Kinetics and equilibrium studies from the methylene blue adsorption on diatomite treated with sodium hydroxide

Diatomite was treated with sodium hydroxide to remove impurity in order to improve its performance as an adsorbent. The raw diatomite and purified diatomite were characterized by scanning electron microscopy, energy dispersive X-ray analysis and Brunauer–Emmett–Teller adsorption. It was found that the surface area was in order of 15.87 m² g^− 1 for raw diatomite and 31.35 m² g^− 1 for purified diatomite. Scanning electron microscopy images showed the well-developed porous structure of purified diatomite. Purified diatomite improved a more than tenfold increase in adsorption amount from 1.72 mg g^− 1 to 18.15 mg g^− 1 and removal efficiency from 8.60% to 90.75% for methyelen blue initial concentration 100 ppm respectively. The kinetics studies showed that experiment data followed pseudo-second-order model better. The equilibrium data was fitted to Langmuir and Freundlich adsorption isotherms and was found that Langmuir model presented the best fit, showing maximum monolayer adsorption capacity of 27.86 mg g^− 1. The thermodynamic parameters such as the standard enthalpy, standard entropy and standard free energy were evaluated. The obtained results indicated the adsorption of methylene blue onto diatomite treated with sodium hydroxide is endothermic and spontaneous process and confirmed the applicability of this purified inorganic material as an efficient adsorbent for basic dyes.     

Synthesis of electrically conducting composite adsorbents for wastewater treatment using adsorption & electrochemical regeneration

Electrically conducting adsorbent materials called Nyex™ 1000 & 2000 have already been reported with comparatively low adsorption capacity for various organic, biologically non-degradable and toxic compounds. Two composite adsorbents called CA₁ & CA₂ were synthesized using synthetic graphite-carbon black and expanded graphite-carbon black respectively. The aim of developing the new adsorbents was to increase the adsorption capacity along with good electrical properties. The developed adsorbents were characterized using N₂ adsorption for specific surface area, Boehm surface titration for surface chemistry, bed electrical conductivity, laser size analyzer for average particle size, and scanning electron microscope (SEM) for particle morphology and shape. Then both the composite adsorbents were tested for the adsorption of acid violet 17 followed by an electrochemical regeneration. The adsorption study revealed that both the adsorbents had almost similar kinetic behavior with a significant increase in adsorption capacity for acid violet 17 (300 & 26 mg g⁻¹ respectively) when compared with the adsorption capacity of previously developed electrically conducting materials called Nyex™ 1000 & 2000 (3.5 and 9 mg g⁻¹ respectively). The composite adsorbent CA₂ was successfully electrochemically regenerated by passing an electric charge of 138 C g⁻¹ at a current density of 14 mA cm⁻² for a treatment time of 60 min, whereas, the composite adsorbent CA₁ could not be regenerated successfully. The regeneration efficiencies of CA₂ were obtained at around 120% during five adsorption–regeneration cycles. The amount of actual charge passed of 138 C g⁻¹ for achieving 100% regeneration efficiency was found to be similar with stoichiometrically calculated amount of charge. The amount of electrical energy required to oxidize each mg of adsorbed acid violet onto CA₂ (24 J mg⁻¹) was found to be significantly lower to that of Nyex™ 1000 & 2000 adsorbents (52 J mg⁻¹ & 32 J mg⁻¹ respectively).     

Removal of Maxilon Yellow GL in a mixed methanogenic anaerobic culture

Degradation of dye Maxilon Yellow GL (MY GL) (Basic Yellow 45) was investigated with anaerobic mixed culture using glucose (3000 mg l⁻¹ COD) as carbon source and electron donor throughout batch experiments. Zero-, first- and second-order reaction kinetics were used to find out the suitable substrate removal and decolorization kinetics. The substrate removal (COD) process is suitable for second-order reaction kinetics among the kinetic models studied. Decolorization process also approximates to second-order kinetics between 50 and 1000 mg l⁻¹ of MY GL concentration. Substrate and color removal rates (mg l⁻¹ h⁻¹) were found to be 6.38, 5.98, 4.6, 4.16, 3.64, 2.86, 2.34 and 0.075, 0.0149, 0.0265, 0.0303, 0.0426, 0.053, respectively, in all serum bottles throughout the incubation period. Color removal efficiencies decreased as the influent dye concentration increased. The highest removal efficiency (80%) was obtained with 50 and 100 mg l⁻¹ of MY GL dye concentrations. However, the lowest removal efficiency (28%) was found with a 1000 mg l⁻¹ of MY GL dye concentration. Complete dye reduction was not found for this basic dye. The results indicate that anaerobic mixed culture can decolorize low concentration of this basic dye.     

Study of competitive adsorption of malachite green and sunset yellow dyes on cadmium hydroxide nanowires loaded on activated carbon

Cadmium hydroxide nanowires loaded on activated carbon (Cd(OH)₂-NW-AC) was applied for removal of malachite green (MG) and sunset yellow (SY) in single and binary component systems. This novel material was characterized and identified by different techniques such as Brunauer, Emmett and Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis. Unique properties such as high surface area (>1271 m² g⁻¹) and low pore size (<35 Å) and average particle size lower than 50 Å in addition to high reactive atom and presence of various functional groups make it possible for efficient removal of these two dyes. In the single component system in this study, maximum adsorption capacity of 80.6 for SY and 19.0 mg g⁻¹ for MG at 25 °C was reported. The Langmuir model had very well fit with the experimental data (R² > 0.996). A better agreement between the adsorption equilibrium data and mono-component Langmuir isotherm model was found. The kinetics of adsorption for single and binary mixture solutions at different initial dye concentrations were evaluated by the nonlinear first-order and second-order models. The second-order kinetic model had very well fit with the dynamical adsorption behavior of a single dye for lower and higher initial dye concentrations. SY and MG without spectra overlapping were chosen and analyzed with high accuracy in binary solutions. The effect of multi-solute systems on the adsorption capacity was investigated. The isotherm constants for SY and MG were also calculated in binary component systems at concentrations within moderate ranges, the Langmuir isotherm model satisfactorily predicted multi-component adsorption equilibrium data. The competitive adsorption favored the SY in the A mixture solution (both SY and MG concentration at 10 mg L⁻¹) and B mixture solution (25 mg L⁻¹ of SY and 10 mg L⁻¹ of MG). Also, in both cases, kinetic data was fairly described by two-step diffusion model. An endothermic and spontaneous nature for the adsorption of the dyes studied were shown from thermodynamic parameters in single and binary component systems.     

Graphene oxide–tripolyphosphate hybrid used as a potent sorbent for cationic dyes

Graphene oxide–tripolyphosphate material (GPM) was synthesized through an ethanolamine (EA) mediated graphene oxide (GO) self-assembly. The synthesis route to GPM is simple and benign. GPM was composed of GO nanosheets as building blocks and the tripolyphosphate as cross-linkers and chelators of cations in solutions. GPM showed higher potency for adsorption of cationic dyes than anionic dyes, and the adsorption process was through electrostatic and π–π interactions. Adsorption was spontaneous and exothermic, and the adsorption capacity of GPM for cationic dyes (>2540 mg g⁻¹) far exceeded those reported in literature for GO materials.     

Self-assembly hydrothermal assisted synthesis of mesoporous anatase in the presence of ethylene glycol

Mesoporous nanocrystalline anatase was prepared hydrothermally employing P123 as structure-directing agent. Ethylene glycol was used as a key synthesis parameter to fine tune the morphology, crystal size and pore size of the resultant mesophases. The incorporation of EG in the synthesis gel resulted in the formation of 1–2 μm sphere-like shapes and led to an increase in the specific surface area from ∼95 to ∼170 m²/g, decrease in the average pore size from ∼11 to ∼4.8 nm, and decrease in the average crystallite size from ∼17 to ∼12 nm. These mesophases were used as photocatalysts for the UV degradation of methylene blue and methyl orange. The mesoporous anatase phases photodegraded MB ∼1.5–3× faster than commercially available P25 and showed limited photocatalytic behavior for methyl orange.     

Physico-chemical treatment applied to compost liquor: Feasibility study

Compost liquor was treated using a combination of physico-chemical processes: (i) lime precipitation, (ii) filtration on a rotary drum vacuum precoat filter, (iii) ultrafiltration, and (iv) reverse osmosis. Laboratory Jar tests showed the interest of using lime to precipitate compost liquor. Yields of ammonium removal up to 90% were obtained for an optimum lime concentration of 6 g L^?1. A test was run at semi-industrial scale on 400 L of highly loaded compost liquor (COD: 15,800 mg L^?1, ammoniacal pollution: 18,433 mg NH₄⁺-N L^?1, conductivity: 74,000 μS cm^?1) to demonstrate the potential of the treatment process proposed. Outstanding purification yields were obtained, especially 95% of COD removal and 93% of ammoniacal pollution removal.     

Principal component analysis-artificial neural network and genetic algorithm optimization for removal of reactive orange 12 by copper sulfide nanoparticles-activated carbon

In this study a green approach described for the synthesis of copper sulfide nanoparticles loaded on activated carbon (CuS-NP-AC) and usability of it for the removal of reactive orange 12 (RO-12). This material was characterized using instruments such as scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effects of variables were optimized using Principal component analysis-artificial neural network (PCA-ANN). Fitting the experimental equilibrium data shows the suitability of the Langmuir isotherm. The small amount of proposed adsorbent (0.017 g) is applicable for successful removal of RO-12 (RE > 95%) in short time (31.09 min) with high adsorption capacity (96.9 mg g⁻¹)     

Extraction and recovery of rhodamine B,methyl violet and methylene blue from industrial wastewater using D2EHPA as an extractant

The extraction behavior of cationic dyes namely rhodamine B (RB), methyl violet (MV) and methylene blue (MB) from industrial wastewater has been investigated using di-(2-ethylhexyl) phosphoric acid (D2EHPA) in hexane as a carrier. The extraction of cationic dyes increases with decreasing feed phase pH and increasing D2EHPA concentration in organic phase. The stripping percentage of dyes using acetic acid as the stripping agent from loaded D2EHPA was found to increase with increasing acid concentration. 98% stripping efficiency of dyes was achieved with 8.5 mol/L acetic acid solution at an organic:aqueous phase ratio (O/A) of 2:1. Parameters examined include D2EHPA concentration, effect of diluents, effect of pH, effect of initial dye concentration, equilibration time, and various stripping agents, aqueous to organic phase ratio in extraction and organic to aqueous phase ratio in stripping.     

Kinetic studies on agrochemicals wastewater treatment by aerobic activated sludge process at high MLSS and high speed agitation

In the present work an effort has been made to study the kinetics of agrochemicals industry wastewater treatment by aerobic activated sludge process at high mixed liquor suspended solids (MLSS) and high speed agitation. MLSS concentration was varied in the range 6000–40,000 mg L^?1 and 2.5 mg L^?1 optimum dissolved oxygen (DO) was employed. Highest chemical oxygen demand (COD) reduction was found to be 76.83% at 9000 mg L^?1 MLSS at 130 rpm and DO 2.5 mg L^?1. Highest COD reduction was observed to be 80.76% at 25,000 mg L^?1 MLSS at higher agitation speed.     

Immobilization of lead by application of zeolite: Leaching column and rhizobox incubation studies

Application of zeolite can reduce lead (Pb) mobility in soil. Leaching columns and rhizobox incubation experiments were carried out to investigate the leaching processes and rhizosphere behavior of Pb in a Pb-contaminated soil amended with zeolite. Zeolite addition reduced Pb release from the contaminated soil as well as increasing leachate pH and decreasing the bioavailable Pb concentration. Leachate pH was not significantly different among different zeolite dose treatments at the same measurement time. Leaching of Pb from the treated soil was lower than that from the untreated soil for the first nine weeks but the trend was reversed for the final weeks of the study. The Pb concentration in the leachate did not appear to be sensitive to changes in pH. It was concluded that when a relatively low amount of zeolite was added (< 20 mg kg^− 1), the cation exchange capacity was the dominant factor for regulating Pb leaching behavior. The DTPA extractable Pb in the rhizosphere was ~ 15% higher than that in the close-root and bulk soil. In addition, the amounts of DTPA extractable Pb in the rhizosphere soil not treated with zeolite were 10% and 16% higher than in the rhizosphere soil with 10 and 20 g kg^− 1 zeolite addition, respectively. It could be concluded that zeolite addition inhibits uptake of Pb by affecting rhizospheric behavior.     

Combustion synthesis of ZnAl2O4 powders with tuned surface area

Zinc aluminate powders with tuned surface area were prepared by solution combustion synthesis, using different oxidizer-fuel ratios. As the amount of urea increased, standard heat of reaction and standard Gibbs free energy decreased, whilst adiabatic temperature increased. The larger amount of energy released during combustion facilitated grain growth and sintering, causing the decrease of specific surface area from 156 to 27 m² g⁻¹. The particle size estimated from TEM increased from 8 to 40 nm. The adsorption capacity of zinc aluminate powders with respect to methyl orange was highly dependent on the specific surface area. For an adsorbent dose of 3 g L⁻¹ the removal efficiency of methyl orange was much larger (86 versus 18%) in the case of the sample with larger surface area. The adsorption kinetics followed a pseudo-second-order model and the equilibrium data were correlated with the Freundlich isotherm.     

Decolorization of azo dyes by photo electro adsorption process using polyaniline coated electrode

This study is a report on the photo electro adsorption (PEA) decolorization of a mixture of three azo dyes, i.e., Acid Red 88 (AR88), Acid Blue 92 (AB92), and Acid Orange 2 (AO2) with polyaniline-modified electrode as a conductive polymer. Aniline was electropolymerized on steel electrode by being immersed in a solution containing HClO₄ as the supporting electrolyte and NaClO₄ as the dopant. This modified electrode was then used in a non-continuous reactor using UV irradiation for the decolorization of azo dyes. To obtain the best conditions for high decolorization efficiency, experiments were carried out at different operational conditions, including initial dye concentration, pH, and bias potential. The morphology of polyaniline film was analyzed by scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectrum was obtained to characterize polyaniline and dyes. Energy consumption was calculated to be 3.6 kWh/m³ after 36 min of treatment process. Maximum removal of 96% was achieved for the mixture of AR88, AB92, and AO2 in aqueous solution at pH 5, initial dye concentration of 30 mg L⁻¹, and bias potential of 1.3 V after 40 min of PEA process. The results indicate that the PEA process could be effectively applied to the removal of industrial effluents.     

Use and recycling of Ca-alginate biocatalyst for removal of phenol from wastewater

The objective of the current work is the exhaustive study of the phenol degradation potential in both free cell and immobilized bacterium (Pseudomonas aeruginosa) in calcium alginate beads (biocatalyst) was investigated for its ability to grow and degrade phenol as its sole source of carbon and energy.The biodegradation assays were performed in liquid medium with phenol being the only substrate. It was found that P. aeruginosa is able to degrade phenol up to 500 mg L^?1 in 50 h as free cell and 900 mg L^?1 in 80 h when immobilized in the calcium alginate beads. However, for 1200 mg L^?1 concentration, the immobilized cells took much more time (290 h) for a complete degradation.The reuse of these beads in different concentrations of phenol (100–900 mg L^?1) showed that the cells keep their phenol degradation ability up to 900 mg L^?1in 78.5 h with 99% removal efficiency.Similarly, the reuse of the biocatalyst in the same initial phenol concentration (500 mg L^?1), allows us to get 9 cycles.     

Preparation and performance of a high purity poly-aluminum chloride

Poly-aluminum chloride (PACl) is one of the common coagulants for water and wastewater treatment. A new Chinese national standard of PACl has been implemented, where the concentration of insoluble substances, iron and heavy metals is to be controlled strictly, then researches on the preparation of high-purity PACl are needed. This paper presents a novel method to prepare high-purity PACl which contains high aluminum oxide content (>10%), high basicity (>90%), and low insoluble substance (<0.04%), iron (<300 mg L^?1) and heavy metals. Samples taken from the Huangpu River were used to evaluate the coagulation performance of high-purity PACl in comparison with conventional PACl. The results demonstrate that for the whole dose range studied, high-purity PACls removed more turbidity than conventional PACl. On the other hand, when the dose was greater than 4 mg L^?1 as Al, the high-purity PACl showed great UV₂₅₄-absorbance removal capacity; which was even much greater at high does (e.g., 10 mg L^?1). This could be partly attributed to the charge effect where a relative high zeta potential in the test water was achieved by dosing high-purity PACl.     

Removal of Cu(II) by biosorption onto coconut shell in fixed-bed column systems

Biosorption of Cu(II) onto coconut shell, an agricultural biomaterial, was studied in a fixed-bed column. The Cu(II) biosorption column had the best performance at 10 mg L^?1 inlet Cu(II) concentration, 10 mL min^?1 flow rate and 20 cm bed depth. The equilibrium uptake of Cu(II) amounted to 7.25 mg g^?1. The simulation of the breakthrough curve was successful with the BDST and Yoon–Nelson models, but the entire breakthrough curve was best predicted by the Clark model. The design of a fixed bed column for Cu(II) removal from wastewater by biosorption onto coconut shell can be done based on these models.     

One 2D anionic coordination polymer with {[Co(H2O)6]}2 + cationic guest for fast and selective adsorption of cationic dyes

One new anionic Coordination Polymer, namely [Co(H₂O)₆]^2 +·[Co₃(bptc)₂(H₂O)₁₀]^2 −·3H₂O (1), where H₄bptc = 3,3′,5,5′-biphenyltetracarboxylate, has been synthesized hydrothermally and characterized. In compound 1, bptc^4 − as tridentate ligands connect the Co^2 + cations to form a 2D layer with 1D pseudo channels encapsulation of [Co(H₂O)₆]^2 + guest. In addition, their adsorption activities for organic dyes were investigated in aqueous solution. The results suggested that the anionic complex 1 show rapid and selective adsorption of cationic dyes for Neutral red, Methylene blue.     

Clarification of red raspberry juice using microfiltration with gas backwashing: A viable strategy to maximize permeate flux and minimize a loss of anthocyanins

Red raspberry (Rubus idaeus) juice was produced by maceration of raspberry pulp at 50 °C for 2 h using 400 mg kg^?1 Klerzyme^®150 enzymatic pectolitic preparation followed by raw juice clarification with gelatin and bentonite or cross-flow membrane filtration. A minimal loss of anthocyanins from 630 to 540 mg l^?1 was obtained when the juice was clarified using a ceramic multichannel microfilter (MF) with a pore size of 0.2 μm. A light transmission at 625 nm in MF permeate was above 85% and the residual pectin (900 mg l^?1) was completely removed. During ultrafiltration through ceramic or polysulfone membranes with a molecular weight cut-off of 30–300 kDa, the content of anthocyanins was reduced to 220–370 mg l^?1, but a light transmission at 625 nm was as high as 96%. The permeate flux in MF was maintained at high values above 170 l m^?2 h^?1 at 3 bar for more than 2 h by backwashing the membrane with a compressed air every 6 min for 1 min. The cake compression at high pressures was avoided by short filtration times between backwashing.     

Chitin as biosorbent for phenol removal from aqueous solution: Equilibrium,kinetic and thermodynamic studies

Phenol removal from aqueous solution was studied employing chitin as low cost biosorbent. Initial biosorption tests carried out in the pH range 2–10 pointed out an optimum pH of 2. Temperature and initial phenol concentration were then varied in the ranges 15 ≤ T ≤ 50 °C and 10.4 ≤ C₀ ≤ 90.8 mg L⁻¹, respectively. The good applicability of Langmuir, Freundlich and Temkin models (R² = 0.990–0.993) to describe equilibrium isotherms suggested an intermediate mono-/multilayer biosorption mechanism along with a semi-homogeneous architecture of biosorbent surface. Biosorption capacity progressively increased from 3.56 to 12.7 mg g⁻¹ when starting phenol concentration was raised from 10.4 to 90.8 mg L⁻¹, and the related sorption kinetics was investigated by pseudo first-order, pseudo second-order and intraparticle diffusion models. The pseudo second-order model, which showed the best fit of experimental data (R² = 0.999), allowed estimating a second-order rate constant of 0.151 g mg⁻¹ h⁻¹ and a theoretical sorption capacity of 7.63 mg g⁻¹. Phenol biosorption capacity increased with temperature up to a maximum value, beyond which it decreased, suggesting the occurrence of a thermoinactivation equilibrium. Finally, to identify the main functional groups involved in phenol biosorption, both raw and phenol-bound materials were explored by FT-IR spectroscopy.     

Removal of aqueous Fe2+ using MnO2–clinoptilolite in a batch slurry reactor: Catalyst synthesis,characterization and modeling of catalytic behavior

An Iranian clinoptilolite has been modified with MnO₂ for the catalytic removal of Fe²⁺ cations from water in a batch slurry reactor. The modified zeolite was subjected to FESEM, XRD, WDX, XRF and specific surface area analysis. A correlation for the intrinsic catalytic reaction rate incorporating both Fe²⁺ and dissolved oxygen concentration as a function of reaction temperature has been presented. The effect of the modified zeolite aggregate particle size on the iron removal kinetics has been investigated. It was shown that for particles larger than 150 μm, diffusion through the mesopores of the zeolite aggregate is rate controlling. The effective diffusion coefficient through the particles at RT has been calculated as 2.3 × 10^?6 cm² s^?1. It is shown that liquid phase molecular diffusion within the mesopores is the dominating mass transfer mechanism.