Search results for: surfactants adsorption

Authors: Tanghourte Mohamed, Ouassou Nazih, El Mesky Mohammed, Znini Mohamed, Mabrouk El Houssine

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In the present study, a distinct organic inhibitor, namely 2,2'-(piperazine-1,4-diyl)bis(N-(4-bromophenyl)acetamide) (PBRA), was synthesized and characterized using ¹H, ¹³C NMR, and IR spectroscopy. Subsequently, the inhibition effect of PBRA on the corrosion of carbon steel in 1 M HCl was studied using electrochemical measurements such as potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS). The results showed that the inhibition efficiency increased with concentration, reaching 87% at 10-³M. Furthermore, PBRA remained effective at temperatures ranging from 298 to 328 K. The adsorption of the inhibitor onto carbon steel was well described by the Langmuir adsorption isotherm. Additionally, a correlation between the molecular structure and quantum chemistry indices was established using density functional theory (DFT).

Keywords: synthesis, corrosion, inhibition, piperazine, efficacy, isotherm, acetamide

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Authors: Othman M. Hakami, Abdul Jabbar Al-Rajab

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Occurrence of heavy metals in water resources increased in the recent years albeit at low concentrations. Lead (PbII) is among the most important inorganic pollutants in ground and surface water. However, removal of this toxic metal efficiently from water is of public and scientific concern. In this study, we developed a rapid and efficient removal method of lead from water using chitosan/magnetite nanoparticles. A simple and effective process has been used to prepare chitosan/magnetite nanoparticles (NPs) (CS/Mag NPs) with effect on saturation magnetization value; the particles were strongly responsive to an external magnetic field making separation from solution possible in less than 2 minutes using a permanent magnet and the total Fe in solution was below the detection limit of ICP-OES (<0.19 mg L-1). The hydrodynamic particle size distribution increased from an average diameter of ~60 nm for Fe3O4 NPs to ~75 nm after chitosan coating. The feasibility of the prepared NPs for the adsorption and desorption of Pb(II) from water were evaluated using Chitosan/Magnetite NPs which showed a high removal efficiency for Pb(II) uptake, with 90% of Pb(II) removed during the first 5 minutes and equilibrium in less than 10 minutes. Maximum adsorption capacities for Pb(II) occurred at pH 6.0 and under room temperature were as high as 85.5 mg g-1, according to Langmuir isotherm model. Desorption of adsorbed Pb on CS/Mag NPs was evaluated using deionized water at different pH values ranged from 1 to 7 which was an effective eluent and did not result the destruction of NPs, then, they could subsequently be reused without any loss of their activity in further adsorption tests. Overall, our results showed the high efficiency of chitosan/magnetite nanoparticles (NPs) in lead removal from water in controlled conditions, and further studies should be realized in real field conditions.

Keywords: chitosan, magnetite, water, treatment

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Authors: K. Sivasubramanin, S. Mahimairaja, S. Pavithrapriya

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Heavy metal pollution originating from industrial wastes is becoming a serious problem in many urban environments. These heavy metals, if not properly managed, could enter into the food chain and cause a serious health hazards in animals and humans. Industrial wastes, sewage sludge, and automobile emissions also contribute to heavy metal like Pb pollution in the urban environment. However, information is scarce on the heavy metal pollution in Coimbatore urban environment. Therefore, the current study was carried out to examine the extent of lead pollution in Coimbatore urban environment the maximum Pb concentration in Coimbatore urban environment was found in ukkadam, whose concentration in soils 352 mg kg-1. In many places, the Pb concentration was found exceeded the permissible limit of 100 mg kg-1. In laboratory, closed incubation experiment showed that the concentration of different species of Pb viz., water soluble Pb(H2O-Pb), exchangeable Pb(KNO3-Pb), organic-Pb(NaOH-Pb), and organic plus metal (Fe & Al) oxides bound-Pb(Na2 EDTA-Pb) was found significantly increased during the 15 days incubation, mainly due to biotransformation processes. Both the moisture content of soil and ambient temperature exerted a profound influence on the transformation of Pb. The results of a batch experiment has shown that the sorption data was adequately described by the Freundlich equation as indicated by the high correlation coefficients (R2= 0.64) than the Langmuir equation (R2 = 0.33). A maximum of 86 mg of Pb was found adsorbed per kilogram of soil. Consistently, a soil column experiment result had shown that only a small amount of Pb( < 1.0 µg g-1 soil) alone was found leached from the soil. This might be due to greater potential of the soil towards Pb adsorption.

Keywords: lead pollution, adsorption, transformation, heavy metal pollution

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Authors: Sabiha Chouchane, Toufik Chouchane, Azzedine Hani

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

Keywords: adsorption, diatomite, crIII, wastewater

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Authors: Virginia Martin Torrejon, Song Hang

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Gelatine foams are widely explored materials due to their biodegradability, biocompatibility, and availability. They exhibit outstanding properties and are currently subject to increasing scientific research due to their potential use in different applications, such as biocompatible cellular materials for biomedical products or biofoams as an alternative to fossil-fuel-derived packaging. Gelatine is a highly surface-active polymer, and its concentrated solutions usually do not require surfactants to achieve low surface tension. Still, anionic surfactants like sodium dodecyl sulfate (SDS) strongly interact with gelatine, impacting its viscosity and rheological properties and, in turn, their foaming behaviour. Foaming behaviour is a key parameter for cellular solids produced by mechanical foaming as it has a significant effect on the processing and properties of cellular materials. Foamability mainly impacts the density and the mechanical properties of the foams, while foam stability is crucial to achieving foams with low shrinkage and desirable pore morphology. This work aimed to investigate the influence of SDS on the foaming behaviour of concentrated gelatine foams by using a dynamic foam analyser. The study of maximum foam height created, foam formation behaviour, drainage behaviour, and foam structure with regard to bubble size and distribution were carried out in 10 wt% gelatine solutions prepared at different SDS/gelatine concentration ratios. Comparative rheological and viscometry measurements provided a good correlation with the data from the dynamic foam analyser measurements. SDS incorporation at optimum dosages and gelatine gelation led to highly stable foams at high expansion ratios. The viscosity increase of the hydrogel solution at SDS content increased was a key parameter for foam stabilization. In addition, the impact of SDS content on gelling time and gel strength also considerably impacted the foams' stability and pore structure.

Keywords: dynamic foam analyser, gelatine foams stability and foamability, gelatine-surfactant foams, gelatine-SDS rheology, gelatine-SDS viscosity

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Authors: Fidelis Chigondo

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This study focuses on investigating the effectiveness of watermelon rind in phenol removal from aqueous solution. The effects of various parameters (pH, initial phenol concentration, biosorbent dosage and contact time) on phenol adsorption were investigated. The pH of 2, initial phenol concentration of 40 ppm, the biosorbent dosage of 0.6 g and contact time of 6 h also deduced to be the optimum conditions for the adsorption process. The maximum phenol removal under optimized conditions was 85%. The sorption data fitted to the Freundlich isotherm with a regression coefficient of 0.9824. The kinetics was best described by the intraparticle diffusion model and Elovich Equation with regression coefficients of 1 and 0.8461 respectively showing that the reaction is chemisorption on a heterogeneous surface and the intraparticle diffusion rate only is the rate determining step. The study revealed that watermelon rind has a potential of removing phenol from industrial wastewaters.

Keywords: biosorption, phenol, biosorbent, watermelon rind

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Authors: Jyh-Cherng Chen, Yi-Jie Lin

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This study tries to reuse the fly ash of municipal solid waste incinerator (MSWI) for the synthesis of zeolites. The fly ashes were treated with NaOH alkali fusion at different temperatures for 40 mins and then synthesized the zeolites with hydrothermal method at 105oC for different operation times. The effects of different operation conditions and the optimum synthesis parameters were explored. The specific surface area, surface morphology, species identification, adsorption capacity, and the reuse potentials of the synthesized zeolites were analyzed and evaluated. Experimental results showed that the optimum operation conditions for the synthesis of zeolite from the mixed fly ash were Si/Al=20, alkali/ash=1.5, alkali fusion reaction with NaOH at 800oC for 40 mins, hydrolysis with L/S=200 at 105oC for 24 hr, and hydrothermal synthesis at 105oC for 48 hr. The largest specific surface area of synthesized zeolite could be increased to 943.05m2/g. The influence of different operation parameters on the synthesis of zeolite from mixed fly ash followed the sequence of Si/Al > hydrolysis L/S> hydrothermal time > alkali fusion temperature > alkali/ash ratio. The XRD patterns of synthesized zeolites were identified to be similar with the ZSM-23 zeolite. The adsorption capacities of synthesized zeolite for pollutants were increased as rising the specific surface area of synthesized zeolite. In summary, MSWI fly ash can be treated and reused to synthesize the zeolite with high specific surface area by the alkali fusion and hydrothermal method. The zeolite can be reuse for the adsorption of various pollutants. They have great potential for development.

Keywords: alkali fusion, hydrothermal, fly ash, zeolite

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Authors: Katya Milenova, Penko Nikolov, Irina Stambolova, Plamen Nikolov, Vladimir Blaskov

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In the recent article, a comparison was made between Cu and TiO2 supported catalysts on activated carbon for ozone decomposition reaction. The activated carbon support in the case of TiO2/AC sample was prepared by physicochemical pyrolysis and for Cu/AC samples the supports are chemically modified carbons. The prepared catalysts were synthesized by impregnation method. The samples were annealed in two different regimes-in air and under vacuum. To examine adsorption efficiency of the samples BET method was used. All investigated catalysts supported on chemically modified carbons have higher specific surface area compared to the specific surface area of TiO2 supported catalysts, varying in the range 590÷620 m2/g. The method of synthesis of the precursors had influenced catalytic activity.

Keywords: activated carbon, adsorption, copper, ozone decomposition, TiO2

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Authors: Angel Villabona-Ortíz, Candelaria Tejada-Tovar, Andrea Viera-Devoz

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Wastewater treatment is an issue of vital importance in these times where the impacts of human activities are most evident, which have become essential tasks for the normal functioning of society. However, they put entire ecosystems at risk by time destroying the possibility of sustainable development. Various conventional technologies are used to remove pollutants from water. Agroindustrial waste is the product with the potential to be used as a renewable raw material for the production of energy and chemical products, and their use is beneficial since products with added value are generated from materials that were not used before. Considering the benefits that the use of residual biomass brings, this project proposes the use of agro-industrial residues from corn crops for the production of natural adsorbents whose purpose is aimed at the remediation of contaminated water bodies with large loads of nutrients. The adsorption capacity of two biomaterials obtained from the processing of corn stalks was evaluated by batch system tests. Biochar impregnated with sulfuric acid and thermally activated was synthesized. On the other hand, the cellulose was extracted from the corn stalks and chemically modified with cetyltrimethylammonium chloride in order to quaternize the surface of the adsorbent. The adsorbents obtained were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), infrared spectrometry with Fourier Transform (FTIR), analysis by Brunauer, Emmett and Teller method (BET) and X-ray Diffraction analysis ( XRD), which showed favorable characteristics for the cellulose extraction process. Higher adsorption capacities of the nutrients were obtained with the use of biochar, with phosphate being the anion with the best removal percentages. The effect of the initial adsorbate concentration was evaluated, with which it was shown that the Freundlich isotherm better describes the adsorption process in most systems. The adsorbent-phosphate / nitrate systems fit better to the Pseudo Primer Order kinetic model, while the adsorbent-sulfate systems showed a better fit to the Pseudo second-order model, which indicates that there are both physical and chemical interactions in the process. Multicomponent adsorption tests revealed that phosphate anions have a higher affinity for both adsorbents. On the other hand, the thermodynamic parameters standard enthalpy (ΔH °) and standard entropy (ΔS °) with negative results indicate the exothermic nature of the process, whereas the ascending values of standard Gibbs free energy (ΔG °). The adsorption process of anions with biocarbon and modified cellulose is spontaneous and exothermic. The use of the evaluated biomateriles is recommended for the treatment of industrial effluents contaminated with sulfate, nitrate and phosphate anions.

Keywords: adsorption, biochar, modified cellulose, corn stalks

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Authors: Jessica Carolina Hernandez Galeano, Juan Carlos Moreno Pirajan, Liliana Giraldo

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Carbon gels are materials whose structure and porous texture can be designed and controlled on a nanoscale. Among their characteristics it is found their low density, large surface area and high degree of porosity. These materials are produced by a sol-gel polymerization of organic monomers using basic or acid catalysts, followed by drying and controlled carbonization. In this work, the synthesis and characterization of carbon aerogels from resorcinol, phenol and formaldehyde in ethanol is described. The aim of this study is obtaining different carbonaceous materials in the form of spheres using the Stöber method to perform a further evaluation of CO₂ adsorption of each material. In general, the synthesis consisted of a sol-gel polymerization process that generates a cluster (cross-linked organic monomers) from the precursors in the presence of NH₃ as a catalyst. This cluster was subjected to specific conditions of gelling and curing (30°C for 24 hours and 100°C for 24 hours, respectively) and CO₂ supercritical drying. Finally, the dry material was subjected to a process of carbonization or pyrolysis, in N₂ atmosphere at 350°C (1° C / min) for 2 h and 600°C (1°C / min) for 4 hours, to obtain porous solids that retain the structure initially desired. For this work, both the concentrations of the precursors and the proportion of ammonia in the medium where modify to describe the effect of the use of phenol and the amount of catalyst in the resulting material. Carbon aerogels were characterized by Scanning Electron Microscope (SEM), N₂ isotherms, infrared spectroscopy (IR) and X-ray Powder Diffraction (XRD) showing the obtention of carbon spheres in the nanometric scale with BET areas around 500 m2g-1.

Keywords: carbon aerogels, carbon spheres, CO₂ adsorption, Stöber method

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Authors: Rahul Madathiparambil Visalakshan, Alex Cavallaro, John Hayball, Krasimir Vasilev

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The role of biomaterial surface nanotopograhy on fibrinogen adsorption and unfolding, and the subsequent immune response were studied. Inconsistent topography and varying chemical functionalities along with a lack of reproducibility pose a challenge in determining the specific effects of nanotopography or chemistry on proteins and cells. It is important to have a well-defined nanotopography with a homogeneous chemistry to study the real effect of nanotopography on biological systems. Therefore, we developed a technique that can produce well-defined and highly reproducible topography to identify the role of specific roughness, size, height and density with the presence of homogeneous chemical functionality. Using plasma polymerisation of oxazoline monomers and immobilized gold nanoparticles we created surfaces with an equal number density of nanoparticles of different sizes. This surface was used to study the role of surface nanotopography and the interplay of surface chemistry on proteins and immune cells. The effect of nanotopography on fibrinogen adsorption was investigated using Quartz Cristal Microbalance with Dissipation and micro BCA. The mass of fibrinogen adsorbed on the surface increased with increasing size of nano-topography. Protein structural changes up on adsorption to the nano rough surface was studied using circular dichroism spectroscopy. Fibrinogen unfolding varied depending on the specific nanotopography of the surfaces. It was revealed that the in vitro immune response to the nanotopography surfaces changed due to this protein unfolding.

Keywords: biomaterial inflammation, protein and cell responses, protein unfolding, surface nanotopography

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Authors: M. Abouleish, R. Umer, Z. Sara

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Nitrate can cause serious environmental and human health problems. Effluent from different industries and excessive use of fertilizers have increased the level of nitrate in ground and surface water. Nitrate can convert to nitrite in the body, and as a result, can lead to Methemoglobinemia and cancer. Therefore, different organizations have set standard limits for nitrate and nitrite. The United States Environmental Protection Agency (USEPA) has set a Maximum Contaminant Level Goal (MCLG) of 10 mg N/L for nitrate and 1 mg N/L for nitrite. The removal of nitrate from water and wastewater is very important to ensure the availability of clean water. Different plant materials such as banana peel, rice hull, coconut and bamboo shells, have been studied as biosorbents for the removal of nitrates from water. The use of abundantly existing plant material as an adsorbent material and the lack of energy requirement for the adsorption process makes biosorption a sustainable approach. Therefore, in this research, the fruit of the plant was investigated for its ability to act as a biosorbent to remove the nitrate from wastewater. The effect of pH on nitrate removal was studied using both the raw and chemically activated fruit (adsorbent). Results demonstrated that the adsorbent needs to be chemically activated before usage to remove the nitrate from wastewater. pH did not have a significant effect on the adsorption process, with maximum adsorption of nitrate occurring at pH 4. SEM/EDX results demonstrated that there is no change in the surface of the adsorbent as a result of the chemical activation. Chemical activation of the adsorbent using NaOH increased the removal of nitrate by 6%; therefore, various methods of activation of the adsorbent will be investigated to increase the removal of nitrate.

Keywords: biosorption, nitrates, plant material, water, and wastewater treatment

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Authors: Jiazhen Zhou, Youcai Zhao

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Waste tea is commonly generated in certain areas of China and its utilization has drawn a lot of concern nowadays. In this paper, highly microporous and mesoporous activated carbons were produced from waste tea by physical activation in the presence of water vapor in a tubular furnace. The effect of activation temperature on yield and pore properties of produced activated carbon are studied. The yield decreased with the increase of activation temperature. According to the Nitrogen adsorption isotherms, the micropore and mesopore are both developed in the activated carbon. The specific surface area and the mesopore volume fractions of the activated carbon increased with the raise of activation temperature. The maximum specific surface area attained 756 m²/g produced at activation temperature 900°C. The results showed that the activation temperature had a significant effect on the micro and mesopore volumes as well as the specific surface area.

Keywords: activated carbon, nitrogen adsorption isotherm, physical activation, waste tea

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Authors: Rujira Jitrwung, Kuntima Krekkeitsakul, Weerawat Patthaveekongka, Chiraphat Kumpidet, Jarukit Tepkeaw, Krissana Jaikengdee, Anantachai Wannajampa

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Flue gas discharging from coal fired or gas combustion power plant contains around 12% Carbon dioxide (CO₂), 6% Oxygen (O₂), and 82% Nitrogen (N₂).CO₂ is a greenhouse gas which has been concerned to the global warming. Carbon Capture, Utilization, and Storage (CCUS) is a topic which is a tool to deal with this CO₂ realization. Flue gas is drawn down from the chimney and filtered, then it is compressed to build up the pressure until 8 bar. This compressed flue gas is sent to three stages Pressure Swing Adsorption (PSA), which is filled with activated carbon. Experiments were showed the optimum adsorption pressure at 7bar, which CO₂ can be adsorbed step by step in 1st, 2nd, and 3rd stage, obtaining CO₂ concentration 29.8, 66.4, and 96.7 %, respectively. The mixed gas concentration from the last step is composed of 96.7% CO₂,2.7% N₂, and 0.6%O₂. This mixed CO₂product gas obtained from 3 stages PSA contained high concentration CO₂, which is ready to use for methanol synthesis. The mixed CO₂ was experimented in 5 Liter/Day of methanol synthesis reactor skid by 3 step processes as followed steam reforming, reverse water gas shift, and then hydrogenation. The result showed that proportional of mixed CO₂ and CH₄ 70/30, 50/50, 30/70 % (v/v), and 10/90 yielded methanol 2.4, 4.3, 5.6, and 6.0 Liter/day and save CO₂ 40, 30, 20, and 5 % respectively. The optimum condition resulted both methanol yield and CO₂ consumption using CO₂/CH₄ ratio 43/57 % (v/v), which yielded 4.8 Liter/day methanol and save CO₂ 27% comparing with traditional methanol production from methane steam reforming (5 Liter/day)and absent CO₂ consumption.

Keywords: carbon capture utilization and storage, pressure swing adsorption, reforming, reverse water gas shift, methanol

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Authors: Elaheh Sadeh, Abdolreza Farhadian, Matvei E. Semenov, Ulukbek Zh. Mirzakimov

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Recent advancements in solidified gas technology have demonstrated substantial potential for applications in carbon capture, storage, and natural gas transportation. The key factor limiting the industrial adoption of hydrates lies in the necessity for efficient and environmentally friendly promoters. This study aims to address this issue by synthesizing two biosurfactants – sodium oleate (SO) and hydroxylated sodium oleate (HSO) – as promoters for methane hydrate formation. The unique properties of these green, bio-based surfactants can potentially optimize solidified methane storage with wide-ranging applications in energy storage and transportation. The synthesis process of these promoters is simple and easily scalable for industrial production. The utilization of water as a solvent in the process helps to mitigate environmental impacts and simplifies the scale-up procedure. High-pressure autoclave experiments revealed a significant acceleration in methane hydrate formation kinetics with minute concentrations of the biosurfactants. Remarkably, just 5 ppm of SO and HSO facilitated a maximum water-to-hydrate conversion of 90%, equating to a storage capacity of 156 v/v in distilled water. Furthermore, SO and HSO demonstrated impressive biodegradability, exceeding 60% within 28 days. Toxicity assessments confirmed the biocompatibility of these biosurfactants, with cell viability above 70% for skin and lung cells at concentrations up to 180 and 90 µg/mL, respectively. These results indicate that SO and HSO could serve as an environmentally friendly alternative to synthetic surfactants, such as SDS, for methane storage. The findings of this study have far-reaching implications for various industries and applications. These biosurfactants' efficiency in methane hydrate formation may contribute to improved seawater desalination processes and more effective carbon capture techniques, ultimately reducing greenhouse gas emissions. Moreover, their application in gas storage could revolutionize the way natural gas is transported and stored. The synthesis of effective biosurfactants like SO and HSO opens up a world of possibilities in environmental sustainability, energy efficiency, and industrial innovation.

Keywords: methane storage, solidified methane, gas hydrate, biosurfactant

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Authors: N. Hamdi, E. Srasra

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In this work geopolymer cement are synthesized from Tunisian (illito-kaolinitic) clay. This product can be used as binding material in place of cement Portland. The clay fractions used were characterized with physico-chemical and thermal analyses. The clays materials react with alkaline solution (10, 14 and 18 mol(NaOH)/L) in order to produce geopolymer cements whose pastes were characterized by determining their water adsorption and compressive strength. The compressive strength of the hardened geopolymer cement paste samples aged 28 days attained its highest value (32.3MPa) around 950°C for NaOH concentration of 14M. The water adsorption value of the prepared samples decreased with increasing the calcination temperature of clay fractions. It can be concluded that the most suitable temperature for the calcination of illitio-kaolinitic clays in view of producing geopolymer cements is around 950°C.

Keywords: compressive strength, geopolymer cement, illitio-kaolinitic clay, mineral

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Authors: S. Nigri, R. Oumeddour, F. Djazi

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The inhibition of the corrosion of copper in 1 M HNO3 solution by oleic acid was investigated by weight loss measurement, potentiodynamic polarization and scanning electron microscope (SEM) studies. The experimental results have showed that this compound revealed a good corrosion inhibition and the inhibition efficiency is increased with the inhibitor concentration to reach 98%. The results obtained revealed that the adsorption of the inhibitor molecule onto metal surface is found to obey Langmuir adsorption isotherm. The temperature effect on the corrosion behavior of copper in 1 M HNO3 without and with inhibitor at different concentration was studied in the temperature range from 303 to 333 K and the kinetic parameters activation such as Ea, ∆Ha and ∆Sa were evaluated. Tafel plot analysis revealed that oleic acid acts as a mixed type inhibitor. SEM analysis substantiated the formation of protective layer over the copper surface.

Keywords: oleic acid, weight loss, electrochemical measurement, SEM analysis

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Authors: Justine Kiiza, Xu Jiafang

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The world’s demand for energy is increasing rapidly due to population growth and a reduction in shallow conventional oil and gas reservoirs, resorting to deeper and mostly unconventional reserves like shale oil and gas. Most shale formations contain a large amount of expansive sodium montmorillonite (Na-Mnt), due to high water adsorption, hydration, and when the drilling fluid filtrate enters the formation with high Mnt content, the wellbore wall can be unstable due to hydration and swelling, resulting to shrinkage, sticking, balling, time wasting etc., and well collapse in extreme cases causing complex downhole accidents and high well costs. Recently, polyamines like 1, 6 – hexane diamine (HEDA) have been used as typical drilling fluid shale inhibitors to minimize and/or cab clay mineral swelling and maintain the wellbore stability. However, their application is limited to shallow drilling due to their sensitivity to elevated temperature and pressure. Inorganic potassium salts i.e., KCl, have long been applied for restriction of shale formation hydration expansion in deep wells, but their use is limited due to toxicity. Understanding the adsorption behaviour of HEDA on Na-Mnt surfaces in present of organo-salts, organic K-salts e.g., HCO₂K - main component of organo-salt drilling fluid, is of great significance in explaining the inhibitory performance of polyamine inhibitors. Molecular dynamic simulations (MD) were applied to investigate the influence of HCO₂K and KCl on the adsorption mechanism of HEDA on the Na-Mnt surface. Simulation results showed that adsorption configurations of HEDA are mainly by terminal amine groups with a flat-lying alkyl hydrophobic chain. Its interaction with the clay surface decreased the H-bond number between H₂O-clay and neutralized the negative charge of the Mnt surface, thus weakening the surface hydration ability of Na-Mnt. The introduction of HCO₂K greatly improved inhibition ability, coordination of interlayer ions with H₂O as they were replaced by K+, and H₂O-HCOO- coordination reduced H₂O-Mnt interactions, mobility and transport capability of H₂O molecules were more decreased. While KCl showed little ability and also caused more hydration with time, HCO₂K can be used as an alternative for offshore drilling instead of toxic KCl, with a maximum concentration noted in this study as 1.65 wt%. This study provides a theoretical elucidation for the inhibition mechanism and adsorption characteristics of HEDA inhibitor on Na-Mnt surfaces in the presence of K+-salts and may provide more insight into the evaluation, selection, and molecular design of new clay-swelling high-performance WBDF systems used in oil and gas complex offshore drilling well sections.

Keywords: shale, hydration, inhibition, polyamines, organo-salts, simulation

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Authors: Edita Baltrėnaitė, Pranas Baltrėnas, Eglė MarčIulaitienė, Mantas PranskevičIus, Valeriia Chemerys

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The growing demand for organic products in the market promotes their use in various fields. One of such products is biochar. Among the innovative environmental applications, biochar has the potential as an adsorbent for retaining contaminants in environmental engineering and agrotechnical systems. Artificial modification of biochar can improve its adsorption capacity. However, indirect/natural change of biochar composition (e.g., contaminated biomass) based on syngenetic elements provides prospects for new applications of biochar as well as decreases the modification costs. Natural lignocellulosic and biochar composition variations would lead to a new field of application of biochar and reduce resources for biochar modifications. The aim of this study was to determine the influence of syngenetic elements of biochar’s feedstock on the physicochemical properties of lignocellulosic biochar. Syngenetic elements (e.g., Zn, Cu, Ni, Pb, Mg) and other intrinsic properties (e.g., lignin, COHN, moisture, ash) of indifferent types of lignocellulosic feedstock on the physicochemical characteristics of biochar are discussed.

Keywords: adsorption, lignocellulosic biochar, instrinsic properties, syngenetic elements

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Authors: Raina J. Olsen, Andrew K. Gillespie, John W. Taylor, Cristian I. Contescu, Peter Pfeifer, James R. Morris

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While adsorbent surfaces such as graphite are known to increase the melting temperature of solid H2, this effect is normally rather small, increasing to 20 Kelvin (K) relative to 14 K in the bulk. An as-yet unidentified phase transition has been observed in a system of H2 adsorbed in a porous, locally graphitic, Saran carbon with sub-nanometer sized pores at temperatures (74-101 K) and pressures ( > 76 bar) well above the critical point of bulk H2 using hydrogen adsorption and neutron scattering experiments. Adsorption data shows a discontinuous pressure jump in the kinetics at 76 bar after nearly an hour of equilibration time, which is identified as an exothermic phase transition. This discontinuity is observed in the 87 K isotherm, but not the 77 K isotherm. At higher pressures, the measured isotherms show greater excess adsorption at 87 K than 77 K. Inelastic neutron scattering measurements also show a striking phase transition, with the amount of high angle scattering (corresponding to large momentum transfer/ large effective mass) increasing by up to a factor of 5 in the novel phase. During the course of the neutron scattering experiment, three of these reversible spectral phase transitions were observed to occur in response to only changes in sample temperature. The novel phase was observed by neutron scattering only at high H2 pressure (123 bar and 187 bar) and temperatures between 74-101 K in the sample of interest, but not at low pressure (30 bar), or in a control activated carbon at 186 bar of H2 pressure. Based on several of the more unusual observations, such as the slow equilibration and the presence of both an upper and lower temperature bound, a reasonable hypothesis is that this phase forms only in the presence of a high concentration of ortho-H2 (nuclear spin S=1). The increase in adsorption with temperature, temperatures which cross the lower temperature bound observed by neutron scattering, indicates that this novel phase is denser. Structural characterization data on the adsorbent shows that it may support a commensurate solid phase denser than those known to exist on graphite at much lower temperatures. Whatever this phase is eventually proven to be, these results show that surfaces can have a more striking effect on hydrogen phases than previously thought.

Keywords: adsorbed phases, hydrogen, neutron scattering, nuclear spin

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Authors: Hyung T. Kwak, Jun Gao, Yao An, Alfred Kleinhammes, Yue Wu

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Surface wettability is a crucial factor in oil recovery. In oil industry, the rock wettability involves the interplay between water, oil, and solid surface. Therefore, studying the interplay between adsorptions of water and hydrocarbon molecules on solid surface would be very informative for understanding rock wettability. Here we use the in-situ Nuclear Magnetic Resonance (NMR) gas isotherm technique to study competitive adsorptions of water and isopropanol, an intermediate step from hydrocarbons. This in-situ NMR technique obtains information on thermodynamic properties such as the isotherm, molecular dynamics via spin relaxation measurements, and adsorption kinetics such as how fast the system can reach thermal equilibrium after changes of vapor pressures. Using surfaces of silica glass beads, which can be modified from hydrophilic to hydrophobic, we obtained information on the influence of surface hydrophilicity on the state of surface water via obtained thermodynamic and dynamic properties.

Keywords: Wettability, NMR, Gas Isotherm, Hydrophilicity, adsorption

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Authors: Hongtao Zhu, Dezhi Sun

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Nitrogen and phosphorus are essential nutrients for biomass growth. But excessive nitrogen and phosphorus can contribute to accelerated eutrophication of lakes and rivers. Constructed wetland is an efficient and eco-friendly wastewater treatment technology with low operating cost and low-energy consumption. Because of high affinity with ammonium ion, zeolite, as a common substrate, is applied in constructed wetlands worldwide. Another substrate seen commonly for constructed wetlands is steel slag, which has high contents of Ca, Al, or Fe, and possesses a strong affinity with phosphate. Due to the excellent ammonium removal ability of zeolite and phosphate removal ability of steel slag, they were considered to be combined in the substrate bed of a constructed wetland in order to enhance the simultaneous removal efficiencies of nitrogen and phosphorus. In our early tests, zeolite and steel slag were combined with each other in order to simultaneously achieve a high removal efficiency of ammonium-nitrogen and phosphate-phosphorus. However, compared with the results when only zeolite was used, the removal efficiency of ammonia was sharply decreased when zeolite and steel slag were used together. The main objective of this study was to establish an overview of the interaction of steel slag and zeolite on ammonium nitrogen removal. The CaO dissolution from slag, as well as the effects of influencing parameters (i.e. pH and Ca2+ concentration) on the ammonium adsorption onto zeolite, was systematically studied. Modeling results of Ca2+ and OH- release from slag indicated that pseudo-second order reaction had a better fitness than pseudo-first order reaction. Changing pH value from 7 to 12 would result in a drastic reduction of the ammonium adsorption capacity on zeolite, from the peak at pH7. High Ca2+ concentration in solution could also inhibit the adsorption of ammonium onto zeolite. The mechanism for steel slag inhibiting the ammonium adsorption capacity of zeolite includes: on one hand, OH- released from steel slag can react with ammonium ions to produce molecular form ammonia (NH3∙H2O), which would cause the dissociation of NH4+ from zeolite. On the other hand, Ca2+ could replace the NH4+ ions to adhere onto the surface of zeolite. An innovative substrate filling configuration that zeolite and steel slag are placed sequentially was proposed to eliminate the disadvantageous effects of steel slag. Experimental results showed that the novel filling configuration was superior to the other two contrast filling configurations in terms of ammonium removal.

Keywords: ammonium nitrogen, constructed wetlands, steel slag, zeolite

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Authors: B. Guezzen, M. A. Didi, B. Medjahed

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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.

Keywords: adsorption, dye, factorial design, kinetic, organo-bentonite

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Authors: Dilip K. Paul

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The most popular mesoporous molecular sieves, Mobil Composition of Matter (MCM) are keenly studied by researchers because of these materials possess amorphous silica wall and have a long range of ordered framework with uniform mesopores. These materials also possess large surface area, which can be up to more than 1000 m2g−1. Herein the investigation is focused upon the synthesis and characterization of chromium and aluminum doped MCM-41 using XRD and FTIR. Acid-base properties of Cr-Al-MCM 41 was investigated by molecularly sensitive transmission FT-IR spectroscopy by adsorbing pyridine. In addition, these MCM nanomaterial was used to catalyze C-C bond formation from acetaldehyde adsorption. The assignment of all infrared peaks during adsorption of pyridine provided detail information on the presence of acid-base sites which in turn helped us to explain the roles of these in the condensation reaction of aldehyde. Reaction mechanisms of C-C bond formation is therefore explored to shed some light on this elusive reaction detail.

Keywords: mesoporous nanomaterial, MCM 41, FTIR studies, acid-base studies

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Authors: P. Gomathi Priya, M. E. Thenmozhi

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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.

Keywords: ammonium ferrous sulfate solution, barium, alginate beads, reactive black WNN dye, zero valent iron nanoparticles

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Authors: Dileep Maarisetty, Janaki Komandur, Saroj S. Baral

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In the current work, photocatalytic degradation of phenol was carried both in UV and visible light to find the slowest step that is limiting the rate of photo-degradation process. Characterization such as XRD, SEM, FT-IR, TEM, XPS, UV-DRS, PL, BET, UPS, ESR and zeta potential experiments were conducted to assess the credibility of catalysts in boosting the photocatalytic activity. To explore the synergy, TiO₂ was doped with graphene and alumina. The orbital hybridization with alumina doping (mediated by graphene) resulted in higher electron transfer from the conduction band of TiO₂ to alumina surface where oxygen reduction reactions (ORR) occur. Besides, the doping of alumina and graphene introduced defects into Ti lattice and helped in improving the adsorptive properties of modified photo-catalyst. Results showed that these defects promoted the oxygen reduction reactions (ORR) on the catalyst’s surface. ORR activity aims at producing reactive oxygen species (ROS). These ROS species oxidizes the phenol molecules which is adsorbed on the surface of photo-catalysts, thereby driving the photocatalytic reactions. Since mass transfer is considered as rate limiting step, various mathematical models were applied to the experimental data to probe the best fit. By varying the parameters, it was found that intra-particle diffusion was the slowest step in the degradation process. Lagergren model gave the best R² values indicating the nature of rate kinetics. Similarly, different adsorption isotherms were employed and realized that Langmuir isotherm suits the best with tremendous increase in uptake capacity (mg/g) of TiO₂-rGO-Al₂O₃ as compared undoped TiO₂. This further assisted in higher adsorption of phenol molecules. The results obtained from experimental, kinetic modelling and adsorption isotherms; it is concluded that apart from changes in surface, optoelectronic and morphological properties that enhanced the photocatalytic activity, the intra-particle diffusion within the catalyst’s pores serve as rate-limiting step in deciding the fate of photo-catalytic degradation of phenol.

Keywords: ORR, phenol degradation, photo-catalyst, rate kinetics

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Authors: Rahma Tibigui, Ikram Hadj Said, Rachid Belkada, Dalila Hammoutene

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The vulnerability of industrial facilities is highly concerned with multiple risks from corrosion. The commonly adopted solution is based on the use of organic inhibitors, which are gradually being replaced by environmentally friendly organic inhibitors. In our work, we carried out a quantum chemical study based on the Density Functional Theory (DFT) method at the B3LYP/6-311G (d,p) level of theory. The inhibitory performance of a derivative of the tetrazole molecule has been investigated and reported as a carbon steel-friendly corrosion inhibitor in hydrochloric acid (HCl) medium. The relationship is likely to exist between the molecular structure of this compound as well as its various global reactivity descriptors, and its corrosion inhibition efficiency, which was examined and then discussed. The results show low values of ΔE, which represent strong adsorption of the inhibitor on the steel surface. Moreover, the flat adsorption orientation confirmed the great ability to donate (accept) electrons to (from) steel, fabricating an anchored barrier to prevent steel from corrosion.

Keywords: eco-friendly, corrosion inhibitors, tetrazole, DFT

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Authors: Sneha Singh, Abhimanyu Dev, Vinod Nigam

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The major issue which decides the impending use of gold nanoparticles (AuNPs) in nanobiotechnological applications is their particle size and stability. Often the AuNPs obtained biomimetically are considered useless owing to their instability in the aqueous medium and thereby limiting the widespread acceptance of this facile green synthesis procedure. So, the use of nontoxic surfactants is warranted to stabilize the biogenic nanoparticles (NPs). But does the surfactant only play a role in stabilizing by being adsorbed to the NPs surface or can it have any other significant contribution in synthesis process and controlling their size as well as shape? Keeping this idea in mind, AuNPs were synthesized by using surfactant treated (lechate) and untreated (cell lysate supernatant) Bacillus licheniformis cell extract. The cell extracts mediated reduction of chloroauric acid (HAuCl 4) in the presence of non-ionic surfactant, Tween 20 (TW20), and its effect on the AuNPs stability was studied. Interestingly, the surfactant used in the study served as potential alternative to harvest cellular enzymes involved in bioreduction process in a hassle free condition. The surfactants ability to solubilize/leach membrane proteins and simultaneously stabilizing the AuNPs could have advantage from process point of view as it will reduce the time and economics involve in the nanofabrication of biogenic NPs. The synthesis was substantiated with UV-Vis spectroscopy, Dynamic light scattering study, FTIR spectroscopy, and Transmission electron microscopy. The Zeta potential of AuNPs solutions was measured routinely to corroborate the stability observations recorded visually. Highly stable, ultra-small AuNPs of 2.6 nm size were obtained from the study. Further, the biological efficacy of the obtained AuNPs as potential antibacterial agent was evaluated against Bacilllus subtilis, Pseudomonas aeruginosa, and Escherichia coli by observing the zone of inhibition. This potential of AuNPs of size < 3 nm as antibacterial agent could pave way for development of new antimicrobials and overcoming the problems of antibiotics resistance

Keywords: antibacterial, bioreduction, nanoparticles, surfactant

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Authors: Rong Sun, Laihong Shen

Abstract:

La-based perovskite oxygen carriers, especially the doped-La(M)FeO₃, showed excellent performances during chemical looping processes. However, the mechanisms of the undoped and doped La(M)FeO₃ are not clear at present, making the mechanisms clear may help the development of chemical looping technologies. In this paper, the method based on the density function theory (DFT) was used to analysis the influence of Ca, Sr, and Ba doping of La on the electronic structure, while the CO oxidation mechanisms on the surface of LaFeO₃ and Ca-doped LaFeO₃ oxygen carriers were also analyzed. The results showed that the band gap was decreased by the doping of low valence. While the doping of low valence element Ca, Sr, and Ba at La site simultaneously resulted to the moving of the valence band toward high energy and made the valence band cross the Fermi energy level. This was resulted from the holes generated by divalent ion substitution. The holes can change the total magnetization from antiferromagnet to weakly ferromagnetism. The calculation results about the formation of oxygen vacancy showed that substitutions of Ca, Sr, and Ba caused a large drop in oxygen vacancy formation energy, indicating that the bulk oxygen transport was improved. Based on the optimized bulk of the undoped and Ca-doped LaFeO₃(010) surface, the CO adsorption was analyzed. The results indicated that the adsorption energy increased by divalent ion substitution, meaning that the adsorption stability decreased. The results can provide a certain theoretical basis for the development of perovskite oxides in chemical looping technologies.

Keywords: chemical looping technologies, lanthanum ferrate (LaFeO₃), divalent ion substitution, CO oxidation

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Authors: Zhandos Tauanov, Dhawal Shah, Grigorios Itskos, Vasileios Inglezakis

Abstract:

Removal of mercury (II) from aqueous phase is of utmost importance, as it is highly toxic and hazardous to the environment and human health. One way of removal of mercury (II) ions from aqueous solutions is by using adsorbents derived from coal fly ash (CFA), such as synthetic zeolites. In this work, we present the hydrothermal production of synthetic zeolites from CFA with conversion rate of 75%. In order to produce silver containing nanocomposites, synthetic zeolites are subsequently impregnated with various amounts of silver nanoparticles, from 0.2 to 2wt.%. All produced zeolites and parent materials are characterized by XRD, XRF, BET, SEM, and TEM to obtain morphological and microstructural data. Moreover, mercury (II) ions removal from aqueous solutions with initial concentration of 10 ppm is studied. According to results, zeolites and Ag-nanocomposites demonstrate much higher removal than parent CFA (up to 98%). In addition to this, we could observe a distinct adsorption behavior depending on the loading of Ag NPs in nanocomposites. A possible reaction mechanism for both zeolites and Ag-nanocomposites is discussed.

Keywords: coal fly ash, mercury (II) removal, nanocomposites, silver nanoparticles, synthetic zeolite

Procedia PDF Downloads 277