon dioxide was studied using a volumetric adsorption apparatus at ambient temperature and low pressures. Slurry and solution impregnation methods were used to compare CO₂ capture capacity of the impregnated activated carbon promoted by Zinc. The obtained adsorption isotherms showed that amount of CO₂ adsorbed on the samples impregnated by Cr₂O was increased about 20% in compare to raw activated carbon. The results also showed that Fe₂O₃ was not an effective impregnating species for activated carbon modification. Moreover slurry impregnation method showed higher CO₂ adsorption capacity in comparison with solution impregnation method. Samples prepared by co-impregnation of two metal species showed more adsorption capacity than samples impregnated by just one metal species individually. Washing the impregnated samples by metal oxide resulted in 15% increase in CO₂ adsorption capacities of activated carbons which can be attributed to the metal oxides removal covering the adsorption surface. Decreasing impregnation temperature from 95 to 25 °C in solution method showed a significant increase in CO₂ adsorption capacity. Sips equation was found a suitable model fitting to the adsorption data in the range studied.     

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic,equilibrium, and thermodynamic studies

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4 h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.     

Experimental investigation of groundwater contamination by surface sources: Determination of adsorption capacity,diffusion, and sorption potential of selected anions in different soils

The present study investigated the fate and transport of two significant anions through soil to explore their potential as groundwater contaminants. The retention properties of chloride and sulfate in soils having several significantly different characteristics (soil‐1 and soil‐2) were determined using adsorption test and adsorption‐diffusion column experiments. The maximum adsorption capacity of chloride was 3.7 and 1.16 mg/g, respectively, in soil‐1 and soil‐2, with organic matter (OM) content of 3.92% and 4.69%, respectively. The sulfate adsorption obtained was 24.09% and 13.83%, respectively, in the two soils. The anions exhibited monolayer adsorption in the soils with replacement of hydroxyl ions from soils as the major mechanism of adsorption. On the other hand, the adsorption capacities obtained from the adsorption‐diffusion column experiment were about 100 times lower compared to that of the column tests of both of the soils. The maximum adsorption capacity of chloride was 0.03 mg/g and 0.01 mg/g, respectively, in soil‐1 and soil‐2, whereas that of sulfate was 0.04 mg/g and 0.03 mg/g. The empirical relation for depth of penetration (d) from a known spillage onto the soil surface was determined as a function of sorption capacity (S) and initial anion concentration (C) as d = 0.0073e^(?57S)C and d = 0.0038e^(?35S)C for chloride and sulfate, respectively.     

Treatment and toxicity evaluation of methylene blue using electrochemical oxidation,fly ash adsorption and combined electrochemical oxidation-fly ash adsorption

Treatment of a basic dye, methylene blue, by electrochemical oxidation, fly ash adsorption, and combined electrochemical oxidation-fly ash adsorption was compared. Methylene blue at 100 mg L^?1 was used in this study. The toxicity was also monitored by the Vibrio fischeri light inhibition test.When electrochemical oxidation was used, 99% color and 84% COD were removed from the methylene blue solution in 20 min at a current density of 428 A m^?2, NaCl of 1000 mg L^?1, and pH₀ of 7. However, the decolorized solution showed high toxicity (100% light inhibition).For fly ash adsorption, a high dose of fly ash (>20,000 mg L^?1) was needed to remove methylene blue, and the Freundlich isotherm described the adsorption behavior well.In the combined electrochemical oxidation-fly ash adsorption treatment, the addition of 4000 mg L^?1 fly ash effectively reduced intermediate toxicity and decreased the COD of the electrochemical oxidation-treated methylene blue solution. The results indicated that the combined process effectively removed color, COD, and intermediate toxicity of the methylene blue solution.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Optimization of the removal of chromium and lead by Penicillium chrysogenum using 2k factorial experiments

This study aims to prepare a low-cost, environmentally friendly, and alternative, biosorbent to remove chromium Cr (III) and lead Pb (II) from polluted water and to find out the highest removal efficiencies using 2^k factorial experiments. The Cr (III) and Pb (II) tolerant fungal strain identified as Penicillium chrysogenum was isolated from ceramic industrial sludge. The impact of process variables on biosorption of Cr (III) and Pb (II) by P. chrysogenum was first evaluated with the Taguchi screening design. Factors and levels were determined to optimize Cr (III) and Pb (II) removal efficiency. According to this, five factors; initial concentration, pH, biosorbent dose, temperature, and inactivation methods were determined for both metals, each factor defined as a fixed factor with two levels. Optimization of the parameters affecting the removal process was determined by the Taguchi method and the signal-to-noise (S/N) ratios are calculated. The maximum removal efficiency (99.92%) was observed at pH 7, biosorbent 1 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Cr (III). On the other hand, the maximum removal efficiency (98.99%) was observed at pH 4, biosorbent 5 mg L^–1, inactivation with autoclaving, and at 20°C with an initial metal concentration of 50 mg L^–1 Pb (II). Furthermore, metal ions removal by P. chrysogenum was also confirmed by scanning electron microscopy (SEM) combined with an energy dispersive X-ray spectrometer (EDS). The presence of functional groups on fungal cells of metal binding was investigated by Fourier transform infrared (FT-IR).     

Utilization of anaerobically treated distillery spent wash for production of cellulases under solid-state fermentation

Pollution caused by distillery spent wash on one hand has stimulated the need to develop new technologies to treat the waste and on the other, forced us to reevaluate the efficient utilization of its nutritive potential for production of various high value compounds. In this study, anaerobically treated distillery spent wash was used for the production of cellulases by Aspergillus ellipticus under solid-state fermentation using wheat straw as a substrate. The interactions between distillery effluent concentration, initial pH, moisture content and inoculum size were investigated and modeled using response surface methodology (RSM) involving Box–Behnken design (BBD). Under optimized conditions, filter paper activity, β-glucosidase and endo-β-1,4-glucanase activities were found to be 13.38, 26.68 and 130.92 U/g of substrate respectively. Characterization of endo-β-1,4-glucanase and β-glucosidase was done after partial purification by ammonium sulfate fractionation followed by desalting. The partially purified endo-β-1,4-glucanase and β-glucosidase showed maximum activity at 60 °C. Saccharification studies performed with different lignocellulosic substrates showed that wheat bran was most susceptible to enzymatic hydrolysis. The study suggests that anaerobically treated distillery spent wash can be used as a viable nutrient source for cellulase production under solid-state fermentation by A. ellipticus.     

Application of a chemically modified green macro alga as a biosorbent for phenol removal

Phenol and substituted phenols are toxic organic pollutants present in tannery waste streams. Environmental legislation defines the maximum discharge limit to be 5–50 ppm of total phenols in sewers. Thus the efforts to develop new efficient methods to remove phenolic compounds from wastewater are of primary concern. The present work aims at the use of a modified green macro alga (Caulerpa scalpelliformis) as a biosorbent for the removal of phenolic compounds from the post-tanning sectional stream. The effects of initial phenol concentration, contact time, temperature and initial pH of the solution on the biosorption potential of macro algal biomass have been investigated. Biosorption of phenol by modified green macro algae is best described by the Langmuir adsorption isotherm model. Biosorption kinetics of phenol onto modified green macro algal biomass were best described by a pseudo second order model. The maximum uptake capacity was found to be 20 mg of phenol per gram of green macro algae. A Boyd plot confirmed the external mass transfer as the slowest step involved in the biosorption process. The average effective diffusion coefficient was found to be 1.44 × 10⁻⁹ cm²/s. Thermodynamic studies confirmed the biosorption process to be exothermic.     

Synthesis of mesoporous magnesium oxide: Its application to CO2 chemisorption

Mesoporous magnesium oxide (MgO) was synthesized using mesoporous carbon CMK-3 obtained from mesoporous SBA-15 as exotemplate. P123 was used as the structure-directing template and rice husk ash (RHA) as the silica source for the synthesis of SBA-15, which was subsequently treated with sucrose and sulphuric acid to obtain mesoporous carbon (CMK-3). X-ray powder diffraction (XRD) results and the type-IV adsorption isotherm with H1 hysteresis obtained by N₂ adsorption/desorption study for SBA-15, CMK-3 and mesoporous MgO suggests its resemblance with materials synthesized using conventional silica sources. Mesoporous MgO was subjected for CO₂ adsorption study in TGA; adsorption was 8 and 10 wt% at 25 and 100 °C, respectively. Finally, mesoporous MgO is selective to CO₂ gas, thermally stable and regenerable. Thus, this study contributes a better route to enhance CO₂ gas adsorption and use ecological waste rice husk for the synthesis of such efficient mesoporous materials.