p-Sulphonatocalix[8]arene functionalized silica resin for the enhanced removal of methylene blue from wastewater: equilibrium and kinetic study

ABSTRACT

The present investigation represents the synthesis of new p-sulphonatocalix[8]arene-based silica resin, p-SC8SR (5) and its application for the enhanced removal of methylene blue (MB) dye from contaminated water. The new p-SC8SR (5) resin was characterized by FT-IR, SEM, and EDX spectroscopy. The adsorption of MB on p-SC8SR (5) was investigated systematically by evaluating the effects of adsorbent dosage, initial pH, contact time, dye concentration, and ionic strength. Excellent adsorption (94%) of MB on p-SC8SR (5) was achieved at pH 9.5, contact time 10 min by using 0.2 mol L^?1 ionic strength and 2 × 10^?5 M initial MB dye concentration. Kinetic behavior of MB dye adsorption process on the newly synthesized p-SC8SR (5) adsorbent follows the pseudo-second-order rate model (R² = 0.998 and 0.999 for 2 × 10^?5 M and 1 × 10^?4 M, respectively). Adsorption isotherms were fitted well by the Freundlich model with excellent value of coefficient of determination (R²) = 0.995 which demonstrated that the adsorption of MB follows multilayer mechanism. Wastewater samples contaminated with MB were used to assess efficiency of the p-SC8SR (5) adsorbent. Results indicated that newly synthesized p-SC8SR (5) was found to be efficient adsorbent. During the removal process, the role of different functional groups’ cyclic structure was scrutinized and found that the ionic property as well as π–π interaction of host molecules played imperative role in the extent of adsorption.     

A study of hydroxyethyl imidazoline as H2S corrosion inhibitor using electrochemical noise and electrochemical impedance spectroscopy

A study of H₂S corrosion inhibition of pipeline steel by hydroxyethyl imidazoline has been carried out by using electrochemical techniques. Inhibitor concentration included 5, 10, 25, 50, and 100 ppm in a H₂S-containing 3% NaCl solution at 50 °C. Techniques included linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), and electrochemical noise (EN) measurements. In addition to the traditional noise in voltage and current, noise resistance (R _n) measurements were used. All techniques showed that the most efficient inhibitor concentration was between 5 and 10 ppm, but inhibitor efficiency decreased after 8 h of testing. Furthermore, EN measurements showed that steel was highly susceptible to localized corrosion at inhibitor doses lower than 10 ppm due to the establishment of a porous inhibitor film. However, with 50 or 100 ppm of inhibitor, the steel was susceptible to a mixture of uniform and localized corrosion. Hurst exponent was higher in presence of inhibitor for times shorter than 8 h, indicating a short residence time of the inhibitor. The data could not be fitted to any adsorption isotherm model, indicating a lack of strong adsorption of the inhibitor to the metal surface.     

Electrochemical Regeneration of Zn-Saturated Granular Activated Carbon from Electroplating Wastewater Plant

An electrically assisted regeneration (EAR) process was used to assess the effectiveness of regenerating exhausted granular activated carbon (GAC) preloaded with electroplating wastewater containing hyper Zn concentration at a concentration of 950.5 mg L ^?1  (1.45 × 10 ^?2  mol L ^?1 ). The electrochemical rege-neration process supplied with direct current was controlled at a constant voltage of 5.0 V. Two regeneration methods were tested and compared: first, acid washing (pH 1.0) and, second, electrically assisted acid washing. Results showed that the Zn adsorption capacity of GAC regenerated by EAR was significantly higher than that of GAC regenerated by acid washing. The effectiveness of the Zn desorbing efficiency from GAC was enhanced by electric current in the electrochemical regeneration process. Using the EAR method, a regeneration efficiency of 88.3% was observed for GAC, whereas using acid regeneration, the efficiency was only 25.3%. These observations reveal that EAR could be a potential alternative to acid washing for the regeneration of GAC saturated with Zn.     

Inhibition and interfacial behaviour of novel amidine inhibitors against brass corrosion in 1 M HNO3 under flow conditions

Abstract

Amidine inhibitors for brass in 1?M HNO₃ were synthesized, and the electrochemical behaviours were investigated by different electrochemical techniques under flow conditions. This type of inhibitor can effectively overcome the fluid impact in flowing HNO₃ solutions for at least 24?h. The amidine inhibitors caused mainly cathodic curves to low current density and significantly strengthened the impedance under flow conditions. The relationship between concentration, flow conditions, and inhibition effects was investigated by weak electrochemical polarization curves, electrochemical impedance spectroscopy, and scanning electron microscopy. Adsorption thermodynamics indicated that all of the inhibitors function via chemisorption processes with Gibbs free energies of approximately -40?kJ/mol. A modified adsorption model was constructed based on the results of electrochemical experiments to explain why higher concentrations resulted in worsened inhibition effects due to fluid impact. The adsorption mechanism was identified by X-ray photoelectron spectroscopy, ATR-FTIR spectroscopy, and quantum chemical calculations. All of the chemistry analyses indicated that the amidine and heteroatoms contributed to surface adsorption.     

Removal of Carbon Dioxide from Light Gas Mixtures using a Porous Strontium(II) Silicoaluminophosphate Fixed Bed: Closed Volume and Portable Applications

A Sr²⁺ -SAPO-34 bed was assembled to study CO₂ dynamic adsorption under conditions that emulate those found in closed volume and portable applications. Although the surface area was reduced by 7% during pelletization, adsorption capacities estimated from breakthrough curves compared well with static volumetric adsorption data. Modeling of the breakthrough adsorption was achieved using a Linear Driving Force mass transfer rate model, showing good agreement with the experimental data and confirming fast kinetics and efficient use of the bed. Fast kinetics were also evidenced by the length of the unused section of the bed as calculated from a Mass Transfer Zone model. Adsorption capacity degradation was not observed after multiple regeneration cycles. Apparent and equilibrium adsorption isotherm data estimated from the bed and static volumetric experiments at 25° C were compared to that of 5A Zeolite. These showed that Sr²⁺ -SAPO-34 is a superior adsorbent for CO₂ removal in the low partial pressure range (<1500 ppm). CO₂ and H₂ O multicomponent adsorption breakthrough curves were also gathered for a CO₂ inlet concentration of 1000 ppm and dew points of ?5 and 8° C. The addition of moisture resulted in a decrease in total processed gas volume by 31 and 47%, respectively.     

Corrosion inhibition of mild steel in sulphuric acid using a bicyclic thiadiazolidine

The inhibitory effect of 3a,6a-diphenyltetrahydro-1H-imidazo [4,5-c] [1, 2, 5] thiadiazole-5(3H)-thione 2,2-dioxide (TTU) on the corrosion behaviour of mild steel in 0.5 M H₂SO₄, at (30 ± 0.5) °C was studied by gravimetric, potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning electron microscopy measurements. The effect of inhibitor concentration on the corrosion rate, surface coverage and inhibition efficiency is investigated. Results show that TTU exerts a strong inhibiting effect on mild steel corrosion and acts as a cathodic-type inhibitor. TTU does not affect the mechanism of the cathodic reaction while the anodic reaction mechanism changes upon addition of the inhibitor. Possible mechanistic pathways for the inhibition process are proposed. The inhibition efficiency of TTU may be due to either the adsorption of inhibitor molecules building a protective film or the formation of an insoluble complex of the inhibitor with metal cations. TTU adsorption obeys the Langmuir model.     

Corrosion inhibition effect of pyrazole derivatives on mild steel in hydrochloric acid solution

Synthesized compounds, namely methyl 5-(4-Chlorobenzoyloxy)-1-phenyl-1H-pyrazole-3-carboxylate (MCPPC) and 5-(4-methoxyphenyl)-3-(4-methylphenyl)4,5-dihydro-1H-pyrazol-1-yl-(pyridin-4-yl)methanone (MMDPPM) were investigated as corrosion inhibitor for mild steel (MS) in 15% HCl solution using weight loss measurement, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods. Inhibition efficiency was found concentration-dependent and increased by increasing the concentration of MCPPC and MMDPPM. Both of inhibitors were efficient even at a very low concentration of 25 ppm. The inhibitors MCPPC and MMDPPM showed inhibition efficiency of 67.1 and 76.8%, respectively, at 25 ppm, whereas it was 92.0 and 95.9%, respectively, at 250 ppm concentration at 303 K. The potentiodynamic polarization curves showed that MCPPC and MMDPPM act as mixed-type inhibitor in 15% HCl solution. The Nyquist plots showed that charge transfer resistance increased and double-layer capacitance decreased on increasing the concentration of studied inhibitors due to adsorption of inhibitor molecules on MS surface. The adsorption of each inhibitor on MS surface obeys Langmuir adsorption isotherm. On the basis of thermodynamic adsorption parameters, mixed-type adsorption (physisorption and chemisorption) for the studied inhibitors on MS surface was suggested. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscopy (AFM) analyses confirmed the existence of a protective film of the inhibitor on MS surface. The density functional theory was employed for theoretical calculations, and the obtained results were found to be consistent with the experimental findings.     

Synthesis and Inhibition Effect of a Novel Tri-cationic Surfactant on Carbon Steel Corrosion in 0.5 M H2SO4 Solution

A novel Tri-cationic surfactant was synthesized, purified and characterized. The critical micelle concentration value of the prepared surfactant was determined by surface tension and conductivity measurements. The surface parameters were calculated by surface tension measurements. The relationship between the surface properties and the corrosion inhibition efficiency of the prepared surfactant was discussed. The inhibition effect of the novel Tri-cationic surfactant on carbon steel corrosion in 0.5 M H₂SO₄ was studied by potentiodynamic polarization, electrochemical impedance spectroscopy and weight loss techniques. Potentiodynamic polarization studies revealed that the inhibitor acted as a mixed-type inhibitor. The high inhibition efficiency was attributed to the blocking of active sites on the steel surface through the adsorption of inhibitor molecules. Inhibitor adsorption on the carbon steel surface was in accordance with the Langmuir adsorption isotherm model. Thermodynamic adsorption and kinetic parameters were obtained from weight losses at different temperatures (20–60 °C).     

Modeling of Adsorptive Filtration of a Leather Dye in a Fixed Bed Column

Abstract

Activated carbons offer an efficient option for the removal of organic and inorganic contaminants from water. However, due to its high costs and difficulty in the regeneration, other low cost adsorbents have been used. In this work, the adsorption capacity of an adsorbent carbon with high iron oxides concentration was compared with that of a commercial activated carbon in the removal of a leather dye from an aqueous solution. The adsorbents were characterized using SEM/EDAX analysis and BET surface area. The capacity of adsorption of the adsorbents was evaluated through the static method at 25°C. The results showed that the color removal was due to the adsorption and precipitation of the dye on the surface of the solids. The adsorption equilibrium was described according to the linear model for the adsorbent carbon and the equilibrium constant was 0.02 L g^?1. The equilibrium of adsorption on activated carbon exhibited a behavior typical of the Langmuir isotherm and the monolayer coverage was 24.33 mg g^?1. A mathematical model was proposed to describe the dynamics of the color removal using a fixed bed considering that the color removal is due to the adsorption and the precipitation of the dye on the adsorbent.     

Removal of Cu(II), Fe(III), and Cr(III) from Aqueous Solution by Aniline Grafted Silica Gel

Abstract

The aniline moiety was covalently grafted onto silica gel surface. The modified silica gel with aniline groups (SiAn) was used for removal of Cu(II), Fe(III), and Cr(III) ions from aqueous solution and industrial effluents using a batch adsorption procedure. The maximum adsorption of the transition metal ions took place at pH 4.5. The adsorption kinetics for all the adsorbates fitted better the pseudo second‐order kinetic model, obtaining the following adsorption rate constants (k₂): 1.233 · 10^?2, 1.902 · 10^?2, and 8.320 · 10^?3 g · mg^?1 min^?1 for Cr(III), Cu(II), and Fe(III), respectively. The adsorption of these transition metal ions were fitted to Langmuir, Freundlich, Sips, and Redlich‐Peterson isotherm models; however, the best isotherm model fitting which presented a lower difference of the q (amount adsorbed per gram of adsorbent) calculated by the model from the experimentally measured, was achieved by using the Sips model for all adsorbates chosen. The SiAn adsorbent was also employed for the removal of the transition metal ions Cr(III) (95%), Cu(II) (95%), and Fe(III) (94%) from industrial effluents, using the batch adsorption procedure.     

1-(2-Hydroxyethyl)-2-imidazolidinone as corrosion inhibitor of mild steel in 0.5 M HCl solution: thermodynamic,electrochemical and theoretical studies

The inhibition effect of 1-(2-Hydroxyethyl)-2-imidazolidinone (2-HEI) on mild steel (MS) corrosion in 0.5?M HCl solution was investigated at different inhibitor concentration and temperature by electrochemical experiments, such as linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and quantum chemical calculations. The inhibitor adsorption process on mild steel in 0.5?M HCl system was studied at different temperatures (20?°C–50?°C). Furthermore, the surface morphology of MS was also investigated with SEM in the absence and the presence of inhibitor. The adsorption of 1-(2-Hydroxyethyl)-2-imidazolidinone on MS surface is an exothermic process and this process obeys the Langmuir adsorption isotherm. The Quantum chemical findings are good agreed with the empirical data.     

Three-dimensional g-C3N4/MgO composites as a high-performance adsorbent for removal of Pb(II) from aqueous solution

ABSTRACT

A novel, three-dimensional material of g-C₃N₄/MgO was prepared by pyrolysis method. The adsorption behavior for Pb(II) onto g-C₃N₄/MgO was systematically investigated. The adsorption experiments confirmed that the g-C₃N₄/MgO exhibited remarkable adsorption performance owing to its rough morphology and abundant active sites on the surface. The maximum adsorption capacities for Pb(II) reached to 220.3, 226.2 and 235.1 mg/g at 308 K, 318 K and 328 K, respectively. The optimum adsorbent dosage was 1.0 g/L. The adsorption kinetics and isotherm could be well described by the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption process was spontaneous and endothermic.     

Diffusive Capture of Magnetic Particles by an Assemblage of Random Cylindrical Collectors

Abstract

We develop an effective medium model describing the capture of ultra-fine magnetic particles (diameter much less than 1 µm) by an assemblage of parallel magnetic cylinders, randomly distributed in static fluid. The continuity equation describing the dynamics of concentration is solved numerically to obtain the concentration in various regions around the collector. The concentration contours are generated and the saturation, accumulation, and depletion regions are indicated. The effect of varying collector packing fractions appears significantly in regions close to the outer boundary of the representative cell where the build-up features of ultra-fine particles near the collector surface are similar for packing fractions in range 5–10%.     

Inhibition of Steel Corrosion in Nitric Acid by Sulfur Containing Compounds

The inhibitive mechanism, thermodynamics, and adsorptive properties of thiobarbituric acid (TBA) and thiourea (TU) on the corrosion of mild steel in 0.5 M HNO₃ solution have been investigated using potentiodynamic, electrochemical impedance spectroscopy techniques, and quantum chemical calculations. Both inhibitors showed good inhibition efficiency in nitric acid solution. TU was the most effective inhibitor and its inhibition efficiency increases with increasing concentration to attain 99% at 6 × 10^?3 mol · L^?1 at 30°C. Theoretical fitting of different isotherms, Langmuir, Flory–Huggins, Temkin, and the kinetic-thermodynamic models were tested to clarify the nature of inhibitors adsorption on mild steel surface. The obtained experimental data fitted all the applied adsorption isotherms except Langmuir. The thermodynamic activation parameters were determined to provide evidence of the inhibitory effect of TBA and TU. To determine the surface charge at the steel surface in nitric acid solution the potential of zero charge was measured using AC measurements at different potentials. Quantum chemical parameters were calculated and explained. The data clarified that the inhibition of steel in nitric acid by TU or TBA takes place through physicochemical adsorption mechanism.     

Removal of Basic Red 46 dye from aqueous solution by adsorption and photocatalysis: equilibrium,isotherms, kinetics,and thermodynamic studies

ABSTRACT

In this study, the main objective is the elimination of Basic Red 46 dye by coupling two processes, adsorption on activated clay followed by photocatalysis over ZnO as photocatalyst. The adsorption was investigated under different conditions of pH, adsorbent dose, dye concentrations, and temperature. The best adsorption yield occurs at neutral pH ~ 7 within 60 min with an uptake percentage of 97% for a concentration of 25 mg/L and a dose of 0.5 g/L. The results at equilibrium were successfully described by the Langmuir model with an adsorption capacity of 175 mg/g. To investigate the mechanism of dye adsorption characteristic, the adsorption constants were determined using pseudo first order, pseudo second-order and intraparticle diffusion model. It was found that the Basic Red 46 dye adsorption is well described by the pseudo second-order kinetic. The second part of this work was dedicated to the photodegradation onto ZnO under solar irradiation of the residual BR 46 concentration, remained after adsorption. For the remaining concentrations, the removal yields reach 100% under.     

Preparation and Evaluation of Fullers Earth Beads for Removal of Cesium from Waste Streams

Abstract

Fullers earth beads and cylinders were prepared using chitosan and sodium silicate as binders, respectively, for removal of cesium ion from aqueous solutions. The cost of the adsorbent is expected to be significantly lower as the raw materials are low cost materials and readily available. The adsorbents were characterized by SEM, EDS, and x‐ray microanalysis. Adsorption capacity of the beads was evaluated under both batch and dynamic conditions. The adsorption capacity for Fullers earth beads was found to be 26.3 mg/g of adsorbent at 293 K when the liquid phase concentration of cesium was 1000 mg/L. The adsorption capacity of Fullers earth cylinder was found to be higher than that of beads, however, it was concluded that the alkaline nature of the cylinder precipitated out cesium increasing its capacity. The capacity of Fullers earth beads decreased by almost 62% when 1 mol/L NaCl and 2.25 mmol/L of strontium were present in the solution. The Freundlich, the Langmuir isotherm equations, and a modified Polanyi's equation were used to correlate the data. The isosteric heats of adsorption suggested the heterogeneity of the surface and multilayer coverage. The first order reversible kinetic model adequately described the dynamic system during the adsorption process. The adsorption (k₁) and desorption (k₂) rate constants were evaluated from the dynamic model.     

Performance of Unmodified Paper Solid Waste for Cadmium Removal From Aqueous Phase: Equilibrium and Kinetic Studies

The reuse of paper solid waste (PSW) as a low-cost sorbent for Cd removal from aqueous phase was investigated. Batch experiments were conducted to study the effects of pH (3.5, 5.5, 7.5), contact time (10–360 min), PSW dose (2.5–20 g L^?1), and Cd concentration (5–50 mg L^?1) at an ionic strength of 0.01 M NaNO₃ on adsorption efficiency and capacity. Cd removal of ～96% occurred in 20 mg L^?1 Cd solution at pH 5.5 containing 20 g L^?1 PSW. Equilibrium was attained after 120 min and the equilibrium adsorption capacity of PSW increased with increasing Cd concentration from 5 to 50 mg L^?1. The kinetic process of Cd adsorption obeyed the pseudo-second-order kinetic model. Langmuir and Freundlich models described equally well the experimental data and the maximum adsorption capacity was 4.89 mg g^?1. PSW can be used for reducing Cd concentration in Cd-contaminated water systems.     

Performance evaluation of poly (methacrylic acid) as corrosion inhibitor in the presence of iodide ions for mild steel in H2SO4 solution

The inhibition performance of poly (methacrylic acid) (PMAA) and the effect of addition of iodide ions on the inhibition efficiency for mild steel corrosion in 0.5 M H₂SO₄ solution were investigated in the temperature range of 303–333 K using electrochemical, weight loss, scanning electron microscopy (SEM), and water contact angles measurements. The results show that PMAA is a moderate inhibitor for mild steel in 0.5 M H₂SO₄ solution. Addition of small amount of KI to PMAA significantly upgraded the inhibition efficiency up to 96.7%. The adsorption properties of PMAA and PMAA + KI are estimated by considering thermodynamic and kinetic parameters. The results reveal that PMAA alone was physically adsorbed onto the mild steel surface, while comprehensive adsorption mode characterized the adsorption of PMAA + KI. Adsorption of PMAA and PMAA + KI followed Temkin adsorption isotherm. The SEM and water contact angle images confirmed the enhanced PMAA film formation on mild steel surface by iodide ions.     

CHAMOMILE (Matricaria recutita) EXTRACT AS A CORROSION INHIBITOR FOR MILD STEEL IN HYDROCHLORIC ACID SOLUTION

The corrosion inhibition of mild steel in hydrochloric acid solution by chamomile (Matricaria recutita) extract (CE) was investigated through electrochemical (polarization, EIS) and surface analysis (optical microscopy/AFM/SEM) techniques. The effects of inhibitor concentration, temperature, and pH were evaluated. Thermodynamic parameters were calculated and adsorption studies were carried out. Finally, the surface morphology was investigated. The electrochemical studies showed that CE acts as a mixed-type corrosion inhibitor with predominantly anodic behavior. CE was adsorbed physically on the metal surface and obeyed the Langmuir adsorption isotherm. It impeded the corrosion processes by changing the activation energy. In the presence of CE, the metal surface was more uniform than the surface in the absence of inhibitor. Maximum inhibition efficiency (IE) was 93.28%, which was obtained at 22°C in 7.2 g/L of inhibitor in 1 M HCl solution.     

The Phase Transformation Mechanism of Bentonite-Stabilized and Cetyltrimethylammonium Bromide-Stabilized Emulsions and Application in Reversible Emulsification Oil-Based Drilling Fluids

We obtained a reversible emulsion system induced by bentonite solid particles and surfactant Cetyltrimethylammonium bromide (CTAB, whose critical micelle concentration (CMC) value is 9.21 × 10⁻⁴ mol L⁻¹). In this study, the zeta potential and contact angle were used to characterize surface wettability of bentonite solid particles in the process of phase transmission behavior. The adsorption amount was calculated at different CTAB concentrations, and then the adsorption isotherm of surfactant CTAB at bentonite solid particles was also studied to confirm the adsorption behavior and adsorption layer structure. The electrical conductivity and microscopic analysis were employed to characterize the phase inversion behavior of emulsion. The results show that the wettability of bentonite particles can be reversed by changing the CTAB concentration, and then the two phase transition behavior of bentonite emulsion can be induced. Additionally, the surfactant CTAB can be used in oil-based drilling fluid systems for the inversion of the emulsion type. The research on the performance of the reversible emulsion oil-based drilling fluid system shows that it has a good thermal stability and a small amount of fluid loss, and successfully reduces the damage of the traditional oil-based drilling fluids on oil well completion.