Graphite intercalation compound (GIC) has been demonstrated to be a useful, low capacity and rapid adsorbent for the removal of organic micropollutants from water. The high electrical conductivity and low capacity of the material lends itself to electrochemical regeneration. Following electrochemical regeneration, equilibrium loading under similar conditions is reported to exceed that achieved by the fresh adsorbent. This behavior is reported in terms of the regeneration efficiency being greater than 100%. In this work, surface analysis techniques are employed to investigate the material in three states: ‘Fresh’, ‘Loaded’ and ‘Regenerated’. ‘Fresh’ GIC is shown to exhibit a hydrogen and oxygen rich surface layer approximately 150 nm thick. ‘Loaded’ GIC shows a similar but slightly thicker surface layer (approximately 370 nm thick) and significant enhancement in the hydrogen and oxygen abundance extending beyond 600 nm from the surface. 'Regenerated’ GIC shows an oxygen rich layer, slightly thicker than the fresh case at approximately 220 nm while showing a very much lower hydrogen enrichment at the surface. Results demonstrate that while the electrochemical regeneration effectively removes the phenol model pollutant, it also oxidizes the exposed carbon surface. These results may have a significant impact on the estimation of adsorbent life.
Spent bleaching earth (SBE) recycling and utilization as an adsorbent to eliminate dyes from aqueous solution was studied. Organic solvents and subsequent thermal treatment were carried out to recover and reactivate the SBE. The effect of pH, temperature, dye’s initial concentration, and contact time on the dye removal using recycled spent bleaching earth (RSBE) was investigated. Recycled SBE showed better removal affinity of cationic than anionic dyes. The maximum removal was achieved at pH 2 and 8 for anionic and cationic dyes, respectively. Kinetic data matched with the pseudo second-order model. The adsorption phenomenon governing this process was identified by the Langmuir and Freundlich isotherms for anionic dye while Freundlich model represented the sorption process for cationic dye. The changes of Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were computed and compared through thermodynamic study for both dyes.
Many of thermosetting resins have application only in filled state, reinforced with different mineral fillers. The co-filling of polymers with mineral filler and gases creates a possibility for production of polymer composites materials with low density. This processing leads to forming of new materials – gas-filled plastics (polymer foams). The properties of these materials are determined mainly by the shape and size of internal structural elements (pores). The interactions on the phase boundaries have influence on the materials properties too. In the present work, the gas-filled urea-formaldehyde resins were reinforced by waste phosphogypsum. The waste phosphogypsum (CaSO4.2H2O) is a solid by-product in wet phosphoric acid production processes. The values of the interactions polymer-filler were increased by using two modifying agents: polyvinyl acetate for polymer matrix and sodium metasilicate for filler. Technological methods for gas-filling and recipes of urea-formaldehyde based materials with apparent density 20-120 kg/m3 were developed. The heat conductivity of the samples is between 0.024 and 0.029 W/moK. Tensile analyses were carried out at 10 and 50% deformation and show values 0.01-0.14 MPa and 0.01-0.09 MPa, respectively. The apparent density of obtained materials is between 20 and 92 kg/m3. The changes in the tensile properties and density of these materials according to sodium metasilicate content were studied too. The mechanism of phosphogypsum adsorption modification was studied using methods of FT-IR spectroscopy. The structure of the gas-filled urea-formaldehyde resins was described by results of electron scanning microscopy at three different magnification ratios – x50, x150 and x 500. The aim of present work is to study the possibility of the usage of phosphogypsum as mineral filler for urea-formaldehyde resins and development of a technology for the production of gas-filled reinforced polymer composite materials. The structure and the properties of obtained composite materials are suitable for thermal and sound insulation applications.
Energy saving and environment friendly applications are turning out to be one of the most important topics nowadays. In this work, a simulation analysis using TRNSYS software has been carried out to study the benefit of employing a solar adsorption cooling system under the climatic conditions of Al-Minya city, Egypt. A theoretical model was carried out on a two bed adsorption cooling system employing granular activated carbon-HFC-404A as working pair. Temporal and averaged history of solar collector, adsorbent beds, evaporator and condenser has been shown. System performance in terms of daily average cooling capacity and average coefficient of performance around the year has been investigated. The results showed that maximum yearly average coefficient of performance (COP) and cooling capacity are about 0.26 and 8 kW respectively. The maximum value of the both average cooling capacity and COP cyclic is directly proportional to the maximum solar radiation. The system performance was found to be increased with the average ambient temperature. Finally, the proposed solar powered adsorption cooling systems can be used effectively under Al-Minya climatic conditions.
Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.
Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH3)3 was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.
Iron nanoparticles were used to cleanup effluents. This paper involves synthesis of iron nanoparticles chemically by sodium borohydride reduction of ammonium ferrous sulfate solution (FAS). Iron oxide nanoparticles have lesser efficiency of adsorption than Zero Valent Iron nanoparticles (nZVI). Glucosamine acts as a stabilizing agent and chelating agent to prevent Iron nanoparticles from oxidation. nZVI particles were characterized using Scanning Electron Microscopy (SEM). Thus, the synthesized nZVI was subjected to entrapment in biopolymer, viz. barium (Ba)-alginate beads. The beads were characterized using SEM. Batch dye degradation studies were conducted using Reactive black Water soluble Nontoxic Natural substances (WNN) dye which is one of the most hazardous dyes used in textile industries. Effect of contact time, effect of pH, initial dye concentration, adsorbent dosage, isotherm and kinetic studies were carried out.
The removal of lead ion (Pb2+) from aqueous solution by activated carbon with phosphoric acid activation employing mangrove propagule as precursor was investigated in a batch adsorption system. Batch studies were carried out to address various experimental parameters including pH and contact time. The Langmuir and Freundlich models were able to describe the adsorption equilibrium, while the pseudo first order and pseudo second order models were used to describe kinetic process of Pb2+ adsorption. The results show that the adsorption data are seen in accordance with Langmuir isotherm model and pseudo-second order kinetic model.
Coatings based on polyaniline (PANI) can improve the resistance of steel against corrosion. In this work, the preparation of stable suspensions of colloidal PANI-SiO2 particles, suitable for obtaining of composite anticorrosive coating on steel, is described. Electrokinetic data as a function of pH are presented, showing that the zeta potentials of the PANI-SiO2 particles are governed primarily by the charged groups at the silica oxide surface. Electrosteric stabilization of the PANI-SiO2 particles’ suspension against aggregation is realized at pH>5.5 (EB form of PANI) by adsorption of positively charged polyelectrolyte molecules onto negatively charged PANI-SiO2 particles. The PANI-SiO2 particles are incorporated by electrodeposition into the metal matrix of zinc in order to obtain composite (hybrid) coatings. The latter are aimed to ensure sacrificial protection of steel mainly in aggressive media leading to local corrosion damages. The surface morphology of the composite zinc coatings is investigated with SEM. The influence of PANI-SiO2 particles on the cathodic and anodic processes occurring in the starting electrolyte for obtaining of the coatings is followed with cyclic voltammetry. The electrochemical and corrosion behavior is evaluated with potentiodynamic polarization curves and polarization resistance measurements. The beneficial effect of the stabilized PANI-SiO2 particles for the increased protective ability of the composites is commented and discussed.
Methanol-to-propylene conversion was carried out in a continuous-flow fixed-bed reactor over nano-sized HZSM-5 zeolites. The HZSM-5 catalysts were synthesized with different Si/Al ratio and silicon sources, and treated with NaOH. The structural property, morphology, and acidity of catalysts were measured by XRD, N2 adsorption, FE-SEM, TEM, and NH3-TPD. The results indicate that the increment of Si/Al ratio decreased the acidity of catalysts and then improved propylene selectivity, while silicon sources had slight impact on the acidity but affected the product distribution. The desilication after alkali treatment could increase intracrystalline mesopores and enhance propylene selectivity.
In this study, malt bagasse, a low-cost waste biomass, was tested as a biosorbent to remove the cationic dye Malachite green (MG) from aqueous solution. Batch biosorption experiments were investigated as functions of different experimental parameters such as initial pH, salt (NaCl) concentration, contact time, temperature and initial dye concentration. Higher removal rates of MG were obtained at pH 8 and 10. The equilibrium and kinetic studies suggest that the biosorption follows Langmuir isotherm and the pseudo-second-order model. The maximum monolayer adsorption capacity was estimated at 117.65 mg/g (at 45 °C). According to Dubinin–Radushkevich (D-R) isotherm model, biosorption of MG onto malt bagasse occurs physically. The thermodynamic parameters such as Gibbs free energy, enthalpy and entropy indicated that the MG biosorption onto malt bagasse is spontaneous and endothermic. The results of the ionic strength effect indicated that the biosorption process under study had a strong tolerance under high salt concentrations. It can be concluded that malt bagasse waste has potential for application as biosorbent for removal of MG from aqueous solution.
In this work, adsorption of chlorophylls a and b pigments in aqueous solution on the inner and outer surfaces of single-walled carbon nanotube (SWCNT) has been studied using molecular dynamics simulation. The linear interaction energy algorithm has been used to calculate the binding free energy. The results show that the adsorption of two pigments is fine on the both positions. Although there is the close similarity between these two pigments, their interaction with the nanotube is different. This result is useful to separate these pigments from one another. According to interaction energy between the pigments and carbon nanotube, interaction between these pigments-SWCNT on the inner surface is stronger than the outer surface. The interaction of SWCNT with chlorophylls phytol tail is stronger than the interaction of SWCNT with porphyrin ring of chlorophylls.
This work concerns with the experimental study of the adsorption of the Ni(II) on bentonite. The effects of various parameters such as contact time, stirring rate, initial concentration of Ni(II), masse of clay, initial pH of aqueous solution and temperature on the adsorption yield, were carried out. The study of the effect of the ionic strength on the yield of adsorption was examined by the identification and the quantification of the present chemical species in the aqueous phase containing the metallic ion Ni(II). The adsorbed species were investigated by a calculation program using CHEAQS V. L20.1 in order to determine the relation between the percentages of the adsorbed species and the adsorption yield. The optimization process was carried out using 23 factorial designs. The individual and combined effects of three process parameters, i.e. initial Ni(II) concentration in aqueous solution (2.10−3 and 5.10−3 mol/L), initial pH of the solution (2 and 6.5), and mass of bentonite (0.03 and 0.3 g) on Ni(II) adsorption, were studied.
An organoclay (HDTMA-B) was prepared from sodium bentonite (Na-B). The starting material was modified using the hexadecyltrimethylammonium ion (HDTMA+) in the amounts corresponding to 100 % of the CEC value. Batch experiments were carried out in order to model and optimize the sorption of Congo red dye from aqueous solution. The pseudo-first order and pseudo-second order kinetic models have been developed to predict the rate constant and the sorption capacity at equilibrium with the effect of temperature, the solid/solution ratio and the initial dye concentration. The equilibrium time was reached within 60 min. At room temperature (20 °C), optimum dye sorption of 49.4 mg/g (98.9%) was achieved at pH 6.6, sorbent dosage of 1g/L and initial dye concentration of 50 mg/L, using surfactant modified bentonite. The optimization of adsorption parameters mentioned above on dye removal was carried out using Box-Behnken design. The sorption parameters were analyzed statistically by means of variance analysis by using the Statgraphics Centurion XVI software.
There is a need for new systems that can be attached to drinking water treatment plants and have the required treatment capacity as well as the selectivity regarding components derived from anthropogenic activities. In a context of high volumes of water and low concentration of contaminants, adsorption/interchange processes are appealing since they meet the required features. Iron oxides such as siderite and molysite, which are respectively based on FeCO3 and FeCl3, can be found in nature. In this work, their observed performance, raw or roasted at different temperatures, as adsorbents of some inorganic anions is discussed. Roasted 1:1 FeCO3: FeCl3 mixture was very selective for arsenic and allowed a 100% removal of As from a 10 mg L-1 As solution. Besides, the 1:1 FeCO3 and FeCl3 mixture roasted at 500 ºC showed good selectivity for, in order of preference, arsenate, bromate, phosphate, fluoride and nitrate anions with distribution coefficients of, respectively, 4200, 2800, 2500 0.4 and 0.03 L g-1.
The main objective of this study is to investigate basic properties of different natural clays, by two methods. The first method is a gas phase conversion of methylbutynol (MBOH). The second method is the application of Pyrrole-tpd. Based on the product distribution from the first method, the acidic, basic and coordinately unsaturated sites were differentiated. It was shown that both the conversion and the selectivity for basic products did not change with reaction time. Nevertheless, a deviation from the stoichiometric ratio R of formed acetylene to acetone was observed (R=0.8…0.97). The conversion normalized to the surface area was used for establishing the activity sequence: White kaolinite > red kaolinite > bentonite > zeolite > diatomite. In addition, the results were compared with synthetic amorphous alumosilicates and typical basic materials like MgO and ZnO. The basic properties were characterized using the Pyrrole-tpd. The Pyrrole-tpd results showed the same basicity sequence as the MBOH gas phase reaction.
The aim of this paper was to study the sorption properties of a blast furnace sludge used as the sorbent. The sorbent was utilized for reduction of content of lead and zinc ions. Sorbent utilized in this work was obtained from metallurgical industry from process of wet gas treatment in iron production. The blast furnace sludge was characterized by X-Ray diffraction, scanning electron microscopy, and XRFS spectroscopy. Sorption experiments were conducted in batch mode. The sorption of metal ions in the sludge was determined by correlation of adsorption isotherm models. The adsorption of lead and zinc ions was best fitted with Langmuir adsorption isotherms. The adsorption capacity of lead and zinc ions was 53.8 mg.g-1 and 10.7 mg.g-1, respectively. The results indicated that blast furnace sludge could be effectively used as secondary material and could be also employed as a low-cost alternative for the removal of heavy metals ions from wastewater.
Ammonia in mining wastewater is a significant problem, and treatment can be especially difficult in cold climates where biological treatment is not feasible. An adsorption process is one of the alternative processes that can be used to reduce ammonia concentrations to acceptable limits, and therefore a LEWATIT resin strongly acidic H+ form ion exchange resin and a Bowie Chabazite Na form AZLB-Na zeolite were tested to assess their effectiveness. For these adsorption tests, two packed bed columns (a mini-column constructed from a 32-cm long x 1-cm diameter piece of glass tubing, and a 60-cm long x 2.5-cm diameter Ace Glass chromatography column) were used containing varying quantities of the adsorbents. A mining wastewater with ammonia concentrations of 22.7 mg/L was fed through the columns at controlled flowrates. In the experimental work, maximum capacities of the LEWATIT ion exchange resin were 0.438, 0.448, and 1.472 mg/g for 3, 6, and 9 g respectively in a mini column and 1.739 mg/g for 141.5 g in a larger Ace column while the capacities for the AZLB-Na zeolite were 0.424, and 0.784 mg/g for 3, and 6 g respectively in the mini column and 1.1636 mg/g for 38.5 g in the Ace column. In the theoretical work, Thomas, Adams-Bohart, and Yoon-Nelson models were constructed to describe a breakthrough curve of the adsorption process and find the constants of the above-mentioned models. In the regeneration tests, 5% hydrochloric acid, HCl (v/v) and 10% sodium hydroxide, NaOH (w/v) were used to regenerate the LEWATIT resin and AZLB-Na zeolite with 44 and 63.8% recovery, respectively. In conclusion, continuous flow adsorption using a LEWATIT ion exchange resin and an AZLB-Na zeolite is efficient when using a co-flow technique for removal of the ammonia from wastewater. Thomas, Adams-Bohart, and Yoon-Nelson models satisfactorily fit the data with R2 closer to 1 in all cases.
In this work, a new composite adsorbent based on a mesoporous silica SBA-15 with platelet morphology and tin salt of tungstomolybdophosphoric (TWMP) acid was synthesized and applied for uranium adsorption from aqueous solution. The sample was characterized by X-ray diffraction, Fourier transfer infra-red, and N2 adsorption-desorption analysis, and then, effect of various parameters such as concentration of metal ions and contact time on adsorption behavior was examined. The experimental result showed that the adsorption process was explained by the Langmuir isotherm model very well, and predominant reaction mechanism is physisorption. Kinetic data of adsorption suggest that the adsorption process can be described by the pseudo second-order reaction rate model.
Activated carbon DSAC36-24 iy is adsorbent materials, characterized by a specific surface area of 548.13 m²g⁻¹. Their manufacture uses the natural raw materials like the nucleus of dates. In this study the treatment is done in two stages: A chemical treatment by H3PO4 followed by a physical treatment under nitrogen for 1 hour then under stream of CO2 for 24 hours. A characterization of the various parameters was determined such as the measurement of the specific surface area, determination of pHPZC, bulk density, iodine value. The study of the adsorption of organic molecules (hydroquinone, paranitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) indicates that the adsorption phenomena are essentially due to the van der Waals interaction. In the case of organic molecules carrying the polar substituents, the existence of hydrogen bonds is also proved by the donor-acceptor forces. The study of the pH effect was done with modeling by different models (Langmuir, Freundlich, Langmuir-Freundlich, Redlich-Peterson), a kinetic treatment is also followed by the application of Lagergren, Weber, Macky.
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.
Periodic DFT calculations were performed to study the chemistry of CsI particles and the possible release of volatile iodine from CsI surfaces for nuclear safety interest. The results show that water adsorbs at low temperature associatively on the (011) surface of CsI, while water desorbs at higher temperatures. On the other hand, removing iodine species from the surface requires oxidizing the surface one time for each removed iodide atom. The activation energy of removing I2 from the surface in the presence of two OH is 1,2 eV.
The objective of this study was to investigate the removal of two organic pollutants; 4-hydroxybenzoic acid (p-hydroxybenzoic acid) and phenol from synthetic wastewater by the adsorption on mesoporous materials. In this context, the aim of this work is to study the adsorption of organic compounds phenol and 4AHB on MCM-41 and FSM-16 non-grafted (NG) and other grafted (G) by trimethylchlorosilane (TMCS). The results of phenol and 4AHB adsorption in aqueous solution show that the adsorption capacity tends to increase after grafting in relation to the increase in hydrophobicity. The materials are distinguished by a higher adsorption capacity to the other NG materials. The difference in the phenol is 14.43% (MCM-41), 14.55% (FSM-16), and 16.72% (MCM-41), 13.57% (FSM-16) in the 4AHB. Our adsorption results show that the grafted materials by TMCS are good adsorbent at 25 °C.