Search results for: exothermic
51 Influence of Silica Fume on the Hydration of Cement Pastes Studied by Simultaneous TG-DSC Analysis
Authors: Anton Trník, Lenka Scheinherrová, Robert Černý
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Silica fume is a by-product of the ferro-silicon and silicon metal industries. It is mainly in the form of amorphous silica. Silica fume belongs to pozzolanic active materials which can be used in concrete to improve its final properties. In this paper, the influence of silica fume on hydration of cement pastes is studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) at various curing times (2, 7, 28, and 90 days) in the temperature range from 25 to 1000 °C in an argon atmosphere. Samples are prepared from Portland cement CEM I 42.5 R which is partially replaced with the silica fume of 4, 8, and 12 wt.%. The water/binder ratio is chosen as 0.5. It is identified and described the liberation of physically bound water, calcium–silicate–hydrates dehydration, portlandite and calcite decomposition in studied samples. Also, it is found out that an exothermic peak at 950 °C is observed without a significant mass change for samples with 12 wt.% of silica fume after two days of hydration. This peak is probably caused by the pozzolanic reaction between silica fume and Portland cement. Its size corresponds to the degree of crystallization between Ca and Si. The portlandite content is lower for the samples with a higher amount of silica fume.Keywords: differential scanning calorimetry, hydration, silica fume, thermogravimetry
Procedia PDF Downloads 24050 Theoretical Analysis and Numerical Evaluation of the Flow inside the Supersonic Nozzle for Chemical Lasers
Authors: Mohammedi Ferhate, Hakim Chadli, Laggoun Chaouki
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The main objectives of work in this area are, first, obtaining the high laser energies in short time durations needed for the feasibility studies of laser induced thermodynamically exothermic chemical reactions , second, investigating the physical principles that can be used to make laser sources capable of delivering high average powers. We note that, in order to reach both objectives, one has to convert electrical or chemical energy into laser energy, using dense gaseous media.. We present results from the early development of an F atom source appropriate for HF and DF chemical laser research. We next explain the very important difficulties encountered in working with dense gases for that purpose, and we shall describe how, especially at Evaluation of downstream-mixing scheme –levels transitions (001) → (100) and (001) → (020) gas dynamic laser The physical phenomena that control the operation of presently existing laser devices are now sufficiently well understood, so that it is possible to predict that new generations of lasers could be designed in the future. The proposed model of excitation and relaxation levels was finally proved by the computational numerical code of Matlab toolboxes of different parameters of nozzle.Keywords: hydrogen, combust, chemical laser, halogen atom
Procedia PDF Downloads 8549 Recovery of Hydrogen Converter Efficiency Affected by Poisoning of Catalyst with Increasing of Temperature
Authors: Enayat Enayati, Reza Behtash
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The purpose of the H2 removal system is to reduce a content of hydrogen and other combustibles in the CO2 feed owing to avoid developing a possible explosive condition in the synthesis. In order to reduce the possibility of forming an explosive gas mixture in the synthesis as much as possible, the hydrogen percent in the fresh CO2, will be removed in hydrogen converter. Therefore the partly compressed CO2/Air mixture is led through Hydrogen converter (Reactor) where the H2, present in the CO2, is reduced by catalytic combustion to values less than 50 ppm (vol). According the following exothermic chemical reaction: 2H2 + O2 → 2H2O + Heat. The catalyst in hydrogen converter consist of platinum on a aluminum oxide carrier. Low catalyst activity maybe due to catalyst poisoning. This will result in an increase of the hydrogen content in the CO2 to the synthesis. It is advised to shut down the plant when the outlet of hydrogen converter increased above 100 ppm, to prevent undesirable gas composition in the plant. Replacement of catalyst will be time exhausting and costly so as to prevent this, we increase the inlet temperature of hydrogen converter according to following Arrhenius' equation: K=K0e (-E_a/RT) K is rate constant of a chemical reaction where K0 is the pre-exponential factor, E_a is the activation energy, and R is the universal gas constant. Increment of inlet temperature of hydrogen converter caused to increase the rate constant of chemical reaction and so declining the amount of hydrogen from 125 ppm to 70 ppm.Keywords: catalyst, converter, poisoning, temperature
Procedia PDF Downloads 82148 Enhanced Biosorption of Copper Ions by Luffa Cylindrica: Biosorbent Characterization and Batch Experiments
Authors: Nouacer Imane, Benalia Mokhtar, Djedid Mabrouk
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The adsorption ability of a powdered activated carbons (PAC) derived from Luffa cylindrica investigated in an attempt to produce more economic and effective sorbents for the control of Cu(II) ion from industrial liquid streams. Carbonaceous sorbents derived from local luffa cylindrica, were prepared by chemical activation methods using ZnCl2 as activating reagents. Adsorption of Cu (II) from aqueous solutions was investigated. The effects of pH, initial adsorbent concentration, the effect of particle size, initial metal ion concentration and temperature were studied in batch experiments. The maximum adsorption capacity of copper onto grafted Luffa cylindrica fiber was found to be 14.23 mg/g with best fit for Langmuir adsorption isotherm. The values of thermodynamic parameters such as enthalpy change, ∆H (-0.823 kJ/mol), entropy change, ∆S (-9.35 J/molK) and free energy change, ∆G (−1.56 kJ/mol) were also calculated. Adsorption process was found spontaneous and exothermic in nature. Finally, the luffa cylindrica has been evaluated by FTIR, MO and x-ray diffraction in order to determine if the biosorption process modifies its chemical structure and morphology, respectively. Luffa cylindrica has been proven to be an efficient biomaterial useful for heavy metal separation purposes that is not altered by the process.Keywords: adsorption, cadmium, isotherms, thermodynamic, luffa sponge
Procedia PDF Downloads 24947 Removal of Pb(II) Ions from Wastewater Using Magnetic Chitosan–Ethylene Glycol Diglycidyl Ether Beads as Adsorbent
Authors: Pyar Singh Jassal, Priti Rani, Rajni Johar
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The adsorption of Pb(II) ions from wastewater using ethylene glycol diglycidyl ether cross-linked magnetic chitosan beads (EGDE-MCB) was carried out by considering a number of parameters. The removal efficiency of the metal ion by magnetic chitosan beads (MCB) and its cross-linked derivatives depended on viz contact time, dose of the adsorbent, pH, temperature, etc. The concentration of Cd( II) at different time intervals was estimated by differential pulse anodic stripping voltammetry (DPSAV) using 797 voltametric analyzer computrace. The adsorption data could be well interpreted by Langmuir and Freundlich adsorption model. The equilibrium parameter, RL values, support that the adsorption (046 Reaction Kinetics for the Pyrolysis of Urea Phosphate
Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus
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The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate
Procedia PDF Downloads 15745 Experimental Study on the Effect of Storage Conditions on Thermal Hazard of Nitrocellulose
Authors: Hua Chai, Qiangling Duan, Huiqi Cao, Mi Li, Jinhua Sun
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Nitrocellulose (NC), a kind of energetic material, has been widely used in the industrial and military fields. However, this material can also cause serious social disasters due to storage conditions. Thermal hazard of nitrocellulose (NC) was experimentally investigated using the CALVET heat flux calorimeter C80, and three kinds of storage conditions were considered in the experiments: (1) drying time, (2) moisture content, (3) cycles. The results showed that the heat flow curves of NC moved to the low-temperature direction firstly and then slightly moved back by increasing the drying hours. Moisture that was responsible for the appearance of small exothermic peaks was proven to be the unfavorable safety factor yet it could increase the onset temperature of the main peak to some extent. And cycles could both lower the onset temperature and the maximum heat flow but enlarged the peak temperature. Besides, relevant kinetic parameters such as the heat of reaction (ΔH) and the activation energy (Ea) were obtained and compared. It was found that all the three conditions could reduce the values of Ea and most of them produced larger reaction heat. In addition, the critical explosion temperature (Tb) of the NC samples were derived. It was clear that not only the drying time but also the cycles would increase the thermal hazard of the NC. Yet, the right amount of water helped to reduce the thermal hazard.Keywords: C80, nitrocellulose, storage conditions, the critical explosion temperature, thermal hazard
Procedia PDF Downloads 16544 Removal of Basic Yellow 28 Dye from Aqueous Solutions Using Plastic Wastes
Authors: Nadjib Dahdouh, Samira Amokrane, Elhadj Mekatel, Djamel Nibou
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The removal of Basic Yellow 28 (BY28) from aqueous solutions by plastic wastes PMMA was investigated. The characteristics of plastic wastes PMMA were determined by SEM, FTIR and chemical composition analysis. The effects of solution pH, initial Basic Yellow 28 (BY28) concentration C, solid/liquid ratio R, and temperature T were studied in batch experiments. The Freundlich and the Langmuir models have been applied to the adsorption process, and it was found that the equilibrium followed well Langmuir adsorption isotherm. A comparison of kinetic models applied to the adsorption of BY28 on the PMMA was evaluated for the pseudo-first-order and the pseudo-second-order kinetic models. It was found that used models were correlated with the experimental data. Intraparticle diffusion model was also used in these experiments. The thermodynamic parameters namely the enthalpy ∆H°, entropy ∆S° and free energy ∆G° of adsorption of BY28 on PMMA were determined. From the obtained results, the negative values of Gibbs free energy ∆G° indicated the spontaneity of the adsorption of BY28 by PMMA. The negative values of ∆H° revealed the exothermic nature of the process and the negative values of ∆S° suggest the stability of BY28 on the surface of SW PMMA.Keywords: removal, Waste PMMA, BY28 dye, equilibrium, kinetic study, thermodynamic study
Procedia PDF Downloads 15543 Generation of Catalytic Films of Zeolite Y and ZSM-5 on FeCrAlloy Metal
Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth
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This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 µm) and structured US–Y catalyst film (Si/Al = 8, thickness 23µm) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550°C). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.Keywords: FeCrAlloy, structured catalyst, zeolite Y, zeolite ZSM-5
Procedia PDF Downloads 38142 Effect of Maize Straw-Derived Biochar on Imidacloprid Adsorption onto Soils Prior to No-Tillage and Rotary Tillage Practices
Authors: Jean Yves Uwamungu, Fiston Bizimana, Chunsheng Hu
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Although pesticides are used in crop productivity, their use is highly harming the soil environment, and measures must be taken in the future to eradicate soil and groundwater pollution. The primary aim was to determine the effect of biochar addition on the imidacloprid adsorption on soil prior to no-tillage (NT) and rotational tillage (RT) conditions. In the laboratory, batch tests were conducted to determine the imidacloprid adsorption on soil using equilibrium and kinetic modelling with the addition of biochar. The clay level of the soil was found to be more significant when no-tillage was applied (22.42) than when rotational tillage was applied (14.27). The imidacloprid adsorption equilibrium was significantly shortened to 25 min after biochar addition. The isotherms and kinetic findings confirmed that the adsorption occurred according to Freundlich and pseudo-second-order kinetic models, respectively. The adsorption capacity of imidacloprid (40<35<25 °C) increased with decreasing temperature, indicating an exothermic adsorption behaviour, whereas negative Gibbs free energy (G) values of -6980.5 and 5983.93 Jmol-1, respectively, for soil prior to NT and RT at 25 °C, asserted spontaneous adsorption. The negative values of entropy (ΔS); -22.83 and -38.15 Jmol-1K-1, prior to NT and RT applications, respectively, described a lowered randomness process. The enthalpy was greater when RT was applied (-17533 J mol-1) than when NT was applied (-450 J mol-1). Lastly, it was shown that NTtreatment enhanced imidacloprid adsorption capacity more than RT treatment and that biochar addition enhanced pesticide adsorption in both treatments.Keywords: adsorption, biochar, imidacloprid, soil, tillage
Procedia PDF Downloads 15041 Kinetics, Equilibrium and Thermodynamic Studies on Adsorption of Reactive Blue 29 from Aqueous Solution Using Activated Tamarind Kernel Powder
Authors: E. D. Paul, A. D. Adams, O. Sunmonu, U. S. Ishiaku
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Activated tamarind kernel powder (ATKP) was prepared from tamarind fruit (Tamarindus indica), and utilized for the removal of Reactive Blue 29 (RB29) from its aqueous solution. The powder was activated using 4N nitric acid (HNO₃). The adsorbent was characterised using infrared spectroscopy, bulk density, ash content, pH, moisture content and dry matter content measurements. The effect of various parameters which include; temperature, pH, adsorbent dosage, ion concentration, and contact time were studied. Four different equilibrium isotherm models were tested on the experimental data, but the Temkin isotherm model was best-fitted into the experimental data. The pseudo-first order and pseudo-second-order kinetic models were also fitted into the graphs, but pseudo-second order was best fitted to the experimental data. The thermodynamic parameters showed that the adsorption of Reactive Blue 29 onto activated tamarind kernel powder is a physical process, feasible and spontaneous, exothermic in nature and there is decreased randomness at the solid/solution interphase during the adsorption process. Therefore, activated tamarind kernel powder has proven to be a very good adsorbent for the removal of Reactive Blue 29 dyes from industrial waste water.Keywords: tamarind kernel powder, reactive blue 29, isotherms, kinetics
Procedia PDF Downloads 24940 Heat Transfer and Entropy Generation in a Partial Porous Channel Using LTNE and Exothermicity/Endothermicity Features
Authors: Mohsen Torabi, Nader Karimi, Kaili Zhang
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This work aims to provide a comprehensive study on the heat transfer and entropy generation rates of a horizontal channel partially filled with a porous medium which experiences internal heat generation or consumption due to exothermic or endothermic chemical reaction. The focus has been given to the local thermal non-equilibrium (LTNE) model. The LTNE approach helps us to deliver more accurate data regarding temperature distribution within the system and accordingly to provide more accurate Nusselt number and entropy generation rates. Darcy-Brinkman model is used for the momentum equations, and constant heat flux is assumed for boundary conditions for both upper and lower surfaces. Analytical solutions have been provided for both velocity and temperature fields. By incorporating the investigated velocity and temperature formulas into the provided fundamental equations for the entropy generation, both local and total entropy generation rates are plotted for a number of cases. Bifurcation phenomena regarding temperature distribution and interface heat flux ratio are observed. It has been found that the exothermicity or endothermicity characteristic of the channel does have a considerable impact on the temperature fields and entropy generation rates.Keywords: entropy generation, exothermicity or endothermicity, forced convection, local thermal non-equilibrium, analytical modelling
Procedia PDF Downloads 41639 Orange Peel Derived Activated Carbon /Chitosan Composite as Highly Effective and Low-Cost Adsorbent for Adsorption of Methylene Blue
Authors: Onur Karaman, Ceren Karaman
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In this study, the adsorption of Methylene Blue (MB), a cationic dye, onto Orange Peel Derived Activated Carbon (OPAC) and chitosan(OPAC/Chitosan composite) composite (a low-cost absorbent) was carried out using a batch system. The composite was characterised using IR spectra, XRD, FESEM and Pore size studies. The effects of initial pH, adsorbent dose rate and initial dye concentration on the initial adsorption rate, capacity and dye removal efficiency were investigated. The Langmuir and Freundlich adsorption models were used to define the adsorption equilibrium of dye-adsorbent system mathematically and it was decided that the Langmuir model was more suitable to describe the adsorption equilibrium for the system. In addition, first order, second order and saturation type kinetic models were applied to kinetic data of adsorption and kinetic constants were calculated. It was concluded that the second order and the saturation type kinetic models defined the adsorption data more accurately. Finally, the evaluated thermodynamic parameters of adsorption show a spontaneous and exothermic behavior. Overall, this study indicates OPAC/Chitosan composite as an effective and low-cost adsorbent for the removal of MB dye from aqueous solutions.Keywords: activated carbon, adsorption, chitosan, methylene blue, orange peel
Procedia PDF Downloads 29938 Effect of Constant and Variable Temperature on the Morphology of TiO₂ Nanotubes Prepared by Two-Step Anodization Method
Authors: Tayyaba Ghani, Mazhar Mehmood, Mohammad Mujahid
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TiO₂ nanotubes are receiving immense attraction in the field of dye-sensitized solar cells due to their well-defined nanostructures, efficient electron transport and large surface area as compared to other one dimensional structures. In the present work, we have investigated the influence of temperature on the morphology of anodically produced self-organized Titanium oxide nanotubes (TiNTs). TiNTs are synthesized by two-step anodization method in an ethylene glycol based electrolytes containing ammonium fluoride. Experiments are performed at constant anodization voltage for two hours. An investigation by the SEM images reveals that if the temperature is kept constant during the anodizing experiment, variation in the average tube diameter is significantly reduced. However, if the temperature is not controlled then due to the exothermic nature of reactions for the formation of TiNTs, the temperature of electrolyte keep on increasing. This variation in electrolyte bath temperature introduced strong variations in tube diameter (20 nm to 160 nm) along the length of tubes. Current profiles, recorded during the anodization experiment, predict the effect of constant and varying experimental temperatures as well. In both cases, XRD results show the complete anatase crystal structure of nanotube upon annealing at 450 °C. Present work highlights the importance of constant temperature during the anodization experiments in order to develop an ordered array of nanotubes with a uniform tube diameter.Keywords: anodization, ordering, temperature, TiO₂ nanotubes
Procedia PDF Downloads 17237 Thermodynamic Analysis of Wet Compression Integrated with Air-Film Blade Cooling in Gas Turbine Power Plants
Authors: Hassan Athari, Alireza Ruhi Sales, Amin Pourafshar, Seyyed Mehdi Pestei, Marc. A. Rosen
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In order to achieve high efficiency and high specific work with lower emissions, the use of advanced gas turbine cycles for power generation is useful and advantageous. Here, evaporative inlet air cooling is analyzed thermodynamically in the form of air film blade cooling of gas turbines. As the ambient temperature increases during summer months, the performance of gas turbines particularly the output power and energy efficiency are significantly decreased. The utilization of evaporative inlet cooling in gas turbine cycles increases gas turbine performance, which can assist to solve the problem in meeting the increasing demands for electrical power and offsetting shortages during peak load times. In the present research, because of the importance of turbine blade cooling, the turbine is investigated with cold compressed air used for cooling the turbine blades. The investigation of the basic and modified cycles shows that, by adding an evaporative cooler to a simple gas turbine cycle, for a turbine inlet temperature of 1400 °C, an ambient temperature of 45 °C and a relative humidity of 15%, the specific work can reach 331 (kJ/kg air), while the maximum specific work of a simple cycle for the same conditions is 273.7 (kJ/kg air). The exergy results reveal that the highest exergy destruction occurs in the combustion chamber, where the large temperature differences and highly exothermic chemical reactions are the main sources of the irreversibility.Keywords: energy, exergy, wet compression, air-film cooling blade, gas turbine
Procedia PDF Downloads 15536 Simulation of Cure Kinetics and Process-Induced Stresses in Carbon Fibre Composite Laminate Manufactured by a Liquid Composite Molding Technique
Authors: Jayaraman Muniyappan, Bachchan Kr Mishra, Gautam Salkar, Swetha Manian Sridhar
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Vacuum Assisted Resin Transfer Molding (VARTM), a cost effective method of Liquid Composite Molding (LCM), is a single step process where the resin, at atmospheric pressure, is infused through a preform that is maintained under vacuum. This hydrodynamic pressure gradient is responsible for the flow of resin through the dry fabric preform. The current study has a slight variation to traditional VARTM, wherein, the resin infuses through the fabric placed on a heated mold to reduce its viscosity. The saturated preform is subjected to a cure cycle where the resin hardens as it undergoes curing. During this cycle, an uneven temperature distribution through the thickness of the composite and excess exothermic heat released due to different cure rates result in non-uniform curing. Additionally, there is a difference in thermal expansion coefficient between fiber and resin in a given plane and between adjacent plies. All these effects coupled with orthotropic coefficient of thermal expansion of the composite give rise to process-induced stresses in the laminate. Such stresses lead to part deformation when the laminate tries to relieve them as the part is released off the mold. The current study looks at simulating resin infusion, cure kinetics and the structural response of composite laminate subject to process-induced stresses.Keywords: cure kinetics, process-induced stresses, thermal expansion coefficient, vacuum assisted resin transfer molding
Procedia PDF Downloads 24035 Effect of Recycled Grey Water on Bacterial Concrete
Authors: T. Deepa, S. R. Inchara, S. V. Venkatesh, Seema Tharannum
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Concrete is the most widely used structural material. It is made using locally available materials. However, Concrete has low tensile strength and may crack in the early days with exothermic hydration. Bacillus subtilis bacteria that form endospores is the biological agent considered in this study for Biomineralization or MICP (Microbially Induced Calcite Precipitation) Technique and to address the increased Construction water demand, Recycled Grey Water which is obtained from STP of PES University, opted in place of Potable water. In this work, M30 grade conventional concrete is designed using OPC 53 grade cement, Manufactured Sand, Natural coarse aggregates, and Potable water. Conventional Concrete (CC), Bacterial Concrete with Potable water (BS), and Recycled Grey Water concrete (RGW) are the three different concrete specimens casted. Experimental studies such as the strength test and the surface hardness test are conducted on Conventional and Bacterial concrete samples after 7, 28, and 56 days of curing. Concrete cubes are subjected to a temperature of 50° C to investigate the effect of higher temperature. Cracked cube specimens are observed for Self-healing - as well as microstructure analysis with Scanning Electron Microscope (SEM), Energy Dispersive X-Ray Analysis (EDAX), and X-Ray Diffraction Analysis (XRD).Noticeable Calcium salt deposition is observed on the surface of BS and RGW cracked specimen. Surface hardness and EDAX test gave promising result on the advantage of using spore-forming bacteria in concrete. This is followed by the strength gain in Compression and Flexure. Results also indicate that Recycled Grey Water can be a substitute for Normal water in concrete.Keywords: bacillus subtilis, bacterial concrete, recycled grey water, self-healing, surface hardness of concrete
Procedia PDF Downloads 13734 Partially Phosphorylated Polyvinyl Phosphate-PPVP Composite: Synthesis and Its Potentiality for Zr (IV) Extraction from an Acidic Medium
Authors: Khaled Alshamari
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Synthesized partially phosphorylated polyvinyl phosphate derivative (PPVP) was functionalized to extract Zirconium (IV) from Egyptian zircon sand. The specifications for the PPVP composite were approved effectively via different techniques, namely, FT-IR, XPS, BET, EDX, TGA, HNMR, C-NMR, GC-MS, XRD and ICP-OES analyses, which demonstrated a satisfactory synthesis of PPVP and zircon dissolution from Egyptian zircon sand. Factors controlling parameters, such as pH values, shaking time, initial zirconium concentration, PPVP dose, nitrate ions concentration, co-ions, temperature and eluting agents, have been optimized. At 25 ◦C, pH 0, 20 min shaking, 0.05 mol/L zirconium ions and 0.5 mol/L nitrate ions, PPVP has an exciting preservation potential of 195 mg/g, equivalent to 390 mg/L zirconium ions. From the extraction–distribution isotherm, the practical outcomes of Langmuir’s modeling are better than the Freundlich model, with a theoretical value of 196.07 mg/g, which is more in line with the experimental results of 195 mg/g. The zirconium ions adsorption onto the PPVP composite follows the pseudo-second-order kinetics with a theoretical capacity value of 204.08 mg/g. According to thermodynamic potential, the extraction process was expected to be an exothermic, spontaneous and beneficial extraction at low temperatures. The thermodynamic parameters ∆S (−0.03 kJ/mol), ∆H (−12.22 kJ/mol) and ∆G were also considered. As the temperature grows, ∆G values increase from −2.948 kJ/mol at 298 K to −1.941 kJ/mol at 338 K. Zirconium ions may be eluted from the working loaded PPVP by 0.025M HNO₃, with a 99% efficiency rate. It was found that zirconium ions revealed good separation factors towards some co-ions such as Hf⁴+ (28.82), Fe³+ (10.64), Ti⁴+ (28.82), V⁵+ (86.46) and U⁶+ (68.17). A successful alkali fusion technique with NaOH flux followed by the extraction with PPVP is used to obtain a high-purity zirconia concentrate with a zircon content of 72.77 % and a purity of 98.29%. As a result of this, the improved factors could finally be used.Keywords: zirconium extraction, partially phosphorylated polyvinyl phosphate (PPVP), acidic medium, zircon
Procedia PDF Downloads 6633 The Mainspring of Controlling of Low Pressure Steam Drum at Lower Pressure than Its Design for Adjusting the Urea Synthesis Pressure
Authors: Reza Behtash, Enayat Enayati
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The pool condenser is in principal a horizontal reactor, containing a bundle of U-tubes for heat exchange, coupling to low pressure steam drum. Condensation of gas takes place in a condensed pool around the tubes of the condenser. The heat of condensation is removed by the generation of low pressure steam on the inner tube side of the bundle. A circulation pump transfers ample boiler feed water to these tubes. The pressure of the steam generated influenced the heat flux. Changing the steam pressure means changing the steam condensate temperature and therefore the temperature difference between the tube side and the shell side. 2NH3 + CO2 ↔ NH2COONH4 + Heat. This reaction is exothermic and according to Le Chatelier's Principle if the heat is not removed enough, it will come back to left side and generate of the gas and so the Urea synthesis pressure will rise. The most principal reasons for high Urea synthesis pressure are non proportional of Ammonia/Dioxide Carbon ratio and too high a pressure in low pressure steam drum. Proportional of Ammonia/Dioxide Carbon ratio is 3.0 and normal pressure for low pressure steam drum is 4.5 bar. As regards these conditions were proportional but we could not control the synthesis pressure the plant endangered, therefore we had to control the steam drum pressure at about 3.5 bar. While we opened the pool condenser, we found the partition plate used to divide inlet and outlet boiler feed water to tubes, was broken partially and so amount of boiler feed water bypass the tubes and the heat was not removed totally and it resulted in the generation of gases and high pressure in synthesis.Keywords: boiler, pressure, pool condenser, partition plate
Procedia PDF Downloads 38432 On the Effect of Carbon on the Efficiency of Titanium as a Hydrogen Storage Material
Authors: Ghazi R. Reda Mahmoud Reda
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Among the metal that forms hydride´s, Mg and Ti are known as the most lightweight materials; however, they are covered with a passive layer of oxides and hydroxides and require activation treatment under high temperature ( > 300 C ) and hydrogen pressure ( > 3 MPa) before being used for storage and transport applications. It is well known that small graphite addition to Ti or Mg, lead to a dramatic change in the kinetics of mechanically induced hydrogen sorption ( uptake) and significantly stimulate the Ti-Hydrogen interaction. Many explanations were given by different authors to explain the effect of graphite addition on the performance of Ti as material for hydrogen storage. Not only graphite but also the addition of a polycyclic aromatic compound will also improve the hydrogen absorption kinetics. It will be shown that the function of carbon addition is two-fold. First carbon acts as a vacuum cleaner, which scavenges out all the interstitial oxygen that can poison or slow down hydrogen absorption. It is also important to note that oxygen favors the chemisorption of hydrogen, which is not desirable for hydrogen storage. Second, during scavenging of the interstitial oxygen, the carbon reacts with oxygen in the nano and microchannel through a highly exothermic reaction to produce carbon dioxide and monoxide which provide the necessary heat for activation and thus in the presence of carbon lower heat of activation for hydrogen absorption which is observed experimentally. Furthermore, the product of the reaction of hydrogen with the carbon oxide will produce water which due to ball milling hydrolyze to produce the linear H5O2 + this will reconstruct the primary structure of the nanocarbon to form secondary structure, where the primary structure (a sheet of carbon) are connected through hydrogen bonding. It is the space between these sheets where physisorption or defect mediated sorption occurs.Keywords: metal forming hydrides, polar molecule impurities, titanium, phase diagram, hydrogen absorption
Procedia PDF Downloads 36431 Producing of Amorphous-Nanocrystalline Composite Powders
Authors: K. Tomolya, D. Janovszky, A. Sycheva, M. Sveda, A. Roosz
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CuZrAl amorphous alloys have attracted high interest due to unique physical and mechanical properties, which can be enhanced by adding of Ni and Ti elements. It is known that this properties can be enhanced by crystallization of amorphous alloys creating nanocrystallines in the matrix. The present work intends to produce nanosized crystalline parti-cle reinforced amorphous matrix composite powders by crystallization of amorphous powders. As the first step the amorphous powders were synthe-tized by ball-milling of crystalline powders. (Cu49Zr45Al6) 80Ni10Ti10 and (Cu49Zr44Al7) 80Ni10Ti10 (at%) alloys were ball-milled for 12 hours in order to reach the fully amorphous structure. The impact en-ergy of the balls during milling causes the change of the structure in the powders. Scanning electron microscopical (SEM) images shows that the phases mixed first and then changed into a fully amorphous matrix. Furthermore, nanosized particles in the amorphous matrix were crystallized by heat treatment of the amorphous powders that was confirmed by TEM measurement. It was of importance to define the tem-perature when the amorphous phase starts to crystal-lize. Amorphous alloys have a special heating curve and characteristic temperatures, which can be meas-ured by differential scanning calorimetry (DSC). A typical DSC curve of an amorphous alloy exhibits an endothermic event characteristic of the equilibrium glass transition (Tg) and a distinct undercooled liquid region, followed by one or two exothermic events corresponding to crystallization processes (Tp). After measuring the DSC traces of the amorphous powders, the annealing temperatures should be determined between Tx and Tp. In our experiments several temperatures from the annealing temperature range were selected and de-pendency of crystallized nanoparticles fraction on their hardness was investigated.Keywords: amorphous structure, composite, mechanical milling, powder, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), transmission electronmocroscopy (TEM)
Procedia PDF Downloads 45030 Biophysical Study of the Interaction of Harmalol with Nucleic Acids of Different Motifs: Spectroscopic and Calorimetric Approaches
Authors: Kakali Bhadra
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Binding of small molecules to DNA and recently to RNA, continues to attract considerable attention for developing effective therapeutic agents for control of gene expression. This work focuses towards understanding interaction of harmalol, a dihydro beta-carboline alkaloid, with different nucleic acid motifs viz. double stranded CT DNA, single stranded A-form poly(A), double-stranded A-form of poly(C)·poly(G) and clover leaf tRNAphe by different spectroscopic, calorimetric and molecular modeling techniques. Results of this study converge to suggest that (i) binding constant varied in the order of CT DNA > poly(C)·poly(G) > tRNAphe > poly(A), (ii) non-cooperative binding of harmalol to poly(C)·poly(G) and poly(A) and cooperative binding with CT DNA and tRNAphe, (iii) significant structural changes of CT DNA, poly(C)·poly(G) and tRNAphe with concomitant induction of optical activity in the bound achiral alkaloid molecules, while with poly(A) no intrinsic CD perturbation was observed, (iv) the binding was predominantly exothermic, enthalpy driven, entropy favoured with CT DNA and poly(C)·poly(G) while it was entropy driven with tRNAphe and poly(A), (v) a hydrophobic contribution and comparatively large role of non-polyelectrolytic forces to Gibbs energy changes with CT DNA, poly(C)·poly(G) and tRNAphe, and (vi) intercalated state of harmalol with CT DNA and poly(C)·poly(G) structure as revealed from molecular docking and supported by the viscometric data. Furthermore, with competition dialysis assay it was shown that harmalol prefers hetero GC sequences. All these findings unequivocally pointed out that harmalol prefers binding with ds CT DNA followed by ds poly(C)·poly(G), clover leaf tRNAphe and least with ss poly(A). The results highlight the importance of structural elements in these natural beta-carboline alkaloids in stabilizing different DNA and RNA of various motifs for developing nucleic acid based better therapeutic agents.Keywords: calorimetry, docking, DNA/RNA-alkaloid interaction, harmalol, spectroscopy
Procedia PDF Downloads 22829 Effect of Treated Grey Water on Bacterial Concrete
Authors: Deepa T., Inchara S. R., Venkatesh S. V., Seema Tharannum
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Concrete is the most widely used structural material. It is usually made using locally available materials. However, concrete has low tensile strength and may crack in the early days with exothermic hydration, for which water is essential. To address the increased construction water demand, treated greywater may be used. Bacillus subtilis bacteria that form endospores is the biological agent considered in this study for biomineralization or Microbially Induced Calcite Precipitation (MICP) technique to heal cracks. Treated grey water which is obtained from STP of PES University, opted in place of Potable water, which had qualities within the standard range as per codal provisions. In this work, M30 grade conventional concrete is designed using OPC 53-grade cement, manufactured sand, natural coarse aggregates, and potable water. Conventional concrete (CC), bacterial concrete with potable water (BS), and treated grey water concrete (TGWBS) are the three different concrete specimens cast. Experimental studies such as the strength test and the surface hardness test are performed on conventional and bacterial concrete samples after 7, 28, and 56 days of curing. Concrete cubes are subjected to a temperature of 50° C to investigate the effect of higher temperature. Cracked cube specimens are observed for self-healing -as well as microstructure analysis with Scanning Electron Microscope (SEM), Energy Dispersive X-Ray Analysis (EDAX), and X-Ray Diffraction Analysis (XRD). Noticeable calcium salt deposition is observed on the surface of the BS and TGWBS cracked specimen. Surface hardness and the EDAX test gave promising results on the advantage of using spore-forming bacteria in concrete. This is followed by the strength gained in compression and flexure. Results also indicate that treated grey water can be a substitute for potable water in concrete.Keywords: Bacillus subtilis concrete, microstructure, temperature, treated greywater
Procedia PDF Downloads 10128 Nano-Enhanced In-Situ and Field Up-Gradation of Heavy Oil
Authors: Devesh Motwani, Ranjana S. Baruah
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The prime incentive behind up gradation of heavy oil is to increase its API gravity for ease of transportation to refineries, thus expanding the market access of bitumen-based crude to the refineries. There has always been a demand for an integrated approach that aims at simplifying the upgrading scheme, making it adaptable to the production site in terms of economics, environment, and personnel safety. Recent advances in nanotechnology have facilitated the development of two lines of heavy oil upgrading processes that make use of nano-catalysts for producing upgraded oil: In Situ Upgrading and Field Upgrading. The In-Situ upgrading scheme makes use of Hot Fluid Injection (HFI) technique where heavy fractions separated from produced oil are injected into the formations to reintroduce heat into the reservoir along with suspended nano-catalysts and hydrogen. In the presence of hydrogen, catalytic exothermic hydro-processing reactions occur that produce light gases and volatile hydrocarbons which contribute to increased oil detachment from the rock resulting in enhanced recovery. In this way the process is a combination of enhanced heavy oil recovery along with up gradation that effectively handles the heat load within the reservoirs, reduces hydrocarbon waste generation and minimizes the need for diluents. By eliminating most of the residual oil, the Synthetic Crude Oil (SCO) is much easier to transport and more amenable for processing in refineries. For heavy oil reservoirs seriously impacted by the presence of aquifers, the nano-catalytic technology can still be implemented on field though with some additional investments and reduced synergies; however still significantly serving the purpose of production of transportable oil with substantial benefits with respect to both large scale upgrading, and known commercial field upgrading technologies currently on the market. The paper aims to delve deeper into the technology discussed, and the future compatibility.Keywords: upgrading, synthetic crude oil, nano-catalytic technology, compatibility
Procedia PDF Downloads 40827 Inhibition Effect of Natural Junipers Extract towards Steel Corrosion in HCl Solution
Authors: L. Bammou, M. Belkhaouda R. Salghi, L. Bazzi, B. Hammouti
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Steel and steel-based alloys of different grades steel are extensively used in numerous applications where acid solutions are widely applied such as industrial acid pickling, industrial acid cleaning and oil-well acidizing. The use of chemical inhibitors is one of the most practical methods for the protection against corrosion in acidic media. Most of the excellent acid inhibitors are organic compounds containing nitrogen, oxygen, phosphorus and sulphur. The use of non-toxic inhibitors called green or eco-friendly environmental inhibitors is one of the solutions possible to prevent the corrosion of the material. These advantages have incited us to draw a large part of program of our laboratory to examine natural substances as corrosion inhibitors such as: prickly pear seed oil, Argan oil, Argan extract, Fennel oil, Rosemary oil, Thymus oil, Lavender oil, Jojoba oil, Pennyroyal Mint oil, and Artemisia. In the present work, we investigate the corrosion inhibition of steel in 1 M HCl by junipers extract using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) methods. The result obtained of junipers extract (JE) shows excellent inhibition properties for the corrosion of C38 steel in 1M HCl at 298K, and the inhibition efficiency increases with increasing of the JE concentration. The inhibitor efficiencies determined by weight loss, Tafel polarisation and EIS methods are in reasonable agreement. Based on the polarisation results, the investigated junipers extract can be classified as mixed inhibitor. The calculated structural parameters show increase of the obtained Rct values and decrease of the capacitance, Cdl, with JE concentration increase. It is suggested to attribute this to the increase of the thickness of the adsorption layer at steel surface. The adsorption model obeys to the Langmuir adsorption isotherm. The adsorption process is a spontaneous and exothermic process.Keywords: corrosion inhibition, steel, friendly inhibitors, Tafel polarisation
Procedia PDF Downloads 52426 Influence of Magnetic Field on Microstructure and Properties of Copper-Silver Composites
Authors: Engang Wang
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The Cu-alloy composites are a kind of high-strength and high-conductivity Cu-based alloys, which have excellent mechanical and electrical properties and is widely used in electronic, electrical, machinery industrial fields. However, the solidification microstructure of the composites, such as the primary or second dendrite arm spacing, have important rule to its tensile strength and conductivity, and that is affected by its fabricating method. In this paper, two kinds of directional solidification methods; the exothermic powder method (EP method) and liquid metal cooling method (LMC method), were used to fabricate the Cu-alloy composites with applied different magnetic fields to investigate their influence on the solidifying microstructure of Cu-alloy, and further the fabricated Cu-alloy composites was drawn to wires to investigate the influence of fabricating method and magnetic fields on the drawing microstructure of fiber-reinforced Cu-alloy composites and its properties. The experiment of Cu-Ag alloy under directional solidification and horizontal magnetic fields with different processing parameters show that: 1) For the Cu-Ag alloy with EP method, the dendrite is directionally developed in the cooling copper mould and the solidifying microstructure is effectively refined by applying horizontal magnetic fields. 2) For the Cu-Ag alloy with LMC method, the primary dendrite arm spacing is decreased and the content of Ag in the dendrite increases as increasing the drawing velocity of solidification. 3) The dendrite is refined and the content of Ag in the dendrite increases as increasing the magnetic flux intensity; meanwhile, the growth direction of dendrite is also affected by magnetic field. The research results of Cu-Ag alloy in situ composites by drawing deforming process show that the micro-hardness of alloy is higher by decreasing dendrite arm spacing. When the dendrite growth orientation is consistent with the axial of the samples. the conductivity of the composites increases with the second dendrite arm spacing increases. However, its conductivity reduces with the applied magnetic fields owing to disrupting the dendrite growth orientation.Keywords: Cu-Ag composite, magnetic field, microstructure, solidification
Procedia PDF Downloads 21425 Comparison Methyl Orange and Malachite Green Dyes Removal by GO, rGO, MWCNT, MWCNT-COOH, and MWCNT-SH as Adsorbents
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
Procedia PDF Downloads 38224 Lightweight Ceramics from Clay and Ground Corncobs
Authors: N.Quaranta, M. Caligaris, R. Varoli, A. Cristobal, M. Unsen, H. López
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Corncobs are agricultural wastes and they can be used as fuel or as raw material in different industrial processes like cement manufacture, contaminant adsorption, chemical compound synthesis, etc. The aim of this work is to characterize this waste and analyze the feasibility of its use as a pore-forming material in the manufacture of lightweight ceramics for the civil construction industry. The characterization of raw materials is carried out by using various techniques: electron diffraction analysis X-ray, differential and gravimetric thermal analyses, FTIR spectroscopy, ecotoxicity evaluation, among others. The ground corncobs, particle size less than 2 mm, are mixed with clay up to 30% in volume and shaped by uniaxial pressure of 25 MPa, with 6% humidity, in moulds of 70mm x 40mm x 18mm. Then the green bodies are heat treated at 950°C for two hours following the treatment curves used in ceramic industry. The ceramic probes are characterized by several techniques: density, porosity and water absorption, permanent volumetric variation, loss on ignition, microscopies analysis, and mechanical properties. DTA-TGA analysis of corncobs shows in the range 20°-250°C a small loss in TGA curve and exothermic peaks at 250°-500°C. FTIR spectrum of the corncobs sample shows the characteristic pattern of this kind of organic matter with stretching vibration bands of adsorbed water, methyl groups, C–O and C–C bonds, and the complex form of the cellulose and hemicellulose glycosidic bonds. The obtained ceramic bodies present external good characteristics without loose edges and adequate properties for the market requirements. The porosity values of the sintered pieces are higher than those of the reference sample without waste addition. The results generally indicate that it is possible to use corncobs as porosity former in ceramic bodies without modifying the usual sintering temperatures employed in the industry.Keywords: ceramic industry, biomass, recycling, hemicellulose glycosidic bonds
Procedia PDF Downloads 40523 Kinetics and Thermodynamics Adsorption of Phenolic Compounds on Organic-Inorganic Hybrid Mesoporous Material
Authors: Makhlouf Mourad, Messabih Sidi Mohamed, Bouchher Omar, Houali Farida, Benrachedi Khaled
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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.Keywords: adsorption, kinetics, isotherm, mesoporous materials, Phenol, P-hydroxy benzoique acid
Procedia PDF Downloads 20822 The Use of Additives to Prevent Fouling in Polyethylene and Polypropylene Gas and Slurry Phase Processes
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All polyethylene processes are highly exothermic, and the safe removal of the heat of reaction is a fundamental issue in the process design. In slurry and gas processes, the velocity of the polymer particles in the reactor and external coolers can be very high, and under certain conditions, this can lead to static charging of these particles. Such static charged polymer particles may start building up on the reactor wall, limiting heat transfer, and ultimately leading to severe reactor fouling and forced reactor shut down. Statsafe™ is an FDA approved anti-fouling additive currently used around the world for polyolefin production as an anti-fouling additive. The unique polymer chemistry aids static discharge, which prevents the build-up of charged polyolefin particles, which could lead to fouling. Statsafe™ is being used and trailed in gas, slurry, and a combination of these technologies around the world. We will share data to demonstrate how the use of Statsafe™ allows more stable operation at higher solids level by eliminating static, which would otherwise prevent closer packing of particles in the hydrocarbon slurry. Because static charge generation depends also on the concentration of polymer particles in the slurry, the maximum slurry concentration can be higher when using Statsafe™, leading to higher production rates. The elimination of fouling also leads to less downtime. Special focus will be made on the impact anti-static additives have on catalyst performance within the polymerization process and how this has been measured. Lab-scale studies have investigated the effect on the activity of Ziegler Natta catalysts when anti-static additives are used at various concentrations in gas and slurry, polyethylene and polypropylene processes. An in-depth gas phase study investigated the effect of additives on the final polyethylene properties such as particle size, morphology, fines, bulk density, melt flow index, gradient density, and melting point.Keywords: anti-static additives, catalyst performance, FDA approved anti-fouling additive, polymerisation
Procedia PDF Downloads 207