Search results for: adsorption equilibrium

Authors: Sudarshan Kalsulkar, Sunil S. Bhagwat

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Biosorption is a physiochemical process that occurs naturally in certain biomass which allows it to passively concentrate and bind contaminants onto its cellular structure. Activated carbons (AC) are one such efficient biosorbents made by utilizing lignocellulosic materials from agricultural waste. Steam activated carbon (AC) was synthesized from Barley husk. Its synthesis parameters of time and temperature were optimized. Its physico-chemical properties like density, surface area, pore volume, Methylene blue and Iodine values were characterized. BET surface area was found to be 42 m²/g. Batch Adsorption tests were carried out to determine the maximum adsorption capacity (qmax) for various metal ions. Cd+2 48.74 mg/g, Pb+2 19.28 mg/g, Hg+2 39.1mg/g were the respective qmax values. pH and time were optimized for adsorption of each ion. Column Adsorptions were carried for each to obtain breakthrough data. Microbial adsorption was carried using E. coli K12 strain. 78% reduction in cell count was observed at operating conditions. Thus the synthesized Barley husk AC can be an economically feasible replacement for commercially available AC prepared from the costlier coconut shells. Breweries and malting industries where barley husk is a primary waste generated on a large scale can be a good source for bulk raw material.

Keywords: activated carbon, Barley husk, biosorption, decontamination, heavy metal removal, water treatment

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Authors: Wei-Neng Wang, Jhy-Yuan Shieh, Jhy-Hwa Chen, Juin-Jen Chang

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This paper incorporate tax evasion into a one-sector real business cycle (RBC) model to explores the quantitative interrelations between income tax rate and equilibrium (in)determinacy, and income tax rate is endogenously determined in order to balance the government budget. We find that the level of the effective income tax rate is key factor for equilibrium (in)determinacy, instead of the level of income tax rate in a tax evasion economy. Under an economy with tax evasion, the higher income tax rate is not sufficiently to lead to equilibrium indeterminate, it must combine with a necessary condition which is the lower fraction of tax evasion and that can result in agents' optimistic expectations to become self-fulfilling and sunspot fluctuation more likely to occur. On the other hand, an economy with tax evasion can see its macroeconomy become more stabilize, and a higher fraction of income tax evasion may has a stronger stabilizing effect.

Keywords: tax evasion, balanced-budget rule, equlibirium (in)determinacy, effective income tax rate

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Authors: Sudipt Agarwal, Siddharth Verma, S. M. Iqbal, Hitik Kalra

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Natural gas as a fuel has created wonders, but on the contrary, the ill-effects of methane have been a great worry for professionals. The largest source of methane emission is the oil and gas industry among all industries. Methane depletes groundwater and being a greenhouse gas has devastating effects on the atmosphere too. Methane remains for a decade or two in the atmosphere and later breaks into carbon dioxide and thus damages it immensely, as it warms up the atmosphere 72 times more than carbon dioxide in those two decades and keeps on harming after breaking into carbon dioxide afterward. The property of a fluid to adhere to the surface of a solid, better known as adsorption, can be a great boon to minimize the hindrance caused by methane. Adsorption of methane during upstream processes can save the groundwater and atmospheric depletion around the site which can be hugely lucrative to earn profits which are reduced due to environmental degradation leading to project cancellation. The paper would deal with reasons why casing and cementing are not able to prevent leakage and would suggest methods to adsorb methane during upstream processes with mathematical explanation using volumetric analysis of adsorption of methane on the surface of activated carbon doped with copper oxides (which increases the absorption by 54%). The paper would explain in detail (through a cost estimation) how the proposed idea can be hugely beneficial not only to environment but also to the profits earned.

Keywords: adsorption, casing, cementing, cost estimation, volumetric analysis

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Authors: Bukunola K. Oguntade, Gareth M. Watkins

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The synthesis and characterization of metal-organic frameworks (MOFs) is an area of coordination chemistry which has grown rapidly in recent years. Worldwide there has been growing concerns about future energy supplies, and its environmental impacts. A good number of MOFs have been tested for the adsorption of small molecules in the vapour phase. An important issue for potential applications of MOFs for gas adsorption and storage materials is the stability of their structure upon sorption. Therefore, study on the thermal stability of MOFs upon adsorption is important. The incorporation of two or more transition metals in a coordination polymer is a current challenge for designed synthesis. This work focused on the synthesis, characterization and small molecule adsorption properties of three microporous (one zinc monometal and two bimetallics) complexes involving Cu(II), Zn(II) and 1,2,4,5-benzenetetracarboxylic acid using the ambient precipitation and solvothermal method. The complexes were characterized by elemental analysis, Infrared spectroscopy, Scanning Electron microscopy, Thermogravimetry analysis and X-ray Powder diffraction. The N2-adsorption Isotherm showed the complexes to be of TYPE III in reference to IUPAC classification, with very small pores only capable for small molecule sorption. All the synthesized compounds were observed to contain water as guest. Investigations of their inclusion properties for small molecules in the vapour phase showed water and methanol as the only possible inclusion candidates with 10.25H2O in the monometal complex [Zn4(H2B4C)2.5(OH)3(H2O)]·10H2O but not reusable after a complete structural collapse. The ambient precipitation bimetallic; [(CuZnB4C(H2O)2]·5H2O, was found to be reusable and recoverable from structure collapse after adsorption of 5.75H2O. In addition, Solvo-[CuZnB4C(H2O)2.5]·2H2O obtained from solvothermal method show two cycles of rehydration with 1.75H2O and 0.75MeOH inclusion while structure remains unaltered upon dehydration and adsorption.

Keywords: adsorption, characterization, copper, metal -organic frameworks, zinc

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Authors: Z. Jamalzadeh, A. Niaei, H. Erfannia, S. G. Hosseini, A. S. Razmgir

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Due to developing the industries, the emission of pollutants such as NOx, SOx, and CO2 are rapidly increased. Generally, NOx is attributed to the mono nitrogen oxides of NO and NO2 that is one of the most important atmospheric contaminants. Hence, controlling the emission of nitrogen oxides is urgent environmentally. Selective Catalytic Reduction of NOx is one of the most common techniques for NOx removal in which Zeolites have wide application due to their high performance. In zeolitic processes, the catalytic reaction occurs mostly in the pores. Therefore, investigation the adsorption phenomena of the molecules in order to gain an insight and understand the catalytic cycle is of important. Hence, in current study, molecular simulations is applied for studying the adsorption phenomena in nanocatalysts applied for SCR of NOx process. The effect of cation addition to the support in the catalysts’ behavior through adsorption step was explored by Mont Carlo (MC). Simulation time of 1 Ns accompanying 1 fs time step, COMPASS27 Force Field and the cut off radios of 12.5 Ȧ was applied for performed runs. It was observed that the adsorption capacity increases in the presence of cations. The sorption isotherms demonstrated the behavior of type I isotherm categories and sorption capacity diminished with increase in temperature whereas an increase was observed at high pressures. Besides, NO sorption showed higher sorption capacity than NH3 in H–ZSM5. In this respect, the Energy distributions signified that the molecules could adsorb in just one sorption site at the catalyst and the sorption energy of NO was stronger than the NH3 in H-ZSM5. Furthermore, the isosteric heat of sorption data showed nearly same values for the molecules; however, it indicated stronger interactions of NO molecules with H-ZSM5 Zeolite compared to the isosteric heat of NH3 which was low in value.

Keywords: Monte Carlo simulation, adsorption, NOx, ZSM5

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Authors: Mohammad Farid

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In this paper, we introduce and study an explicit iterative method based on hybrid extragradient method to approximate a common solution of generalized mixed equilibrium problem and fixed point problem for a nonexpansive semigroup in Hilbert space. Further, we prove that the sequence generated by the proposed iterative scheme converge strongly to the common solution of generalized mixed equilibrium problem and fixed point problem for a nonexpansive semigroup. This common solution is the unique solution of a variational inequality problem and is the optimality condition for a minimization problem. The results presented in this paper are the supplement, extension and generalization of the previously known results in this area.

Keywords: generalized mixed equilibrium problem, fixed-point problem, nonexpansive semigroup, variational inequality problem, iterative algorithms, hybrid extragradient method

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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: Hakimeh Sharififard, Mansooreh Soleimani

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In this work, the magnetic activated carbon nanocomposite (Fe-CAC) has been synthesized by anchorage iron hydr(oxide) nanoparticles onto commercial activated carbon (CAC) surface and characterized using BET, XRF, SEM techniques. The influence of various removal parameters such as pH, contact time and initial concentration of vanadium on vanadium removal was evaluated using CAC and Fe-CAC in batch method. The sorption isotherms were studied using Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. These equilibrium data were well described by the Freundlich model. Results showed that CAC had the vanadium adsorption capacity of 37.87 mg/g, while the Fe-AC was able to adsorb 119.01 mg/g of vanadium. Kinetic data was found to confirm pseudo-second-order kinetic model for both adsorbents.

Keywords: magnetic activated carbon, remove, vanadium, nanocomposite, freundlich

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Authors: Al-Sayed A. Bakr, W. A. Makled

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The precipitated low magnesium calcite ooids in assembled softening unit from natural Mediterranean seawater samples were used as adsorbent media in a comparative study with granular activated carbon media in a two separated single-media filtration vessels (operating in parallel) for removal of iron from aqueous solutions. In each vessel, the maximum bed capacity, which required to be filled, was 13.2 l and the bed filled in the vessels of ooids and GAC were 8.6, and 6.6 l, respectively. The operating conditions applied to the semi-pilot filtration unit were constant pH (7.5), different temperatures (293, 303 and 313 k), different flow rates (20, 30, 40, 50 and 60 l/min), different initial Fe(II) concentrations (15–105 mg/ l) and the calculated adsorbent masses were 34.1 and 123 g/l for GAC and calcite ooids, respectively. At higher temperature (313 k) and higher flow rate (60 l/min), the maximum adsorption capacities for ferrous ions by GAC and calcite ooids filters were 3.87 and 1.29 mg/g and at lower flow rate (20 l/min), the maximum adsorption capacities were 2.21 and 3.95 mg/g, respectively. From the experimental data, Freundlich and Langmuir adsorption isotherms were used to verify the adsorption performance. Therefore, the calcite ooids could act as new highly effective materials in iron removal from aqueous solutions.

Keywords: water treatment, calcite ooids, activated carbon, Fe(II) removal, filtration

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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: Özge Alptoğa, Nuray Uçar, Nilgün Karatepe Yavuz, Ayşen Önen

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Sulfur dioxide (SO₂) is a very toxic air pollutant gas and it causes the greenhouse effect, photochemical smog, and acid rain, which threaten human health severely. Thus, the capture of SO₂ gas is very important for the environment. Graphene which is two-dimensional material has excellent mechanical, chemical, thermal properties, and many application areas such as energy storage devices, gas adsorption, sensing devices, and optical electronics. Further, graphene oxide (GO) is examined as a good adsorbent because of its important features such as functional groups (epoxy, carboxyl and hydroxyl) on the surface and layered structure. The SO₂ adsorption properties of the fibers are usually investigated on carbon fibers. In this study, potential adsorption capacity of GO fibers was researched. GO dispersion was first obtained with Hummers’ method from graphite, and then GO fibers were obtained via wet spinning process. These fibers were converted into a disc shape, dried, and then subjected to SO₂ gas adsorption test. The SO₂ gas adsorption capacity of GO fiber discs was investigated in the fields of utilization of different coagulation baths and reduction by hydrazine hydrate. As coagulation baths, single and triple baths were used. In single bath, only ethanol and CaCl₂ (calcium chloride) salt were added. In triple bath, each bath has a different concentration of water/ethanol and CaCl₂ salt, and the disc obtained from triple bath has been called as reference disk. The fibers which were produced with single bath were flexible and rough, and the analyses show that they had higher SO₂ adsorption capacity than triple bath fibers (reference disk). However, the reduction process did not increase the adsorption capacity, because the SEM images showed that the layers and uniform structure in the fiber form were damaged, and reduction decreased the functional groups which SO₂ will be attached. Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) analyzes were performed on the fibers and discs, and the effects on the results were interpreted. In the future applications of the study, it is aimed that subjects such as pH and additives will be examined.

Keywords: coagulation bath, graphene oxide fiber, reduction, SO2 gas adsorption

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Authors: A. Rajabpour, A. Hadizadeh Kheirkhah

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Heat transfer is of great importance to biological systems in order to function properly. In the present study, specific heat capacity as one of the most important heat transfer properties is calculated for a soluble in water Lysozyme protein. Using equilibrium molecular dynamics (MD) simulation, specific heat capacities of pure water, dry lysozyme, and lysozyme-water solution are calculated at 300K for different weight fractions. It is found that MD results are in good agreement with ideal binary mixing rule at small weight fractions. Results of all simulations have been validated with experimental data.

Keywords: specific heat capacity, molecular dynamics simulation, lysozyme protein, equilibrium

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Authors: A. Ghribi, M. Bagane

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The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removals of such compounds at such low levels are a difficult problem. Physicochemical technique such as coagulation, flocculation, ozonation, reverse osmosis and adsorption on activated carbon, manganese oxide, silica gel and clay are among the methods employed. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. Dye molecules also have very high affinity for clay surfaces and are readily adsorbed when added to clay suspension. The elimination of the organic dye by clay was studied by serval researchers. The focus of this research was to evaluate the adsorption potential of the raw clay in removing congo red from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 7.Experiments were carried out at different bed heights (5-20 cm), influent flow rates (1.6- 8 mL/min) and influent congo red concentrations (10-50 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of congo red from aqueous solution. Uptake of congo red through a fixed-bed column was dependent on the bed depth, influent congo red concentration and flow rate.

Keywords: adsorption, breakthrough curve, clay, congo red, fixed bed column, regeneration

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Authors: A. Ghribi, M. Bagane

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The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removal of such compounds at such low levels is a difficult problem. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. The focus of this research was to evaluate the adsorption potential of the raw clay in removing rhodamine B from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height, and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 8.5. Experiments were carried out at different bed heights (5 - 20 cm), influent flow rates (1.6- 8 mL/min) and influent rhodamine B concentrations (20 - 80 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of rhodamine B from aqueous solution. Uptake of rhodamine B through a fixed-bed column was dependent on the bed depth, influent rhodamine B concentration, and flow rate.

Keywords: adsorption, breakthrough curve, clay, fixed bed column, rhodamine b, regeneration

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Authors: Omid Moradi, Mostafa Rajabi

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Graphene oxide (GO), reduced graphene oxide (rGO), multi-walled carbon nanotubes MWCNT), multi-walled carbon nanotube functionalized carboxyl (MWCNT-COOH), and multi-walled carbon nanotube functionalized thiol (MWCNT-SH) were used as efficient adsorbents for the rapid removal two dyes methyl orange (MO) and malachite green (MG) from the aqueous phase. The impact of several influential parameters such as initial dye concentrations, contact time, temperature, and initial solution pH was well studied and optimized. The optimize time for adsorption process of methyl orange dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were determined at 100, 100, 60, 25, and 60 min, respectively and The optimize time for adsorption process of malachite green dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were determined at 100, 100, 60, 15, and 60 min, respectively. The maximum removal efficiency for methyl orange dye by GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were occurred at optimized pH 3, 3, 6, 2, and 6 of aqueous solutions, respectively and for malachite green dye were occurred at optimized pH 3, 3, 6, 9, and 6 of aqueous solutions, respectively. The effect of temperature showed that adsorption process of malachite green dye on GO, rGO, MWCNT, and MWCNT-SH surfaces were endothermic and for adsorption process of methyl orange dye on GO, rGO, MWCNT, and MWCNT-SH surfaces were endothermic but while adsorption of methyl orange and malachite green dyes on MWCNT-COOH surface were exothermic.On increasing the initial concentration of methyl orange dye adsorption capacity on GO surface was decreased and on rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were increased and with increasing the initial concentration of malachite green dye on GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH surfaces were increased.

Keywords: adsorption, graphene oxide, reduced graphene oxide, multi-walled carbon nanotubes, methyl orange, malachite green, removal

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Authors: Mohamed Habila, Ahmed Mohamed El-Toni, Mohamed Sheikh Moshab, Abdulrhman Al-Awadi, Zeid AL Othman

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Water pollution with dyes is a critical environmental issue because off the huge amount of dyes disbarred annually, which cause severe damage for the ecosystem and human life. The main raison for this severs pollution is the rapid industrial development which led to more production of harmful pollutants. on the other hand, the core shell based magnetic materials have showed amazing character for controlling the material synthesis with the targeted structure to enhance the adsorptive removal of pollutants. Herein, the Fe3O4core-meso SiO2/TiO2 double shell have been prepared for methylene blue dye adsorption. the preparation procedure is controlled to prepare the magnetic core with further coating layers from silica and titania. The prepared Fe3O4core-meso SiO2/TiO2 double shell showed adsorption capacity for methylene blue removal about 50 mg/g at pH 6 after 80 min contact time form 50 ppm methylene blue solution. The adsorption process of methylene blue onto Fe3O4core-meso SiO2/TiO2 double shell was well fitted with the pseudo-second-order kinetic model and freundlish isotherm, indicating a quick and multilayer adsorption mechanism.

Keywords: magnetic core, silica shell, titania shell, water treatment, methylene blue, solvo-thermal process, adsorption

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Authors: Manisha Choudhary, Sudarsan Neogi

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Malachite green (MG), an organic basic dye, has been widely used for the dyeing purpose, as well as a fungicide and antiseptic in aquaculture industry to control fish parasites and disease. However, MG has now turned out to be an extremely controversial compound due to its adverse impact on living beings. Due to high toxicity, proper treatment of wastewater containing MG is utmost important. Among different available technologies, adsorption process is one of the most efficient and cost-effective treatment method due to its simplicity of design, ease of operation and regeneration of used materials. Nonetheless, commercial activated carbon is expensive leading the researchers to focus on utilizing natural resources. In the present work, a species of cactus, Opuntia ficus-indica (OFI), was used to develop a highly efficient, low-cost powdered activated carbon by chemical activation using NaOH. The biosorbent was characterized by Fourier-transform infrared spectroscopy, field emission scanning electron microscope, energy-dispersive X-ray spectroscopy, Brunauer–Emmett–Teller (BET) and X-ray diffraction analysis. Batch adsorption studies were performed to remove MG from an aqueous solution as a function of contact time, initial solution pH, initial dye concentration, biosorbent dosages, the presence of salt and temperature. By increasing the initial dye concentration from 100 to 500 mg/l, adsorption capacity increased from 165.45 to 831.58 mg/g. The adsorption kinetics followed the pseudo-second-order model and the chemisorption mechanisms were revealed. The electrostatic attractions and chemical interactions were observed between amino and hydroxyl groups of the biosorbent and amine groups of the dye. The adsorption was solely controlled by film diffusion. Different isotherm models were used to fit the adsorption data. The excellent recovery of adsorption efficiency after the regeneration of biosorbent indicated the high potential of this adsorbent to remove MG from aqueous solution and an excellent cost-effective biosorbent for wide application in wastewater treatment.

Keywords: adsorption, biosorbent, cactus, malachite green

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Authors: Anirban Dey, Sukanta Kumar Dash, Bishnupada Mandal

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Carbondioxide (CO2) is a major greenhouse gas responsible for global warming and fossil fuel power plants are the main emitting sources. Therefore the capture of CO2 is essential to maintain the emission levels according to the standards. Carbon capture and storage (CCS) is considered as an important option for stabilization of atmospheric greenhouse gases and minimizing global warming effects. There are three approaches towards CCS: Pre combustion capture where carbon is removed from the fuel prior to combustion, Oxy-fuel combustion, where coal is combusted with oxygen instead of air and Post combustion capture where the fossil fuel is combusted to produce energy and CO2 is removed from the flue gases left after the combustion process. Post combustion technology offers some advantage as existing combustion technologies can still be used without adopting major changes on them. A number of separation processes could be utilized part of post –combustion capture technology. These include (a) Physical absorption (b) Chemical absorption (c) Membrane separation (d) Adsorption. Chemical absorption is one of the most extensively used technologies for large scale CO2 capture systems. The industrially important solvents used are primary amines like Monoethanolamine (MEA) and Diglycolamine (DGA), secondary amines like diethanolamine (DEA) and Diisopropanolamine (DIPA) and tertiary amines like methyldiethanolamine (MDEA) and Triethanolamine (TEA). Primary and secondary amines react fast and directly with CO2 to form stable carbamates while Tertiary amines do not react directly with CO2 as in aqueous solution they catalyzes the hydrolysis of CO2 to form a bicarbonate ion and a protonated amine. Concentrated Piperazine (PZ) has been proposed as a better solvent as well as activator for CO2 capture from flue gas with a 10 % energy benefit compared to conventional amines such as MEA. However, the application of concentrated PZ is limited due to its low solubility in water at low temperature and lean CO2 loading. So following the performance of PZ its derivative 2-Aminoethyl piperazine (AEP) which is a cyclic amine can be explored as an activator towards the absorption of CO2. Vapour liquid equilibrium (VLE) in CO2 capture systems is an important factor for the design of separation equipment and gas treating processes. For proper thermodynamic modeling accurate equilibrium data for the solvent system over a wide range of temperatures, pressure and composition is essential. The present work focuses on the determination of VLE data for (AEP + H2O) system at 40 °C for various composition range.

Keywords: absorption, aminoethyl piperazine, carbondioxide, vapour liquid equilibrium

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Authors: Tizi Hayet, Berrama Tarek, Bounif Nadia

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Phenol and its derivatives are organic compounds utilized in the chemical industry. They are introduced into the environment by accidental spills and the illegal release of industrial and municipal wastewater. Phenols are organic intermediaries that are considered potential pollutants. Adsorption is one of the purification and separation techniques used in this area. Algeria annually produces 131000 tons of fig; therefore, a large amount of fig leaves is generated, and the conversion of this waste into adsorbent allows the valorization of agricultural residue. The main purpose of this present work is to describe an application of a statistical method for modeling and to optimize the conditions of the phenol adsorption from agricultural by-products, locally available (fig leaves). The best experimental performance of phenol elimination on the adsorbent was obtained with: Adsorbent concentration (X₂) = 200 mg L⁻¹; Initial concentration (X₃) = 150 mg L⁻¹; Speed agitation (X₁) = 300 rpm.

Keywords: low-cost adsorbents, adsorption, fig leaves, phenol, factorial design

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Authors: C. E. Madubueze, S. C. Madubueze, S. Ajama

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Cholera is a disease that is predominately common in developing countries due to poor sanitation and overcrowding population. In this paper, a deterministic model for the dynamics of cholera is developed and control measures such as health educational message, therapeutic treatment, and vaccination are incorporated in the model. The effective reproduction number is computed in terms of the model parameters. The existence and stability of the equilibrium states, disease free and endemic equilibrium states are established and showed to be locally and globally asymptotically stable when R0 < 1 and R0 > 1 respectively. The existence of backward bifurcation of the model is investigated. Furthermore, numerical simulation of the model developed is carried out to show the impact of the control measures and the result indicates that combined control measures will help to reduce the spread of cholera in the population

Keywords: backward bifurcation, cholera, equilibrium, dynamics, stability

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Authors: Fatima Zahra Mahjoubi, Abderrahim Khalidi, Mohammed Abdennouri, Noureddine Barka

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Zn-Al layered double hydroxides containing carbonate, nitrate and dodecylsulfate as the interlamellar anions have been prepared through a coprecipitation method. The resulting compounds were characterized using XRD, ICP, FTIR, TGA/DTA, TEM/EDX and pHPZC analysis. The XRD patterns revealed that carbonate and nitrate could be intercalated into the interlayer structure with basal spacing of 22.74 and 26.56 Å respectively. Bilayer intercalation of dodecylsulfate molecules was achieved in Zn-Al LDH with a basal spacing of 37.86 Å. The TEM observation indicated that the materials synthesized via coprecipitation present nanoscale LDH particle. The average particle size of Zn-AlCO3 is 150 to 200 nm. Irregular circular to hexagonal shaped particles with 30 to 40 nm in diameter was observed in the Zn-AlNO3 morphology. TEM image of Zn-AlDs display nanostructured sheet like particles with size distribution between 5 to 10 nm. The sorption characteristics and mechanisms of methyl orange dye on organic LDH were investigated and were subsequently compared with that on the inorganic Zn-Al layered double hydroxides. Adsorption experiments for MO were carried out as function of solution pH, contact time and initial dye concentration. The adsorption behavior onto inorganic LDHs was obviously influenced by initial pH. However, the adsorption capacity of organic LDH was influenced indistinctively by initial pH and the removal percentage of MO was practically constant at various value of pH. As the MO concentration increased, the curve of adsorption capacity became L-type onto LDHs. The adsorption behavior for Zn-AlDs was proposed by the dissolution of dye in a hydrophobic interlayer region (i.e., adsolubilization). The results suggested that Zn-AlDs could be applied as a potential adsorbent for MO removal in a wide range of pH.

Keywords: adsorption, dodecylsulfate, kinetics, layered double hydroxides, methyl orange removal

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Authors: Thidarat Imyen, Paisan Kongkachuichay

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Cu-Zn/core-shell Al-MCM-41 catalyst with various copper species, prepared by a combination of three methods—substitution, ion-exchange, and impregnation, was studied for the selective catalytic reduction (SCR) of NO with NH3 at 300 °C for 150 min. In order to investigate the effects of Zn introduction on the nature of the catalyst, Cu/core-shell Al-MCM-41 and Zn/core-shell Al-MCM-41 catalysts were also studied. The roles of Zn promoter in the acidity and the NOx adsorption properties of the catalysts were investigated by in situ Fourier transform infrared spectroscopy (FTIR) of NH3 and NOx adsorption, and temperature-programmed desorption (TPD) of NH3 and NOx. The results demonstrated that the acidity of the catalyst was enhanced by the Zn introduction, as exchanged Zn(II) cations loosely bonded with Al-O-Si framework could create Brønsted acid sites by interacting with OH groups. Moreover, Zn species also provided the additional sites for NO adsorption in the form of nitrite (NO2–) and nitrate (NO3–) species, which are the key intermediates for SCR reaction. In addition, the effect of Zn on the nature of copper was studied by in situ FTIR of CO adsorption and in situ X-ray adsorption near edge structure (XANES). It was found that Zn species hindered the reduction of Cu(II) to Cu(0), resulting in higher Cu(I) species in the Zn promoted catalyst. The Cu-Zn/core-shell Al-MCM-41 exhibited higher catalytic activity compared with that of the Cu/core-shell Al-MCM-41 for the whole reaction time, as it possesses the highest amount of Cu(I) sites, which are responsible for SCR catalytic activity. The Cu-Zn/core-shell Al-MCM-41 catalyst also reached the maximum NO conversion of 100% with the average NO conversion of 76 %. The catalytic performance of the catalyst was further improved by using Zn promoter in the form of ZnO instead of reduced Zn species. The Cu-ZnO/core-shell Al-MCM-41 catalyst showed better catalytic performance with longer working reaction time, and achieved the average NO conversion of 81%.

Keywords: Al-MCM-41, copper, nitrogen oxide, selective catalytic reduction, zinc

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Authors: Qian Zhao

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With global increasing demand for phosphorus and intensively depleting reserves, it is urgent need to explore innovative approaches towards capturing phosphate from sewage, which is also an effective way to reduce phosphate contamination and avoid eutrophication of water bodies. In the present article, the superparamagnetic nano-sorbents containing Fe₃O₄ core and hafnium-modified MgAl/MgFe layered double hydroxides shell (abbreviated as MgAlHf-NP and MgFeHf-NP) was developed using a simple and low-cost synthesis protocol. The obtained Hf-coated nano-materials showed well-defined crystal structure and sufficient saturation magnetization and exhibited higher adsorption capacity for phosphate. Meanwhile, high selectivity was also confirmed since coexisting foreign anions and biomacromolecules showed little competitive effect on phosphate adsorption. The enhancement via doping with Hf should be explained by the stronger ligand complexation built by the pair of hard acid Hf ion and hard base phosphate that matched up the bonding preferences. Sufficient OH⁻ concentration and clear pH shift during the desorption/regeneration allowed for regeneration rate of higher than 90% after 5 cycles of adsorption desorption. This article attempts to provide a competitive candidate for phosphate-capture, which is highly effective, easily separable and repeatedly usable.

Keywords: phosphate recovery, nanoparticles, superparamagnetic, adsorption, reusability

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Authors: Rasha Al-Saedi, Anthony Meijer

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The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

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Authors: Wenwen Lei, David R. Mckenzie

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Recent findings of anomalously high gas flow rates in carbon nanotubes show smooth hydrophobic walls can increase specular reflection of molecules and reduce the tangential momentum accommodation coefficient (TMAC). Here we report the first measurements of water vapor flows in microtubes over a wide humidity range and show that for hydrophobic silica there is a range of humidity over which an adsorbed water layer reduces TMAC and accelerates flow. Our results show that this association between hydrophobicity and accelerated moisture flow occurs in readily available materials. We develop a hierarchical theory that unifies Maxwell’s ideas on TMAC with Langmuir’s ideas on adsorption. We fit the TMAC data as a function of humidity with the hierarchical theory based on two stages of Langmuir adsorption and derive total adsorption isotherms for water on hydrophobic silica that agree with direct observations. We propose structures for each stage of the water adsorption, the first reducing TMAC by a passivation of adsorptive patches and a smoothing of the surface, the second resembling bulk water with large TMAC. We find that leak testing of moisture barriers with an ideal gas such as helium may not be accurate enough for critical applications and that direct measurements of the water leak rate should be made.

Keywords: water vapor flows, silica microtubes, TMAC, enhanced flow rates

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Authors: Z. Jamalzadeh, A. Niaei, H. Erfannia

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Due to developing industries, the emission of pollutants such as NOx, SOx, and CO2 are rapidly increased. Generally, NOx is attributed to the mono nitrogen oxides of NO and NO2 that is one of the most important atmospheric contaminants. Hence, controlling the emission of nitrogen oxides is environmentally urgent. Selective catalytic reduction of NOx is one of the most common techniques for NOx removal in which zeolites have wide application due to their high performance. In zeolitic processes, the catalytic reaction occurs mostly in the pores. Therefore, investigation of the adsorption phenomena of the molecules in order to gain an insight and understand the catalytic cycle is of important. Hence, in current study, benefiting from molecular simulations, the adsorption phenomena in the nanocatalysts of SCR of NOx process was investigated in order to get a good insight of the catalysts’ behavior. The effect of cation addition to the support in the catalysts’ behavior through adsorption step was explored by Mont Carlo (MC) using Materials Studio Package. Simulation time of 1 Ns accompanying 1 fs time step, COMPASS27 Force Field and the cut off radios of 12.5 Ȧ was applied for performed runs. It was observed that the adsorption capacity increases in the presence of cations. The sorption isotherms demonstrated the behavior of type I isotherm categories and sorption capacity diminished with increase in temperature whereas an increase was observed at high pressures. Besides, NO sorption showed higher sorption capacity than NH3 in H–ZSM5. In this respect, the energy distributions signified that the molecules could adsorb in just one sorption site at the catalyst and the sorption energy of NO was stronger than the NH3 in H-ZSM5. Furthermore, the isosteric heat of sorption data showed nearly same values for the molecules; however, it indicated stronger interactions of NO molecules with H-ZSM5 zeolite compared to the isosteric heat of NH3 which was low in value.

Keywords: Monte Carlo simulation, adsorption, NOx, ZSM5

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Authors: Indrasen Raghupatruni, Michael Glora, Ralf Diekmann, Thomas Demmer

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As the trend in automotive technology is fast moving towards hybridization and electrification to curb emissions as well as to improve the fuel efficiency, air-conditioning systems in passenger cars have not caught up with this trend and still remain as the major energy consumers amongst others. Adsorption based air-conditioning systems, e.g. with silica-gel water pair, which are already in use for residential and commercial applications, are now being considered as a technology leap once proven feasible for the passenger cars. In this paper we discuss a methodology, challenges and feasibility of implementing an adsorption based air-conditioning system in a passenger car utilizing the exhaust waste heat. We also propose an optimized control strategy with interfaces to the engine control unit of the vehicle for operating this system with reasonable efficiency supported by our simulation and validation results in a prototype vehicle, additionally comparing to existing implementations, simulation based as well as experimental. Finally we discuss the influence of start-stop and hybrid systems on the operation strategy of the adsorption air-conditioning system.

Keywords: adsorption air-conditioning, feasibility study, optimized control strategy, prototype vehicle

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Authors: H. Hammoudi, S. Bendenia, I. Batonneau-Gener, J. Comparot, K. Marouf-Khelifa, A. Khelifa

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X zeolites were prepared by ion-exchange with Cu2+ and/or Zn2+ cations, at different concentrations of the exchange solution, and characterised by thermal analysis and nitrogen adsorption. The acidity of the samples was investigated by pyridine adsorption–desorption followed by in situ Fourier transform infrared (FTIR) spectroscopy. Desorption was carried out at 150, 250 and 350 °C. The objective is to estimate the nature and concentration of acid sites. A comparison between the binary (Cu(x)X, Zn(x)X) and ternary (CuZn(x)X) exchanges was also established (x = level of exchange) through the Cu(43)X, Zn(48)X and CuZn(50)X samples. Lewis acidity decreases overall with desorption temperature and the level of exchange. As the latter increases, there is a conversion of some Lewis sites into those of Brønsted during thermal treatment. In return, the concentration of Brønsted sites increases with the degree of exchange. The Brønsted acidity of CuZn(50)X at 350 °C is more important than the sum of those of Cu(43)X and Zn(48)X. The found values were 73, 32 and 15 μmol g-1, respectively. Besides, the concentration of Brønsted sites for CuZn(50)X increases with desorption temperature. These features indicate the presence of a synergistic effect amplifying the strength of these sites when Cu2+ and Zn2+ cations compete for the occupancy of sites distributed inside zeolitic cavities.

Keywords: acidity, adsorption, pyridine, zeolites

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Authors: Nedal N. Marei, Nashaat Nassar

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Many treatment techniques have been used to remove the soluble pollutants from wastewater as; dyes and metal ions which could be found in rich amount in the used water of the textile and tanneries industry. The effluents from these industries are complex, containing a wide variety of dyes and other contaminants, such as dispersants, acids, bases, salts, detergents, humectants, oxidants, and others. These techniques can be divided into physical, chemical, and biological methods. Adsorption has been developed as an efficient method for the removal of heavy metals from contaminated water and soil. It is now recognized as an effective method for the removal of both organic and inorganic pollutants from wastewaters. Nanosize materials are new functional materials, which offer high surface area and have come up as effective adsorbents. Nano alumina is one of the most important ceramic materials widely used as an electrical insulator, presenting exceptionally high resistance to chemical agents, as well as giving excellent performance as a catalyst for many chemical reactions, in microelectronic, membrane applications, and water and wastewater treatment. In this study, methylene blue (MB) dye has been used as model dye of textile wastewater in order to synthesize a synthetic MB wastewater. NiO nanoparticles were added in small percentage in the sand packed bed adsorption columns to remove the MB from the synthetic textile wastewater. Moreover, different parameters have been evaluated; flow of the synthetic wastewater, pH, height of the bed, percentage of the NiO to the sand in the packed material. Different mathematical models where employed to find the proper model which describe the experimental data and help to analyze the mechanism of the MB adsorption. This study will provide good understanding of the dyes adsorption using metal oxide nanoparticles in the classical sand bed.

Keywords: adsorption, column, nanoparticles, methylene

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Authors: Hacer Sule Gonul, Vedat Uyak

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Intensive use of pesticides in agricultural activity causes mixing of these compounds into water sources with surface flow. Especially after the 1970s, a number of limitations imposed on the use of chlorinated pesticides that have a carcinogenic risk potential and regulatory limit have been established. These chlorinated pesticides discharge to water resources, transport in the water and land environment and accumulation in the human body through the food chain raises serious health concerns. Carbon nanotubes (CNTs) have attracted considerable attention from on all because of their excellent mechanical, electrical, and environmental characteristics. Due to CNT particles' high degree of hydrophobic surfaces, these nanoparticles play critical role in the removal of water contaminants of natural organic matters, pesticides and phenolic compounds in water sources. Health concerns associated with chlorinated pesticides requires the removal of such contaminants from aquatic environment. Although the use of aldrin and atrazine was restricted in our country, repatriation of illegal entry and widespread use of such chemicals in agricultural areas cause increases for the concentration of these chemicals in the water supply. In this study, the compounds of chlorinated pesticides such as aldrin and atrazine compounds would be tried to eliminate from drinking water with carbon nanotube adsorption method. Within this study, 2 different types of CNT would be used including single-wall (SWCNT) and multi-wall (MWCNT) carbon nanotubes. Adsorption isotherms within the scope of work, the parameters affecting the adsorption of chlorinated pesticides in water are considered as pH, contact time, CNT type, CNT dose and initial concentration of pesticides. As a result, under conditions of neutral pH conditions with MWCNT respectively for atrazine and aldrin obtained adsorption capacity of determined as 2.24 µg/mg ve 3.84 µg/mg. On the other hand, the determined adsorption capacity rates for SWCNT for aldrin and atrazine has identified as 3.91 µg/mg ve 3.92 µg/mg. After all, each type of pesticide that provides superior performance in relieving SWCNT particles has emerged.

Keywords: pesticide, drinking water, carbon nanotube, adsorption

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