Search results for: adsorption kinetics/isotherms

Authors: Laroussi Chaabane, Amel El Ghali, Emmanuel Beyou, Mohamed Hassen V. Baouab

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In this research, the functionalization of graphene oxide sheets by ethylenediamine (EDA) was accomplished and followed by the grafting of bis(2-pyridylmethyl) amino group (BPED) onto the activated graphene oxide sheets in the presence of chloroacetylchloride (CAC) and then combined with magnetic nanoparticles (Fe₃O₄NPs) to produce a magnetic graphene-based composite [(Go-EDA-CAC)@Fe₃O₄NPs-BPED]. The physicochemical properties of [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] composites were investigated by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA). Additionally, the catalysts can be easily recycled within ten seconds by using an external magnetic field. Moreover, [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] was used for removing Cu(II) ions from aqueous solutions using a batch process. The effect of pH, contact time and temperature on the metal ions adsorption were investigated, however weakly dependent on ionic strength. The maximum adsorption capacity values of Cu(II) on the [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] at the pH of 6 is 3.46 mmol.g⁻¹. To examine the underlying mechanism of the adsorption process, pseudo-first, pseudo-second-order, and intraparticle diffusion models were fitted to experimental kinetic data. Results showed that the pseudo-second-order equation was appropriate to describe the Cu (II) adsorption by [(Go-EDA-CAC)@Fe₃O₄NPs-BPED]. Adsorption data were further analyzed by the Langmuir, Freundlich, and Jossens adsorption approaches. Additionally, the adsorption properties of the [(Go-EDA-CAC)@Fe₃O₄NPs-BPED], their reusability (more than 6 cycles) and durability in the aqueous solutions open the path to removal of Cu(II) from water solution. Based on the results obtained, we report the activity of Cu(II) supported on [(Go-EDA-CAC)@Fe₃O₄NPs-BPED] as a catalyst for the cross-coupling of symmetric alkynes.

Keywords: graphene, magnetic nanoparticles, adsorption kinetics/isotherms, cross coupling

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Authors: Laroussi Chaabane, Emmanuel Beyou, Amel El Ghali, Mohammed Hassen V. Baouab

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The functionalization of graphene oxide sheets by ethylenediamine (EDA) was accomplished followed by the grafting of bis(2-pyridylmethyl)amino group (BPED) onto the activated graphene oxide sheets in the presence of chloroacetylchloride (CAC) produced the martial [(Go-EDA-CAC)-BPED]. The physic-chemical properties of [(Go-EDA-CAC)-BPED] composites were investigated by Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPs), Scanning electron microscopy (SEM) and Thermogravimetric analysis (TGA). Moreover, [(Go-EDA-CAC)-BPED] was used for removing M(II) (where M=Cu, Ni and Co) ions from aqueous solutions using a batch process. The effect of pH, contact time and temperature were investigated. More importantly, the [(Go-EDA-CAC)-BPED] adsorbent exhibited remarkable performance in capturing heavy metal ions from water. The maximum adsorption capacity values of Cu(II), Ni(II) and Co(II) on the [(GO-EDA-CAC)-BPED] at the pH of 7 is 3.05 mmol.g⁻¹, 3.25 mmol.g⁻¹ and 3.05 mmol.g⁻¹ respectively. To examine the underlying mechanism of the adsorption process, pseudo-first, pseudo-second-order, and intraparticle diffusion models were fitted to experimental kinetic data. Results showed that the pseudo-second-order equation was appropriate to describe the three metal ions adsorption by [(Go-EDA-CAC)-BPED]. Adsorption data were further analyzed by the Langmuir, Freundlich, and Jossensadsorption approaches. Additionally, the adsorption properties of the [(Go-EDA-CAC)-BPED], their reusability (more than 10 cycles) and durability in the aqueous solutions open the path to removal of metal ions (Cu(II), Ni(II) and Co(II) from water solution. Based on the results obtained, we conclude that [(Go-EDA-CAC)-BPED] can be an effective and potential adsorbent for removing metal ions from an aqueous solution.

Keywords: graphene oxide, bis(2-pyridylmethyl)amino, adsorption kinetics, isotherms

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Authors: Jean Yves Uwamungu, Fiston Bizimana, Chunsheng Hu

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Although pesticides are used in crop productivity, their use is highly harming the soil environment, and measures must be taken in the future to eradicate soil and groundwater pollution. The primary aim was to determine the effect of biochar addition on the imidacloprid adsorption on soil prior to no-tillage (NT) and rotational tillage (RT) conditions. In the laboratory, batch tests were conducted to determine the imidacloprid adsorption on soil using equilibrium and kinetic modelling with the addition of biochar. The clay level of the soil was found to be more significant when no-tillage was applied (22.42) than when rotational tillage was applied (14.27). The imidacloprid adsorption equilibrium was significantly shortened to 25 min after biochar addition. The isotherms and kinetic findings confirmed that the adsorption occurred according to Freundlich and pseudo-second-order kinetic models, respectively. The adsorption capacity of imidacloprid (40<35<25 °C) increased with decreasing temperature, indicating an exothermic adsorption behaviour, whereas negative Gibbs free energy (G) values of -6980.5 and 5983.93 Jmol-1, respectively, for soil prior to NT and RT at 25 °C, asserted spontaneous adsorption. The negative values of entropy (ΔS); -22.83 and -38.15 Jmol-1K-1, prior to NT and RT applications, respectively, described a lowered randomness process. The enthalpy was greater when RT was applied (-17533 J mol-1) than when NT was applied (-450 J mol-1). Lastly, it was shown that NTtreatment enhanced imidacloprid adsorption capacity more than RT treatment and that biochar addition enhanced pesticide adsorption in both treatments.

Keywords: adsorption, biochar, imidacloprid, soil, tillage

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Authors: Sajjad Hussain, Sabir Khan, Maria Del Pilar Taboada Sotomayor

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This work demonstrates the synthesis of magnetic molecularly imprinted polymers (MMIPs) for determination of a selected pesticide (ametryne) using high performance liquid chromatography (HPLC). Computational simulation can assist the choice of the most suitable monomer for the synthesis of polymers. The (MMIPs) were polymerized at the surface of Fe3O4@SiO2 magnetic nanoparticles (MNPs) using 2-vinylpyradine as functional monomer, ethylene-glycol-dimethacrylate (EGDMA) is a cross-linking agent and 2,2-Azobisisobutyronitrile (AIBN) used as radical initiator. Magnetic non-molecularly imprinted polymer (MNIPs) was also prepared under the same conditions without analyte. The MMIPs were characterized by scanning electron microscopy (SEM), Brunauer, Emmett and Teller (BET) and Fourier transform infrared spectroscopy (FTIR). Pseudo first order and pseudo second order model were applied to study kinetics of adsorption and it was found that adsorption process followed the pseudo first order kinetic model. Adsorption equilibrium data was fitted to Freundlich and Langmuir isotherms and the sorption equilibrium process was well described by Langmuir isotherm mode. The selectivity coefficients (α) of MMIPs for ametryne with respect to atrazine, ciprofloxacin and folic acid were 4.28, 12.32, and 14.53 respectively. The spiked recoveries ranged between 91.33 and 106.80% were obtained. The results showed high affinity and selectivity of MMIPs for pesticide ametryne in the food samples.

Keywords: molecularly imprinted polymer, pesticides, magnetic nanoparticles, adsorption

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Authors: Faroudja Mohellebi, Fayrouz Khalida Kies, Moncef Rezzik El Marhoun, Feriel Yahiat

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The purpose of this study is to valorize an agro-food waste (orange peels) by its use as an adsorbent in the treatment of water loaded with pharmaceutical micropollutant present in aquatic environments, oxytetracycline. The tests, carried out in batch mode, made it possible to study the influence on the sorptive capacity of calcined orange peels of several parameters: the contact time, the initial concentration of oxytetracycline, the adsorbent dose, and the initial pH of the solution. The pseudo-second-order model is best adapted to represent the adsorption kinetics. The Langmuir model describes the adsorption isotherm of oxytetracycline. The adsorption is favored in a basic environment.

Keywords: adsorption, emerging pollutants, oxytetracycline, water treatment

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Authors: Pham-Thi Huong, Byeong-Kyu Lee, Jitae Kim, Chi-Hyeon Lee

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Fe-nano zeolite adsorbent was used for removal of Ni (II) ions from aqueous solution. The adsorbent was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and the surface area Brunauer–Emmett–Teller (BET) using for analysis of functional groups, morphology and surface area. Bath adsorption experiments were analyzed on the effect of pH, time, adsorbent doses and initial Ni (II) concentration. The optimum pH for Ni (II) removal using Fe-nano zeolite was found at 5.0 and 90 min of reaction time. The maximum adsorption capacity of Ni (II) was 231.68 mg/g based on the Langmuir isotherm. The kinetics data for the adsorption process was fitted with the pseudo-second-order model. The desorption of Ni (II) from Ni-loaded Fe-nano zeolite was analyzed and even after 10 cycles 72 % desorption was achieved. These finding supported that Fe-nano zeolite with high adsorption capacity, high reuse ability would be utilized for Ni (II) removal from water.

Keywords: Fe-nano zeolite, adsorption, Ni (II) removal, regeneration

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Authors: Emanuele Bonamente, Andrea Aquino, Franco Cotana

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This paper presents experimental results from the analysis of Tuff for CO2 and H2S removal from biogas. Synthetic zeolites, commonly used for biogas upgrading, are characterized by excellent performance in terms of carbon dioxide adsorption, however, cost and environmental footprint represent a negative contribute to their sustainability. Natural zeolites contained in Tuff, a totally inexpensive byproduct of the construction industry, show very interesting selective adsorption properties, associated with its availability in regions, as central Italy, where biogas production from small scale plants is rapidly increasing. An in-house experimental device was assembled to measure the adsorption capacity of Tuff as a function of partial CO2 pressure for different temperatures (i.e. adsorption isotherms). Results show performances as high as 66% with respect to commercial zeolites (13X). A sensitivity analysis of different regeneration processes is also presented. A comparative analysis of natural and synthetic zeolites was finally performed using biogas samples obtained from different types of feedstock and characterized by varying CO2 and H2S content.

Keywords: biogas upgrading, CO2 adsorption, sustainable energy, tuff

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Authors: Umar Hayatu Sidik

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The natural gas vehicle represents a cost-competitive, lower-emission alternative to the gasoline-fuelled vehicle. The immediate challenge that confronts natural gas is increasing its energy density. This paper addresses the question of energy density by reviewing the storage technologies for natural gas with improved adsorbent. Technical comparisons are made between storage systems containing adsorbent and conventional compressed natural gas based on the associated amount of moles contained with Compressed Natural Gas (CNG) and Adsorbed Natural Gas (ANG). We also compare gas storage in different cylinder types (1, 2, 3 and 4) based on weight factor and storage capacity. For the storage tank system, we discussed the concept of carbon adsorbents, when used in CNG tanks, offer a means of increasing onboard fuel storage and, thereby, increase the driving range of the vehicle. It confirms that the density of the stored gas in ANG is higher than that of compressed natural gas (CNG) operated at the same pressure. The obtained experimental data were correlated using linear regression analysis with common adsorption kinetic (Pseudo-first order and Pseudo-second order) and isotherm models (Sip and Toth). The pseudo-second-order kinetics describe the best fitness with a correlation coefficient of 9945 at 35 bar. For adsorption isotherms, the Sip model shows better fitness with the regression coefficient (R2) of 0.9982 and with the lowest RSMD value of 0.0148. The findings revealed the potential of adsorbent in natural gas storage applications.

Keywords: natural gas, adsorbent, compressed natural gas, adsorption

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Authors: L. Khalfa, M. Bagane, M. L. Cervera, S. Najjar

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The aim of this work is to present a low cost adsorbent for removing toxic heavy metals from aqueous solutions. Therefore, we are interested to investigate the efficiency of natural clay minerals collected from south Tunisia and their modified form using sulfuric acid in the removal of toxic metal ions: Zn(II) and Pb(II) from synthetic waste water solutions. The obtained results indicate that metal uptake is pH-dependent and maximum removal was detected to occur at pH 6. Adsorption equilibrium is very rapid and it was achieved after 90 min for both metal ions studied. The kinetics results show that the pseudo-second-order model describes the adsorption and the intraparticle diffusion models are the limiting step. The treatment of natural clay with sulfuric acid creates more active sites and increases the surface area, so it showed an increase of the adsorbed quantities of lead and zinc in single and binary systems. The competitive adsorption study showed that the uptake of lead was inhibited in the presence of 10 mg/L of zinc. An antagonistic binary adsorption mechanism was observed. These results revealed that clay is an effective natural material for removing lead and zinc in single and binary systems from aqueous solution.

Keywords: heavy metal, activated clay, kinetic study, competitive adsorption, modeling

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Authors: Vusumzi E. Pakade, Themba D. Ntuli, Augustine E. Ofomaja

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Macadamia nutshell biosorbents treated in three different methods (raw Macadamia nutshell powder (RMN), acid-treated Macadamia nutshell (ATMN) and base-treated Macadamia nutshell (BTMN)) were investigated for the adsorption of Cr(VI) from aqueous solutions. Fourier transform infrared spectroscopy (FT-IR) spectra of free and Cr(VI)-loaded sorbents as well as thermogravimetric analysis (TGA) revealed that the acid and base treatments modified the surface properties of the sorbents. The optimum conditions for the adsorption of Cr(VI) by sorbents were pH 2, contact time 10 h, adsorbent dosage 0.2 g L-1, and concentration 100 mg L-1. The different treatment methods altered the surface characteristics of the sorbents and produced different maximum binding capacities of 42.5, 40.6 and 37.5 mg g-1 for RMN, ATMN and BTMN, respectively. The data was fitted into the Langmuir, Freundlich, Redlich-Peterson and Sips isotherms. No single model could clearly explain the data perhaps due to the complexity of process taking place. The kinetic modeling results showed that the process of Cr(VI) biosorption with Macadamia sorbents was better described by a process of chemical sorption in pseudo-second order. These results showed that the three treatment methods yielded different surface properties which then influenced adsorption of Cr(VI) differently.

Keywords: biosorption, chromium(VI), isotherms, Macadamia, reduction, treatment

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Authors: Sabir Khan, Sajjad Hussain, Ademar Wong, Maria Del Pilar Taboada Sotomayor

Abstract:

The present work aims to develop magnetic molecularly imprinted polymers (MMIPs) for determination of a selected pesticide (ametryne) using high-performance liquid chromatography (HPLC). Computational simulation can assist the choice of the most suitable monomer for the synthesis of polymers. The (MMIPs) were polymerized at the surface of Fe3O4@SiO2 magnetic nanoparticles (MNPs) using 2-vinylpyradine as functional monomer, ethylene-glycol-dimethacrylate (EGDMA) is a cross-linking agent and 2,2-Azobisisobutyronitrile (AIBN) used as radical initiator. Magnetic non-molecularly imprinted polymer (MNIPs) was also prepared under the same conditions without analyte. The MMIPs were characterized by scanning electron microscopy (SEM), Brunauer, Emmett and Teller (BET) and Fourier transform infrared spectroscopy (FTIR). Pseudo first-order and pseudo second order model were applied to study kinetics of adsorption and it was found that adsorption process followed the pseudo-first-order kinetic model. Adsorption equilibrium data was fitted to Freundlich and Langmuir isotherms and the sorption equilibrium process was well described by Langmuir isotherm mode. The selectivity coefficients (α) of MMIPs for ametryne with respect to atrazine, ciprofloxacin and folic acid were 4.28, 12.32 and 14.53 respectively. The spiked recoveries ranged between 91.33 and 106.80% were obtained. The results showed high affinity and selectivity of MMIPs for pesticide ametryne in the food samples.

Keywords: molecularly imprinted polymer, pesticides, magnetic nanoparticles, adsorption

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Authors: T. Moremedi, L. Katata-Seru, S. Sardar, A. Bandyopadhyay, E. Makhado, M. Joseph Hato

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The rapid industrialisation and population growth have led to a steady fall in freshwater supplies worldwide. As a result, water systems are affected by modern methods upon use due to secondary contamination. The application of novel adsorbents derived from natural polymer holds a great promise in addressing challenges in water treatment. In this study, the UV irradiation technique was used to prepare acrylamide (AAm) monomer, and acrylic acid (AA) monomer grafted xanthan gum (XG) copolymer. Furthermore, the factors affecting rhodamine B (RhB) adsorption from aqueous media, such as pH, dosage, concentration, and time were also investigated. The FTIR results confirmed the formation of graft copolymer by the strong vibrational bands at 1709 cm^-1 and 1612 cm^-1 for AA and AAm, respectively. Additionally, more irregular, porous and wrinkled surface observed from SEM of XG-g-AAm/AA indicated copolymerization interaction of monomers. The optimum conditions for removing RhB dye with a maximum adsorption capacity of 313 mg/g at 25 ⁰C from aqueous solution were pH approximately 5, initial dye concentration = 200 ppm, adsorbent dose = 30 mg. Also, the detailed investigation of the isothermal and adsorption kinetics of RhB from aqueous solution showed that the adsorption of the dye followed a Freundlich model (R² = 0.96333) and pseudo-second-order kinetics. The results further indicated that this absorbent based on XG had the universality to remove dye through the mechanism of chemical adsorption. The outstanding adsorption potential of the grafted copolymer could be used to remove cationic dyes from aqueous solution as a low-cost product.

Keywords: xanthan gum, adsorbents, rhodamine B, Freundlich

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Authors: Aimad Oulebsir, Toufik Chaabane, Venkataraman Sivasankar, André Darchen, Titus A. M. Msagati

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Currently, the presence of pharmaceutical substances in the environment is an emerging pollution leading to the disruption of ecosystems. Indeed, water loaded with pharmaceutical residues is an issue that has raised the attention of researchers. The aim of this study was to monitor the effectiveness of the alumina electro-generated by the adsorption process the iron of well water for the production of drugs. The Fe2+ was removed from wastewater by adsorption in a batch cell. Performance results of iron removal by alumina electro-generated revealed that the efficiency of the carrier in the method of electro-generated adsorption. The overall Fe2+ of the synthetically solutions and simulated effluent removal efficiencies reached 75% and 65%, respectively. The application of models and isothermal adsorption kinetics complement the results obtained experimentally. Desorption of iron was investigated using a solution of 0.1M NaOH. Regeneration of the tests shows that the adsorbent maintains its capacity after five adsorption/desorption cycles.

Keywords: electrocoagulation, aluminum electrode, electrogenerated alumina, iron, adsorption/desorption

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Authors: L. Rozumová, J. Seidlerová

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The aim of this paper was to study the sorption properties of a blast furnace sludge used as the sorbent. The sorbent was utilized for reduction of content of lead and zinc ions. Sorbent utilized in this work was obtained from metallurgical industry from process of wet gas treatment in iron production. The blast furnace sludge was characterized by X-Ray diffraction, scanning electron microscopy, and XRFS spectroscopy. Sorption experiments were conducted in batch mode. The sorption of metal ions in the sludge was determined by correlation of adsorption isotherm models. The adsorption of lead and zinc ions was best fitted with Langmuir adsorption isotherms. The adsorption capacity of lead and zinc ions was 53.8 mg.g^-1 and 10.7 mg.g^-1, respectively. The results indicated that blast furnace sludge could be effectively used as secondary material and could be also employed as a low-cost alternative for the removal of heavy metals ions from wastewater.

Keywords: blast furnace sludge, lead, zinc, sorption

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Authors: S. Agarwal, A. Rani

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Catechol is a natural polyphenolic compound that widely exists in higher plants such as teas, vegetables, fruits, tobaccos, and some traditional Chinese medicines. The fly ash-based zeolites are capable of absorbing a wide range of pollutants. But the process of zeolite synthesis is time-consuming and requires technical setups by the industries. The marketed costs of zeolites are quite high restricting its use by small-scale industries for the removal of phenolic compounds. The present research proposes a simple method of alkaline treatment of FA to produce an effective adsorbent for catechol removal from wastewater. The experimental parameter such as pH, temperature, initial concentration and adsorbent dose on the removal of catechol were studied in batch reactor. For this purpose the adsorbent materials were mixed with aqueous solutions containing catechol ranging in 50 – 200 mg/L initial concentrations and then shaken continuously in a thermostatic Orbital Incubator Shaker at 30 ± 0.1 °C for 24 h. The samples were withdrawn from the shaker at predetermined time interval and separated by centrifugation (Centrifuge machine MBL-20) at 2000 rpm for 4 min. to yield a clear supernatant for analysis of the equilibrium concentrations of the solutes. The concentrations were measured with Double Beam UV/Visible spectrophotometer (model Spectrscan UV 2600/02) at the wavelength of 275 nm for catechol. In the present study, the use of low-cost adsorbent (BTFA) derived from coal fly ash (FA), has been investigated as a substitute of expensive methods for the sequestration of catechol. The FA and BTFA adsorbents were well characterized by XRF, FE-SEM with EDX, FTIR, and surface area and porosity measurement which proves the chemical constituents, functional groups and morphology of the adsorbents. The catechol adsorption capacities of synthesized BTFA and native material were determined. The adsorption was slightly increased with an increase in pH value. The monolayer adsorption capacities of FA and BTFA for catechol were 100 mg g⁻¹ and 333.33 mg g⁻¹ respectively, and maximum adsorption occurs within 60 minutes for both adsorbents used in this test. The equilibrium data are fitted by Freundlich isotherm found on the basis of error analysis (RMSE, SSE, and χ²). Adsorption was found to be spontaneous and exothermic on the basis of thermodynamic parameters (ΔG°, ΔS°, and ΔH°). Pseudo-second-order kinetic model better fitted the data for both FA and BTFA. BTFA showed large adsorptive characteristics, high separation selectivity, and excellent recyclability than FA. These findings indicate that BTFA could be employed as an effective and inexpensive adsorbent for the removal of catechol from wastewater.

Keywords: catechol, fly ash, isotherms, kinetics, thermodynamic parameters

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Authors: Abdallah Bouguettoucha, Derradji Chebli, Tariq Yahyaoui, Hichem Attout

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The effect of acid -basic treatment of lingocellulosic material (forest wastes wild carob) on Ethyl violet adsorption was investigated. It was found that surface chemistry plays an important role in Ethyl violet (EV) adsorption. HCl treatment produces more active acidic surface groups such as carboxylic and lactone, resulting in an increase in the adsorption of EV dye. The adsorption efficiency was higher for treated of lingocellulosic material with HCl than for treated with KOH. Maximum biosorption capacity was 170 and 130 mg/g, for treated of lingocellulosic material with HCl than for treated with KOH at pH 6 respectively. It was also found that the time to reach equilibrium takes less than 25 min for both treated materials. The adsorption of basic dye (i.e., ethyl violet or basic violet 4) was carried out by varying some process parameters, such as initial concentration, pH and temperature. The adsorption process can be well described by means of a pseudo-second-order reaction model showing that boundary layer resistance was not the rate-limiting step, as confirmed by intraparticle diffusion since the linear plot of Qt versus t^0.5 did not pass through the origin. In addition, experimental data were accurately expressed by the Sips equation if compared with the Langmuir and Freundlich isotherms. The values of ΔG° and ΔH° confirmed that the adsorption of EV on acid-basic treated forest wast wild carob was spontaneous and endothermic in nature. The positive values of ΔS° suggested an irregular increase of the randomness at the treated lingocellulosic material -solution interface during the adsorption process.

Keywords: adsorption, isotherm models, thermodynamic parameters, wild carob

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Authors: E. Gil, A. Zepeda, J. Rivera, C. Ben-Youssef, S. Rincón

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Water pollution has become one of the most serious environmental problems. Multiple methods have been proposed for the removal of Pb(II) from contaminated water. Among these, adsorption processes have shown to be more efficient, cheaper and easier to handle with respect to other treatment methods. However, research for adsorbents with high adsorption capacities is still necessary. For this purpose, we proposed in this work the study of metal-organic Framework [Co2(btec)(bipy)(DMF)2]n (MOF-Co) as adsorbent material of Pb (II) in aqueous media. MOF-Co was synthesized by a simple method. Firstly 4, 4’ dipyridyl, 1,2,4,5 benzenetetracarboxylic acid, cobalt (II) and nitrate hexahydrate were first mixed each one in N,N dimethylformamide (DMF) and then, mixed in a reactor altogether. The obtained solution was heated at 363 K in a muffle during 68 h to complete the synthesis. It was washed and dried, obtaining MOF-Co as the final product. MOF-Co was characterized before and after the adsorption process by Fourier transforms infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS). The Pb(II) in aqueous media was detected by Absorption Atomic Spectroscopy (AA). In order to evaluate the adsorption process in the presence of Pb(II) in aqueous media, the experiments were realized in flask of 100 ml the work volume at 200 rpm, with different MOF-Co quantities (0.0125 and 0.025 g), pH (2-6), contact time (0.5-6 h) and temperature (298,308 and 318 K). The kinetic adsorption was represented by pseudo-second order model, which suggests that the adsorption took place through chemisorption or chemical adsorption. The best adsorption results were obtained at pH 5. Langmuir, Freundlich and BET equilibrium isotherms models were used to study the adsorption of Pb(II) with 0.0125 g of MOF-Co, in the presence of different concentration of Pb(II) (20-200 mg/L, 100 mL, pH 5) with 4 h of reaction. The correlation coefficients (R2) of the different models show that the Langmuir model is better than Freundlich and BET model with R2=0.97 and a maximum adsorption capacity of 833 mg/g. Therefore, the Langmuir model can be used to best describe the Pb(II) adsorption in monolayer behavior on the MOF-Co. This value is the highest when compared to other materials such as the graphene/activated carbon composite (217 mg/g), biomass fly ashes (96.8 mg/g), PVA/PAA gel (194.99 mg/g) and MOF with Ag12 nanoparticles (120 mg/g).

Keywords: adsorption, heavy metals, metal-organic frameworks, Pb(II)

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Authors: Harsha Nagar, Vineet Aniya, Alka Kumari, Satyavathi B.

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In the present study, engineered bio-coal was produced from pressed seed cake, which otherwise is non-edible in origin. The production process involves a slow pyrolysis wherein, based on the optimization of process parameters; a substantial reduction in H/C and O/C of 77% was achieved with respect to the original ratio of 1.67 and 0.8, respectively. The bio-coal, so the product was found to have a higher heating value of 29899 kJ/kg with surface area 17 m²/g and pore volume of 0.002 cc/g. The functional characterization of bio-coal and its subsequent modification was carried out to enhance its active sites, which were further used as an adsorbent material for removal of 2,4,6-Trichlorophenol (2,4,6-TCP) herbicide from the aqueous stream. The point of zero charge for the bio-coal was found to be pH < 3 where its surface is positively charged and attracts anions resulting in the maximum 2, 4, 6-TCP adsorption at pH 2.0. The parametric optimization of the adsorption process was studied based on the Box-Behken design with the desirability approach. The results showed optimum values of adsorption efficiency of 74.04% and uptake capacity of 118.336 mg/g for an initial metal concentration of 250 mg/l and particle size of 0.12 mm at pH 2.0 and 1 g/L of bio-coal loading. Negative Gibbs free energy change values indicated the feasibility of 2,4,6-TCP adsorption on biochar. Decreasing the ΔG values with the rise in temperature indicated high favourability at low temperatures. The equilibrium modeling results showed that both isotherms (Langmuir and Freundlich) accurately predicted the equilibrium data, which may be attributed to the different affinity of the functional groups of bio-coal for 2,4,6-TCP removal. The possible mechanism for 2,4,6-TCP adsorption is found to be physisorption (pore diffusion, p*_p electron donor-acceptor interaction, H-bonding, and van der Waals dispersion forces) and chemisorption (phenolic and amine groups chemical bonding) based on the kinetics data modeling.

Keywords: engineered biocoal, 2, 4, 6-trichlorophenol, box behnken design, biosorption

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Authors: Carlos Alberto Rivera-corredor, Angie Dayana Vargas-Ceballos, Edison Gilpavas, Izabela Dobrosz-Gómez, Miguel Ángel Gómez-García

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Hexavalent chromium, Cr (VI) is present in the effluents from different industries such as electroplating, mining, leather tanning, etc. This compound is of great academic and industrial concern because of its toxic and carcinogenic behavior. Its dumping to both environmental and public health for animals and humans causes serious problems in water sources. The amount of Cr (VI) in industrial wastewaters ranges from 0.5 to 270,000 mgL-1. According to the Colombian standard for water quality (NTC-813-2010), the maximum allowed concentration for the Cr (VI) in drinking water is 0.05 mg L-1. To comply with this limit, it is essential that industries treat their effluent to reduce the Cr (VI) to acceptable levels. Numerous methods have been reported for the treatment removing metal ions from aqueous solutions such as: reduction, ion exchange, electrodialysis, etc. Adsorption has become a promising method for the purification of metal ions in water, since its application corresponds with an economic and efficient technology. The absorbent selection and the kinetic and thermodynamic study of the adsorption conditions are key to the development of a suitable adsorption technology. The Ce0.25Zr0.75O2.nH2O presents higher adsorption capacity between a series of hydrated mixed oxides Ce1-xZrxO2 (x = 0, 0.25, 0.5, 0.75, 1). This work presents the kinetic and thermodynamic study of Cr (VI) adsorption on Ce0.25Zr0.75O2.nH2O. Experiments were performed under the following experimental conditions: initial Cr (VI) concentration = 25, 50 and 100 mgL-1, pH = 2, adsorbent charge = 4 gL-1, stirring time = 60 min, temperature=20, 28 and 40 °C. The Cr (VI) concentration was spectrophotometrically estimated by the method of difenilcarbazide with monitoring the absorbance at 540 nm. The Cr (VI) adsorption over hydrated Ce0.25Zr0.75O2.nH2O models was analyzed using pseudo-first and pseudo-second order kinetics. The Langmuir and Freundlich models were used to model the experimental data. The convergence between the experimental values and those predicted by the model, is expressed as a linear regression correlation coefficient (R2) and was employed as the model selection criterion. The adsorption process followed the pseudo-second order kinetic model and obeyed the Langmuir isotherm model. The thermodynamic parameters were calculated as: ΔH°=9.04 kJmol-1,ΔS°=0.03 kJmol-1 K-1, ΔG°=-0.35 kJmol-1 and indicated the endothermic and spontaneous nature of the adsorption process, governed by physisorption interactions.

Keywords: adsorption, hexavalent chromium, kinetics, thermodynamics

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Authors: Vincenzo Piemonte

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The liver is a complex, large-scale biochemical reactor which plays a unique role in the human physiology. When liver ceases to perform its physiological activity, a functional replacement is required. Actually, liver transplantation is the only clinically effective method of treating severe liver disease. Anyway, the aforementioned therapeutic approach is hampered by the disparity between organ availability and the number of patients on the waiting list. In order to overcome this critical issue, research activities focused on liver support device systems (LSDs) designed to bridging patients to transplantation or to keep them alive until the recovery of native liver function. In recirculating albumin dialysis devices, such as MARS (Molecular Adsorbed Recirculating System), adsorption is one of the fundamental steps in albumin-dialysate regeneration. Among the albumin-bound toxins that must be removed from blood during liver-failure therapy, bilirubin and tryptophan can be considered as representative of two different toxin classes. The first one, not water soluble at physiological blood pH and strongly bounded to albumin, the second one, loosely albumin bound and partially water soluble at pH 7.4. Fixed bed units are normally used for this task, and the design of such units requires information both on toxin adsorption equilibrium and kinetics. The most common adsorptive media used in LSDs are activated carbon, non-ionic polymeric resins and anionic resins. In this paper, bilirubin adsorption isotherms on different adsorptive media, such as polymeric resin, albumin-coated resin, anionic resin, activated carbon and alginate beads with entrapped albumin are presented. By comparing all the results, it can be stated that the adsorption capacity for bilirubin of the five different media increases in the following order: Alginate beads < Polymeric resin < Albumin-coated resin < Activated carbon < Anionic resin. The main focus of this paper is to provide useful guidelines for the optimization of liver support devices which implement adsorption columns to remove albumin-bound toxins from albumin dialysate solutions.

Keywords: adsorptive media, adsorption equilibrium, artificial liver devices, bilirubin, mathematical modelling

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Authors: Nouacer Imane, Benalia Mokhtar, Djedid Mabrouk

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The adsorption ability of a powdered activated carbons (PAC) derived from Luffa cylindrica investigated in an attempt to produce more economic and effective sorbents for the control of Cu(II) ion from industrial liquid streams. Carbonaceous sorbents derived from local luffa cylindrica, were prepared by chemical activation methods using ZnCl2 as activating reagents. Adsorption of Cu (II) from aqueous solutions was investigated. The effects of pH, initial adsorbent concentration, the effect of particle size, initial metal ion concentration and temperature were studied in batch experiments. The maximum adsorption capacity of copper onto grafted Luffa cylindrica fiber was found to be 14.23 mg/g with best fit for Langmuir adsorption isotherm. The values of thermodynamic parameters such as enthalpy change, ∆H (-0.823 kJ/mol), entropy change, ∆S (-9.35 J/molK) and free energy change, ∆G (−1.56 kJ/mol) were also calculated. Adsorption process was found spontaneous and exothermic in nature. Finally, the luffa cylindrica has been evaluated by FTIR, MO and x-ray diffraction in order to determine if the biosorption process modifies its chemical structure and morphology, respectively. Luffa cylindrica has been proven to be an efficient biomaterial useful for heavy metal separation purposes that is not altered by the process.

Keywords: adsorption, cadmium, isotherms, thermodynamic, luffa sponge

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Authors: Saeb Ahmadi, Mohsen Vafaie Sefti, Mohammad Mahdi Shadman, Ebrahim Tangestani

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Carbon nanotube has shown great potential for the removal of various inorganic and organic components due to properties such as large surface area and high adsorption capacity. Central composite design is widely used method for determining optimal conditions. Also due to the economic reasons and wide application, the rare earth elements are important components. The analyses of cerium (Ce(III)) adsorption as one of the Rare Earth Elements (REEs) adsorption on Multiwall Carbon Nanotubes (MWCNTs) have been studied. The optimization process was performed using Response Surface Methodology (RSM). The optimum amount conditions were pH of 4.5, initial Ce (III) concentration of 90 mg/l and MWCNTs dosage of 80 mg. Under this condition, the optimum adsorption percentage of Ce (III) was obtained about 96%. Next, at the obtained optimum conditions the kinetic and isotherm studied and result showed the pseudo-second order and Langmuir isotherm are more fitted with experimental data than other models.

Keywords: cerium, rare earth element, MWCNTs, adsorption, optimization

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Authors: Liu De-jun, Fu Jing, Zhang Rong, Luo Tian, Ma Ning

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Cs-137, the radioactive fission products of uranium, can be easily dissolved in water during the accident of nuclear power plant, such as Chernobyl, Three Mile Island, Fukushima accidents. The concentration of Cs in the groundwater around the nuclear power plant exceeded the standard value almost 10,000 times after the Fukushima accident. The adsorption capacity of Titanate nano-materials for radioactive cation (Cs+) is very strong. Moreover, the radioactive ion can be tightly contained in the nanotubes or nanofibers without reversible adsorption, and it can safely be fixed. In addition, the nano-material has good chemical stability, thermal stability and mechanical stability to minimize the environmental impact of nuclear waste and waste volume. The preparation of titanate nanotubes or nanofibers was studied by hydrothermal methods, and chemical kinetics of removal of Cs by nano-materials was obtained. The adsorption time with maximum adsorption capacity and the effects of pH, coexisting ion concentration and the optimum adsorption conditions on the removal of Cs by titanate nano-materials were also obtained. The adsorption boundary curves, adsorption isotherm and the maximum adsorption capacity of Cs-137 as tracer on the nano-materials were studied in the research. The experimental results showed that the removal rate of Cs-137 in 0.01 tons of waste water with only 1 gram nano-materials could reach above 98%, according to the optimum adsorption conditions.

Keywords: preparation, titanate, cs-137, removal, nuclear

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Authors: Michael Leo L. Dela Cruz, Khryslyn G. Arano, Eden May B. Dela Pena, Leslie Joy Diaz

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Arsenic adsorbents were continuously being researched to ease the detrimental impact of arsenic to human health. A comparative study on the adsorption mechanism of arsenic on iron modified nanoclays was undertaken. Iron intercalated montmorillonite (Fe-MMT) and montmorillonite supported zero-valent iron (ZVI-MMT) were the adsorbents investigated in this study. Fe-MMT was produced through ion-exchange by replacing the sodium intercalated ions in montmorillonite with iron (III) ions. The iron (III) in Fe-MMT was later reduced to zero valent iron producing ZVI-MMT. Adsorption study was performed by batch technique. Obtained data were fitted to intra-particle diffusion, pseudo-first order, and pseudo-second-order models and the Elovich equation to determine the kinetics of adsorption. The adsorption of arsenic on Fe-MMT followed the intra-particle diffusion model with intra-particle rate constant of 0.27 mg/g-min0.5. Arsenic was found to be chemically bound on ZVI-MMT as suggested by the pseudo-second order and Elovich equation. The derived pseudo-second order rate constant was 0.0027 g/mg-min with initial adsorption rate computed from the Elovich equation was 113 mg/g-min.

Keywords: adsorption mechanism, arsenic, montmorillonite, zero valent iron

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Authors: Tsegaye Adane Birhan

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Recently, rapid industrialization has led to the excessive release of heavy metals such as Cr (VI) into the environment. Exposure to chromium (VI) can cause kidney and liver damage, depressed immune systems, and a variety of cancers. Therefore, treatment of Cr (VI) containing wastewater is mandatory. This study aims to optimize the removal of Cr (VI) from an aqueous solution using locally available Teff husk-activated carbon adsorbent. The laboratory-based study was conducted on the optimization of Cr (VI) removal efficiency of Teff husk-activated carbon from aqueous solution. A central composite design was used to examine the effect of the interaction of process parameters and to optimize the process using Design Expert version 7.0 software. The optimized removal efficiency of Teff husk activated carbon (95.597%) was achieved at 1.92 pH, 87.83mg/L initial concentration, 20.22g/L adsorbent dose and 2.07Hrs contact time. The adsorption of Cr (VI) on Teff husk-activated carbon was found to be best fitted with pseudo-second-order kinetics and Langmuir isotherm model of the adsorption. Teff husk-activated carbon can be used as an efficient adsorbent for the removal of chromium (VI) from contaminated water. Column adsorption needs to be studied in the future.

Keywords: batch adsorption, chromium (VI), teff husk activated carbon, response surface methodology, tannery wastewater

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Authors: Ungwanen John Ahile, Sylvester Obaike Adejo, Simon Terver Ubwa, Raymond Lubem Tyohemba, Pius Utange, Mnena G. Ikyagh

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The adsorption of tetracycline from aqueous solution was carried out using melon husk as a low-cost adsorbent. The adsorption was characterized using standard methods and values obtained were; pH = 7.80, bulk density = 0.43 g/mL, ash content = 2.2 %, moisture content = 8.27 %, attrition = 1%, and iodine number = 552 mg/g. Adsorption capacity was found to vary with initial concentration, adsorbent dosage, pH, contact time and temperature, the maximum adsorption capacity in each case was found to be at; 30 mg/L for concentration, 0.8 g for adsorbent dose, 5 for pH, 60 minutes for time and 30 °C for temperature. FTIR analysis was done to analyses the surface functional groups which shows the presence of O-H stretch, at 3743.92 corresponding to alcohol, phenols, C-H stretch at 2923.27 indicative of alkanes, H-C=O: C-H stretch at 2725.76 corresponding to aldehyde, C-C stretch at 1462.72 corresponding to aromatic, SEM analysis carried out revealed a rough and smooth morphology of the uncontacted and contacted adsorbent respectively. The experimental data judging from the R2 values fitted best into the Temkin isotherm. The fitting of tetracycline adsorption into the pseudo second order kinetic model (R2 of 0.9992) is suggestive of chemisorption for the adsorbent.

Keywords: adsorption, adsorbent isotherm, antibiotics, tertracycline

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Authors: Ceren Karaman, Onur Karaman

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The adsorption of Remazol Black B (RBB), an anionic dye, onto dried orange pulp (DOP) adsorbent prepared by only drying and by treating with cetyltrimetylammonium bromide (CTAB), a cationic surfactant, surface-modified orange pulp (SMOP) was studied in a stirred batch experiments system at 25°C. The adsorption of RBB on each adsorbent as a function of surfactant dosage, initial pH of the solution and initial dye concentration was investigated. The optimum amount of CTAB was found to be 25g/l. For RBB adsorption studies, while working pH value for the DOP adsorbent system was determined as 2.0, it was observed that this value shifted to 8.0 when the 25 g/l CTAB treated-orange pulp (SMOP) adsorbent was used. It was obtained that the adsorption rate and capacity increased to a certain value, and the adsorption efficiency decreased with increasing initial RBB concentration for both DOP and SMOP adsorbents at pH 2.0 and pH 8.0. While the highest adsorption capacity for DOP was determined as 62.4 mg/g at pH 2.0, and as 325.0 mg/g for SMOP at pH 8.0. As a result, it can be said that permanent cationic coating of the adsorbent surface by CTAB surfactant shifted the working pH from 2.0 to 8.0 and it increased the dye adsorption rate and capacity of orange pulp much more significantly at pH 8.0. The equilibrium RBB adsorption data on each adsorbent were best described by the Langmuir isotherm model. The adsorption kinetics of RBB on each adsorbent followed a pseudo-second-order model. Moreover, the intraparticle diffusion model was used to describe the kinetic data. It was found that diffusion is not the only rate controlling step. The adsorbent was characterized by the Brunauer–Emmett–Teller (BET) analysis, Fourier-transform-infrared (FTIR) spectroscopy, and scanning-electron-microscopy (SEM). The mechanism for the adsorption of RBB on the SMOP may include hydrophobic interaction, van der Waals interaction, stacking and electrostatic interaction.

Keywords: adsorption, Cetyltrimethylammonium Bromide (CTAB), orange pulp, Remazol Black B (RBB), surface modification

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Authors: Khanom Simarani

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Rice husk has been widely reported as a good sorbent for heavy metals. Pre treatment of rice husk minimizes cellulose crystallinity and increases the surface area thus ensuring better adsorption capacity. Commercial base and natural base-treated rice husk were used to investigate the potential of Ni(II) adsorption from synthetic solutions and waste water in batch systems. Effects of process variables such as pH, contact time, adsorbent dose, initial Ni (II) concentration were studied. Optimum Ni (II) adsorption was observed at pH 6 within 60 min of contact time. Experimental data showed increased amount of adsorbed Ni(II) with increasing adsorbent dose and decreased percent of adsorption with increasing initial Ni(II) concentration. Kinetic isotherms (Langmuir, Freundlich) were also applied. Biosorption mechanism of rice husk was analyzed using SEM/EDS, FT-IR, and XRD. The results revealed that natural base produced from agroindustrial waste could be used as efficient as commercial bases during pre treatment rice husk in removing Ni(II) from waste waters within 15 min.

Keywords: Nickel removal, adsorbent, heavy metal, biomass

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Authors: Bienvenu Gael Fouda Mbanga

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This study reports a new approach of preparation of carbon nanoparticles coated cerium oxide nanorods (CNPs/CeONRs) nanocomposite and reusing the spent adsorbent of Cd2+- CNPs/CeONRs nanocomposite for latent fingerprint detection (LFP) after removing Cd2+ ions from aqueous solution. CNPs/CeONRs nanocomposite was prepared by using CNPs and CeONRs with adsorption processes. The prepared nanocomposite was then characterized by using UV-visible spectroscopy (UV-visible), Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction pattern (XRD), scanning electron microscope (SEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDS), Zeta potential, X-ray photoelectron spectroscopy (XPS). The average size of the CNPs was 7.84nm. The synthesized CNPs/CeONRs nanocomposite has proven to be a good adsorbent for Cd2+ removal from water with optimum pH 8, dosage 0. 5 g / L. The results were best described by the Langmuir model, which indicated a linear fit (R2 = 0.8539-0.9969). The adsorption capacity of CNPs/CeONRs nanocomposite showed the best removal of Cd2+ ions with qm = (32.28-59.92 mg/g), when compared to previous reports. This adsorption followed pseudo-second order kinetics and intra particle diffusion processes. ∆G and ∆H values indicated spontaneity at high temperature (40oC) and the endothermic nature of the adsorption process. CNPs/CeONRs nanocomposite therefore showed potential as an effective adsorbent. Furthermore, the metal loaded on the adsorbent Cd2+- CNPs/CeONRs has proven to be sensitive and selective for LFP detection on various porous substrates. Hence Cd2+-CNPs/CeONRs nanocomposite can be reused as a good fingerprint labelling agent in LFP detection so as to avoid secondary environmental pollution by disposal of the spent adsorbent.

Keywords: Cd2+-CNPs/CeONRs nanocomposite, cadmium adsorption, isotherm, kinetics, thermodynamics, reusable for latent fingerprint detection

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Authors: Sabiha Chouchane, Toufik Chouchane, Azzedine Hani

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The wastewater was treated with a natural asorbent “Diatomite” to eliminate chromium three. Diatomite is an element that comes from Sig (west of Algeria). The physicochemical characterization revealed that the diatomite is mainly made up of silica, lime and a lower degree of alumina. The process considered in static regime, at 20°C, an ion stirring speed of 150 rpm, a pH = 4 and a grain diameter of between 100 and 150µm, shows that one gram of diatomite purified can fix according to the Langmuir model up to 39.64 mg/g of chromium with pseudo 1st order kinetics. The pseudo-equilibrium time highlighted is 25 minutes. The affinity between the adsorbent and the adsorbate follows the value of the RL ratio indicates us that the solid used has a good adsorption capacity. The external transport of the metal ions from the solution to the adsorbent seems to be a step controlling the speed of the overall process. On the other hand, internal transport in the pores is not the only limiting mechanism of sorption kinetics. Thermodynamic parameters show that chromium sorption is spontaneous and exothermic with negative entropy.

Keywords: adsorption, diatomite, crIII, wastewater

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