Search results for: adsorption isotherm models

Authors: Souhila Bendenia, Chahrazed Bendenia, Hanaa Merad-Dib, Sarra Merabet, Samia Moulebhar, Sid Ahmed Khantar

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Today, environmental pollution is a major concernworldwide, threateninghumanhealth. Various techniques have been used, includingdegradation, filtration, advancedoxidationprocesses, ion exchange, membrane processes, and adsorption. The latter is one of the mostsuitablemethods, usinghighly efficient materials. In this study, NaX zeolite was modified with Cu or Ni at various rates. Following ion exchange, the samples were characterized by XRD, BET and SEM/EDX. After characterization, the exchanged zeolites were used for adsorption of various pollutants as CO2. Different thermodynamic parameters were studied such as Qst. XRD results show that the most intense peaks characteristic of 13X persist after the exchange reaction for all samples. The SEM images of our samples have uniform and regular crystal shapes. The results show that ion exhange with Cu or Ni affect the textural properties of X zeolites and prove that the exchange zeolites can be used as an adsorbent for depollution.

Keywords: X zeolites (NaX), ion exchange, characterization, adsorption

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Authors: Rakesh Namdeti

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The liquid waste-wastewater- is essentially the water supply of the community after it has been used in a variety of applications. In recent years, heavy metal concentrations, besides other pollutants, have increased to reach dangerous levels for the living environment in many regions. Among the heavy metals, Lead has the most damaging effects on human health. It can enter the human body through the uptake of food (65%), water (20%), and air (15%). In this background, certain low-cost and easily available biosorbent was used and reported in this study. The scope of the present study is to remove Lead from its aqueous solution using Olea EuropaeaResin as biosorbent. The results showed that the biosorption capacity of Olea EuropaeaResin biosorbent was more for Lead removal. The Langmuir, Freundlich, Tempkin, and Dubinin-Radushkevich (D-R) models were used to describe the biosorption equilibrium of Lead Olea EuropaeaResin biosorbent, and the biosorption followed the Langmuir isotherm. The kinetic models showed that the pseudo-second-order rate expression was found to represent well the biosorption data for the biosorbent.

Keywords: novel biosorbent, central composite design, Lead, isotherms, kinetics

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Authors: Tsung-Lin Hsieh, Jiun-Jen Chen, Yuhao Kang

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Metal-organic frameworks (MOFs) have drawn scientists’ attention for decades due to its high specific surface area, tunable pore size, and relatively low temperature for regeneration. Bearing with those mentioned properties, MOFs has been widely used in various applications, such as adsorption/separation and catalysis. However, the current challenge for practical use of MOFs is to effectively shape these crystalline powder material into controllable forms such as pellets, granules, and monoliths with sufficient mechanical and chemical stability, while maintaining the excellent properties of MOFs powders. Herein, we have successfully synthesized an Al-based MOF powder which exhibits a high water capacity at relatively low humidity conditions and relatively low temperature for regeneration. Then the synthesized Al-MOF was shaped into granules with particle size of 2-4 mm by (1) tumbling granulation, (2) High shear mixing granulation, and (3) Extrusion techniques. Finally, the water vapor adsorption rate and crush strength of Al-MOF granules by different shaping techniques were measured and compared.

Keywords: granulation, granules, metal-organic frameworks, water vapor adsorption

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Authors: Saad Mohamed Elsaid Abdelrahman

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The adsorption method is one of the best modern techniques used in removing pollutants, especially organic hydrocarbon compounds, from polluted water. Through this research, bentonite clay can be used to remove organic hydrocarbon compounds, such as heptane and octane, resulting from oil spills in seawater. Bentonite clay can be obtained from the Kholayaz area, located north of Jeddah, at a distance of 80 km. Chemical analysis shows that bentonite clay consists of a mixture of silica, alumina and oxides of some elements. Bentonite clay can be activated in order to raise its adsorption efficiency and to make it suitable for removing pollutants using an ionic organic solvent. It is necessary to study some of the factors that could be in the efficiency of bentonite clay in removing oily organic compounds, such as the time of contact of the clay with heptane and octane solutions, pH and temperature, in order to reach the highest adsorption capacity of bentonite clay. The temperature can be a few degrees Celsius higher. The adsorption capacity of the clay decreases when the temperature is raised more than 4°C to reach its lowest value at the temperature of 50°C. The results show that the friction time of 30 minutes and the pH of 6.8 is the best conditions to obtain the highest adsorption capacity of the clay, 467 mg in the case of heptane and 385 mg in the case of octane compound. Experiments conducted on bentonite clay were encouraging to select it to remove heavy molecular weight pollutants such as petroleum compounds under study.

Keywords: adsorbent, bentonite clay, oil spills, removal

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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: Srinivasulu Dasaiah, Kalyan Yakkala, Gangadhar Battala, Pavan Kumar Pindi, Ramakrishna Naidu Gurijala

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Tinospora cordifolia leaves biomass used for the removal fluoride from aqueous solutions. Batch biosorption technique was applied, pH, contact time, biosorbent dose and initial fluoride concentration was studied. The Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) techniques used to study the surface characteristics and the presence of chemical functional groups on the biosorbent. Biosorption isotherm models and kinetic models were applied to understand the sorption mechanism. Results revealed that pH, contact time, biosorbent dose and initial fluoride concentration played a significant effect on fluoride removal from aqueous solutions. The developed biosorbent derived from Tinospora cordifolia leaves biomass found to be a low-cost biosorbent and could be used for the effective removal of fluoride in synthetic as well as real water samples.

Keywords: biosorption, contact time, fluoride, isotherms

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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: 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: 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. 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: 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: 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: 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: 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

Procedia PDF Downloads 146

Authors: Saidur R. Chowdhury, Mamme K. Addai, Ernest K. Yanful

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The research was performed to assess the potential of nickel smelter slag, an industrial waste, as an adsorbent in the removal of metals from aqueous solution. An investigation was carried out for Arsenic (As), Copper (Cu), lead (Pb) and Cadmium (Cd) adsorption from aqueous solution. Smelter slag was obtain from Ni ore at the Vale Inco Ni smelter in Sudbury, Ontario, Canada. The batch experimental studies were conducted to evaluate the removal efficiencies of smelter slag. The slag was characterized by surface analytical techniques. The slag contained different iron oxides and iron silicate bearing compounds. In this study, the effect of pH, contact time, particle size, competition by other ions, slag dose and distribution coefficient were evaluated to measure the optimum adsorption conditions of the slag as an adsorbent for As, Cu, Pb and Cd. The results showed 95-99% removal of As, Cu, Pb, and almost 50-60% removal of Cd, while batch experimental studies were conducted at 5-10 mg/L of initial concentration of metals, 10 g/L of slag doses, 10 hours of contact time and 170 rpm of shaking speed and 25oC condition. The maximum removal of Arsenic (As), Copper (Cu), lead (Pb) was achieved at pH 5 while the maximum removal of Cd was found after pH 7. The column experiment was also conducted to evaluate adsorption depth and service time for metal removal. This study also determined adsorption capacity, adsorption rate and mass transfer rate. The maximum adsorption capacity was found to be 3.84 mg/g for As, 4 mg/g for Pb, and 3.86 mg/g for Cu. The adsorption capacity of nickel slag for the four test metals were in decreasing order of Pb > Cu > As > Cd. Modelling of experimental data with Visual MINTEQ revealed that saturation indices of < 0 were recorded in all cases suggesting that the metals at this pH were under- saturated and thus in their aqueous forms. This confirms the absence of precipitation in the removal of these metals at the pHs. The experimental results also showed that Fe and Ni leaching from the slag during the adsorption process was found to be very minimal, ranging from 0.01 to 0.022 mg/L indicating the potential adsorbent in the treatment industry. The study also revealed that waste product (Ni smelter slag) can be used about five times more before disposal in a landfill or as a stabilization material. It also highlighted the recycled slags as a potential reactive adsorbent in the field of remediation engineering. It also explored the benefits of using renewable waste products for the water treatment industry.

Keywords: adsorption, industrial waste, recycling, slag, treatment

Procedia PDF Downloads 121

Authors: Hamza Simsir, Nurettin Eltugral, Selhan Karagöz

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Surface modification and functionalization has been an important tool for scientists in order to open new frontiers in nano science and nanotechnology. Desired surface characteristics for the intended applications can be achieved with surface functionalization. In this work, the effect of water soluble ligands on the adsorption capabilities of silver nanoparticles onto AC which was synthesized from German beech wood, was investigated. Sodium borohydride (NaBH4) and polyvinyl alcohol (PVA) were used as the ligands. Silver nanoparticles with different surface coatings have average sizes range from 10 to 13 nm. They were synthesized in aqueous media by reducing Ag (I) ion in the presence of ligands. These particles displayed adsorption tendencies towards AC when they were mixed together and shaken in distilled water. Silver nanoparticles (NaBH4-AgNPs) reduced and stabilized by NaBH4 adsorbed onto AC with a homogenous dispersion of aggregates with sizes in the range of 100-400 nm. Beside, silver nanoparticles, which were prepared in the presence of both NaBH4 and PVA (NaBH4/PVA-Ag NPs), demonstrated that NaBH4/PVA-Ag NPs adsorbed and dispersed homogenously but, they aggregated with larger sizes on the AC surface (range from 300 to 600 nm). In addition, desorption resistance of Ag nanoparticles were investigated in distilled water. According to the results AgNPs were not desorbed on the AC surface in distilled water.

Keywords: Silver nanoparticles, ligand, activated carbon, adsorption

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Authors: Maziar Noei

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Calculation showed that when the nanosheet is doped by Si, the adsorption energy is about -85.62 to -87.43kcal/mol and also the amount of HOMO/LUMO energy gap (Eg) will reduce significantly. Boron nitride nanosheet is a suitable adsorbent for cyanogen and can be used in separation processes cyanogen. It seems that nanosheet (BNNS) is a suitable semiconductor after doping. The doped BNNS in the presence of cyanogens (C2N2) an electrical signal is generating directly and, therefore, can potentially be used for cyanogen sensors.

Keywords: nanosheet, DFT, cyanogen, sensors

Procedia PDF Downloads 263

Authors: Lucky Malise, Hilary Rutto, Tumisang Seodigeng

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The use of tires in automobiles is very important in the automobile industry. However, there is a serious environmental problem concerning the disposal of these rubber tires once they become worn out. The main aim of this study was to prepare activated carbon from waste tire pyrolysis char by impregnating KOH on pyrolytic char. Adsorption studies on lead onto chemically activated carbon was carried out using response surface methodology. The effect of process parameters such as temperature (°C), adsorbent dosage (g/1000ml), pH, contact time (minutes) and initial lead concentration (mg/l) on the adsorption capacity were investigated. It was found that the adsorption capacity increases with an increase in contact time, pH, temperature and decreases with an increase in lead concentration. Optimization of the process variables was done using a numerical optimization method. Fourier Transform Infrared Spectra (FTIR) analysis, XRay diffraction (XRD), Thermogravimetric analysis (TGA) and scanning electron microscope was used to characterize the pyrolytic carbon char before and after activation. The optimum points 1g/ 100 ml for adsorbent dosage, 7 for pH value of the solution, 115.2 min for contact time, 100 mg/l for initial metal concentration, and 25°C for temperature were obtained to achieve the highest adsorption capacity of 93.176 mg/g with a desirability of 0.994. Fourier Transform Infrared Spectra (FTIR) analysis and Thermogravimetric analysis (TGA) show the presence of oxygen-containing functional groups on the surface of the activated carbon produced and that the weight loss taking place during the activation step is small.

Keywords: waste tire pyrolysis char, chemical activation, central composite design (CCD), adsorption capacity, numerical optimization

Procedia PDF Downloads 191

Authors: J. Gómez, J. Rodriguez, N. Santos, E. Mejía-Ospino

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The wettability of the minerals present in a reservoir is a determining property in the recovery factor. One of the strategies proposed to increase recovery is based on altering the wettability of oil reservoir rocks. Approximately 60% of world crude oil reservoirs have sandstone-type host rocks; for that, it is very important to develop efficient methodologies to alter the wettability of these rocks. In this study, the alteration of the wettability of a sandstone rock due to graphene oxide (GO) adsorption was evaluated. The effect of GO concentration, salinity, Ca2+ ions, and pH on interfacial tension and contact angle was determined. The results show that GO adsorption induces significant changes in rock wettability. For high GO concentrations and low salinity, pH proved to be a determining factor in the alteration of wettability. Under certain conditions, surface wettability changes from highly oleophilic (144,8°) to intermediate oil wettability (91,2°).

Keywords: enhanced oil recovery, graphene oxide, interfacial tension, nanofluid, wettability

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Authors: Hanane Belayachi, Sarra Bourahla, Amel Belayachi, Fadela Nemchi, Mostefa Belhakem

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The most used techniques to remove pollutants from wastewater are adsorption onto activated carbon (AC) and oxidation using a photocatalyst slurry. The aim of this work is to eliminate such drawbacks by combining AC and titanium dioxide (TiO₂) in a photocatalytically Regenerative Activated Carbon. Anatase titania was deposited on powder-activated carbon made from grape seeds by the impregnation method, and then the composite photocatalyst was employed for the removal of reactive black 5, which is an anionic azo dye, from water. The AGS/TiO₂ was characterized by BET, MEB, RDX and optical absorption spectroscopy. The BET surface area and the pore structure of composite photocatalysts (AGS/TiO₂) and activated grape seeds (AGS) were evaluated from nitrogen adsorption data at 77 K in relation to process conditions. Our results indicate that the photocatalytic activity of AGS/TiO₂ was much higher than single-phase titania. The adsorption equilibrium of reactive black 5 from aqueous solutions on the examined materials was investigated. Langmuir, Freundlich, and Redlich–Petersen models were fitted to experimental equilibrium data, and their goodness of fit is compared. The degradation kinetics fitted well to the Langmuir-Hinselwood pseudo first order rate low. The photocatalytic activity of AGS/TiO₂ was much higher than virgin TiO₂. Chemical oxygen demand (COD) removal was measured at regular intervals to quantify the mineralization of the dye. Above 96% mineralization was observed. These results suggest that UV-irradiated TiO₂ immobilized on activated carbon may be considered an adequate process for the treatment of diluted colored textile wastewater.

Keywords: activated carbon, pollutant, catalysis, TiO₂

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Authors: Aura Alejandra Burbano Patino, Mariela Agotegaray, Veronica Lassalle, Fernanda Horst

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Water pollution is of worldwide concern due to its importance as an essential resource for life. Industrial and urbanistic growth are anthropogenic activities that have caused an increase of undesirable compounds in water. In the last decade, emerging pollutants have become of great interest since, at very low concentrations (µg/L and ng/L), they exhibit a hazardous effect on wildlife, aquatic ecosystems, and human organisms. One group of emerging pollutants that are a matter of study are pharmaceuticals. Their high consumption rate and their inappropriate disposal have led to their detection in wastewater treatment plant influent, effluent, surface water, and drinking water. In consequence, numerous technologies have been developed to efficiently treat these pollutants. Adsorption appears like an easy and cost-effective technology. One of the most used adsorbents of emerging pollutants removal is carbon-based materials such as hydrochars. This study aims to use a magnetic hydrochar nanocomposite to be employed as an adsorbent for diclofenac removal. Kinetics models and the adsorption efficiency in real water samples were analyzed. For this purpose, a magnetic hydrochar nanocomposite was synthesized through the hydrothermal carbonization (HTC) technique hybridized to co-precipitation to add the magnetic component into the hydrochar, based on iron oxide nanoparticles. The hydrochar was obtained from sunflower husk residue as the precursor. TEM, TGA, FTIR, Zeta potential as a function of pH, DLS, BET technique, and elemental analysis were employed to characterize the material in terms of composition and chemical structure. Adsorption kinetics were carried out in distilled water and real water at room temperature, pH of 5.5 for distilled water and natural pH for real water samples, 1:1 adsorbent: adsorbate dosage ratio, contact times from 10-120 minutes, and 50% dosage concentration of DCF. Results have demonstrated that magnetic hydrochar presents superparamagnetic properties with a saturation magnetization value of 55.28 emu/g. Besides, it is mesoporous with a surface area of 55.52 m²/g. It is composed of magnetite nanoparticles incorporated into the hydrochar matrix, as can be proven by TEM micrographs, FTIR spectra, and zeta potential. On the other hand, kinetic studies were carried out using DCF models, finding percent removal efficiencies up to 85.34% after 80 minutes of contact time. In addition, after 120 minutes of contact time, desorption of emerging pollutants from active sites took place, which indicated that the material got saturated after that t time. In real water samples, percent removal efficiencies decrease up to 57.39%, ascribable to a possible mechanism of competitive adsorption of organic or inorganic compounds, ions for active sites of the magnetic hydrochar. The main suggested adsorption mechanism between the magnetic hydrochar and diclofenac include hydrophobic and electrostatic interactions as well as hydrogen bonds. It can be concluded that the magnetic hydrochar nanocomposite could be valorized into a by-product which appears as an efficient adsorbent for DCF removal as a model emerging pollutant. These results are being complemented by modifying experimental variables such as pollutant’s initial concentration, adsorbent: adsorbate dosage ratio, and temperature. Currently, adsorption assays of other emerging pollutants are being been carried out.

Keywords: environmental remediation, emerging pollutants, hydrochar, magnetite nanoparticles

Procedia PDF Downloads 168

Authors: Karoline Reis de Sena

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Endocrine disruptors are unregulated or not fully regulated compounds, even in the most developed countries, and which can be a danger to the environment and human health. They pass untreated through the secondary stage of conventional wastewater treatment plants, then the effluent from the wastewater treatment plants is discharged into the rivers, upstream and downstream from the drinking water treatment plants that use the same river water as the tributary. Long-term consumption of drinking water containing low concentrations of these compounds can cause health problems; these are persistent in nature and difficult to remove. In this way, research on emerging pollutants is expanding and is fueled by progress in finding the appropriate method for treating wastewater. Adsorption is the most common separation process, it is a simple and low-cost operation, but it is not eco-efficient. Concomitant to this, biosorption arises, which is a subcategory of adsorption where the biosorbent is biomass and which presents numerous advantages when compared to conventional treatment methods, such as low cost, high efficiency, minimization of the use of chemicals, absence of need for additional nutrients, biosorbent regeneration capacity and the biomass used in the production of biosorbents are found in abundance in nature. Thus, the use of alternative materials, such as sewage sludge, for the synthesis of adsorbents has proved to be an economically viable alternative, together with the importance of valuing the generated by-product flows, as well as managing the problem of their correct disposal. In this work, an alternative for the management of sewage sludge is proposed, transforming it into activated carbon and using it in the adsorption process of 17a-ethinylestradiol.

Keywords: 17α-ethinylestradiol, adsorption, activated carbon, sewage sludge, micropollutants

Procedia PDF Downloads 71

Authors: N. Ouslimani, M. T. Abadlia

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Wastewater from manufacturing industries are responsible for many organic micropollutants such as some detergents and dyes. It is estimated that 10-15 % of these chemical compounds in the effluents are discharged. In the method of dyeing the dyes are often used in excess to improve the dye and thereby the waste water are highly concentrated dye. The treatment of effluents containing dye has become a necessity given its negative repercussions on ecosystems mainly due to the pollutant nature of synthetic dyes and particularly soluble dyes such as acid dyes. Technology adsorptive separation is now a separation technologies of the most important treatments. The choice led to the use of bentonite occurs in order to use an equally effective and less costly than replacing charcoal. This choice is also justified by the importance of the material developed by, the possibility of cation exchange and high availability in our country surface. During this study, therefore, we test the clay, the main constituent is montmorillonite, whose most remarkable properties are its swelling resulting from the presence of water in the space between the sheets and the fiber structure to the adsorption of acid dye "red Bemacid. "The study of various parameters i.e. time, temperature, and pH showed that the adsorption is more favorable to the temperature of 19 °C for 240 minutes at a Ph equal to 2.More styles and Langmuir adsorption Freundlich were applied to describe the isotherms. The results show that sodium bentonite seems to affect the ability and effectiveness to adsorb colorant.Les ultimate quantities are respectively 0.629 mg/g and 0.589 mg/g for sodium bentonite and bentonite gross.

Keywords: Bentonite, treatment of polluted water, acid dyes, adsorption

Procedia PDF Downloads 235