Search results for: bubbling fluidized bed reactor

Authors: Muhammad Shoaib, Hassan M Al-Swaidan

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Saudi Arabia is the major date producer in the world. In order to maximize the production from date tree, pruning of the date trees is required annually. Large amount of this agriculture waste material (palm tree fronds) is available in Saudi Arabia and considered as an ideal source as a precursor for production of activated carbon (AC). The single step procedure for the preparation of micro porous activated carbon (AC) from Saudi date tree fronds using mixture of gases (N2 and CO2) is carried out at carbonization/activation temperature at 850°C and at different ramp rates of 10, 20 and 30 degree per minute. Alloy 330 horizontal reactor is used for tube furnace. Flow rate of nitrogen and carbon dioxide gases are kept at 150 ml/min and 50 ml/min respectively during the preparation. Characterization results reveal that the BET surface area, pore volume, and average pore diameter of the resulting activated carbon generally decreases with the increase in ramp rate. The activated carbon prepared at a ramp rate of 10 degrees/minute attains larger surface area and can offer higher potential to produce activated carbon of greater adsorption capacity from agriculture wastes such as date fronds. The BET surface areas of the activated carbons prepared at a ramp rate of 10, 20 and 30 degree/minute after 30 minutes activation time are 1094, 1020 and 515 m2/g, respectively. Scanning electron microscopy (SEM) for surface morphology, and FTIR for functional groups was carried out that also verified the same trend. Moreover, by increasing the ramp rate from 10 and 20 degrees/min the yield remains same, i.e. 18%, whereas at a ramp rate of 30 degrees/min the yield increases from 18 to 20%. Thus, it is feasible to produce high-quality micro porous activated carbon from date frond agro waste using N2 carbonization followed by physical activation with CO2 and N2 mixture. This micro porous activated carbon can be used as adsorbent of heavy metals from wastewater, NOx SOx emission adsorption from ambient air and electricity generation plants, purification of gases, sewage treatment and many other applications.

Keywords: activated carbon, date tree fronds, agricultural waste, applied chemistry

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Authors: Elaf Ahmed, Shahid Rasul, Ohoud Alharbi, Peng Wang

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Ultra-Small Nanoparticles of metals (USNPs) have attracted the attention from the perspective of both basic and developmental science in a wide range of fields. These NPs exhibit electrical, optical, magnetic, and catalytic phenomena. In addition, they are considered effective catalysts because of their enormously large surface area. Many chemical methods of synthesising USNPs are reported. However, the drawback of these methods is the use of different capping agents and ligands in the process of the production such as Polyvinylpyrrolidone, Thiol and Ethylene Glycol. In this research ultra-small nanoparticles of gold, palladium and platinum metal have been successfully produced using electrochemically active biofilm (EAB) after optimising the pH of the media. The production of ultra-small nanoparticles has been conducted in a reactor using a simple two steps method. Initially biofilm was grown on the surface of a carbon paper for 7 days using Shewanella Loihica bacteria. Then, biofilm was employed to synthesise platinum, palladium and gold nanoparticles in water using sodium lactate as electron donor without using any toxic chemicals at mild operating conditions. Electrochemically active biofilm oxidise the electron donor and produces electrons in the solution. Since these electrons are a strong reducing agent, they can reduce metal precursors quite effectively and quickly. The As-synthesized ultra-small nanoparticles have a size range between (2-7nm) and showed excellent catalytic activity on the degradation of methyl orange. The growth of metal USNPs is strongly related to the condition of the EAB. Where using low pH for the synthesis was not successful due to the fact that it might affect and destroy the bacterial cells. However, increasing the pH to 7 and 9, led to the successful formation of USNPs. By changing the pH value, we noticed a change in the size range of the produced NPs. The EAB seems to act as a Nano factory for the synthesis of metal nanoparticles by offering a green, sustainable and toxic free synthetic route without the use of any capping agents or ligands and depending only on their respiration pathway.

Keywords: electrochemically active biofilm, electron donor, shewanella loihica, ultra-small nanoparticles

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Authors: Vincenzo Piemonte

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The liver is a complex, large-scale biochemical reactor which plays a unique role in the human physiology. When liver ceases to perform its physiological activity, a functional replacement is required. Actually, liver transplantation is the only clinically effective method of treating severe liver disease. Anyway, the aforementioned therapeutic approach is hampered by the disparity between organ availability and the number of patients on the waiting list. In order to overcome this critical issue, research activities focused on liver support device systems (LSDs) designed to bridging patients to transplantation or to keep them alive until the recovery of native liver function. In recirculating albumin dialysis devices, such as MARS (Molecular Adsorbed Recirculating System), adsorption is one of the fundamental steps in albumin-dialysate regeneration. Among the albumin-bound toxins that must be removed from blood during liver-failure therapy, bilirubin and tryptophan can be considered as representative of two different toxin classes. The first one, not water soluble at physiological blood pH and strongly bounded to albumin, the second one, loosely albumin bound and partially water soluble at pH 7.4. Fixed bed units are normally used for this task, and the design of such units requires information both on toxin adsorption equilibrium and kinetics. The most common adsorptive media used in LSDs are activated carbon, non-ionic polymeric resins and anionic resins. In this paper, bilirubin adsorption isotherms on different adsorptive media, such as polymeric resin, albumin-coated resin, anionic resin, activated carbon and alginate beads with entrapped albumin are presented. By comparing all the results, it can be stated that the adsorption capacity for bilirubin of the five different media increases in the following order: Alginate beads < Polymeric resin < Albumin-coated resin < Activated carbon < Anionic resin. The main focus of this paper is to provide useful guidelines for the optimization of liver support devices which implement adsorption columns to remove albumin-bound toxins from albumin dialysate solutions.

Keywords: adsorptive media, adsorption equilibrium, artificial liver devices, bilirubin, mathematical modelling

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Authors: Ahmed AlNouss, Salim Ahmed

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Process control refers to the techniques to control the variables in a process in order to maintain them at their desired values. Advanced process control (APC) is a broad term within the domain of control where it refers to different kinds of process control and control related tools, for example, model predictive control (MPC), statistical process control (SPC), fault detection and classification (FDC) and performance assessment. APC is often used for solving multivariable control problems and model predictive control (MPC) is one of only a few advanced control methods used successfully in industrial control applications. Advanced control is expected to bring many benefits to the plant operation; however, the extent of the benefits is plant specific and the application needs a large investment. This requires an analysis of the expected benefits before the implementation of the control. In a real plant simulation studies are carried out along with some experimentation to determine the improvement in the performance of the plant due to advanced control. In this research, such an exercise is undertaken to realize the needs of APC application. The main objectives of the paper are as follows: (1) To apply MPC to a number of simulations set up to realize the need of MPC by comparing its performance with that of proportional integral derivatives (PID) controllers. (2) To study the effect of controller parameters on control performance. (3) To develop appropriate performance index (PI) to compare the performance of different controller and develop novel idea to present tuning map of a controller. These objectives were achieved by applying PID controller and a special type of MPC which is dynamic matrix control (DMC) on the multi-tanks process simulated in loop-pro. Then the controller performance has been evaluated by changing the controller parameters. This performance was based on special indices related to the difference between set point and process variable in order to compare the both controllers. The same principle was applied for continuous stirred tank heater (CSTH) and continuous stirred tank reactor (CSTR) processes simulated in Matlab. However, in these processes some developed programs were written to evaluate the performance of the PID and MPC controllers. Finally these performance indices along with their controller parameters were plotted using special program called Sigmaplot. As a result, the improvement in the performance of the control loops was quantified using relevant indices to justify the need and importance of advanced process control. Also, it has been approved that, by using appropriate indices, predictive controller can improve the performance of the control loop significantly.

Keywords: advanced process control (APC), control loop, model predictive control (MPC), proportional integral derivatives (PID), performance indices (PI)

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Authors: Kazunori Nomura, Hiromichi Ogi, Masaumi Nakahara, Sou Watanabe, Atsuhiro Shibata

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Chemical Processing Facility of Japan Atomic Energy Agency is a basic research field for advanced back-end technology developments with using actual high-level radioactive materials such as irradiated fuels from the fast reactor, high-level liquid waste from reprocessing plant. In the nature of a research facility, various kinds of chemical reagents have been offered for fundamental tests. Most of them were treated properly and stored in the liquid waste vessel equipped in the facility, but some were not treated and remained at the experimental space as a kind of legacy waste. It is required to treat the waste in safety. On the other hand, we formulated the Medium- and Long-Term Management Plan of Japan Atomic Energy Agency Facilities. This comprehensive plan considers Chemical Processing Facility as one of the facilities to be decommissioned. Even if the plan is executed, treatment of the “legacy” waste beforehand must be a necessary step for decommissioning operation. Under this circumstance, we launched a collaborative research project called the STRAD project, which stands for Systematic Treatment of Radioactive liquid waste for Decommissioning, in order to develop the treatment processes for wastes of the nuclear research facility. In this project, decomposition methods of chemicals causing a troublesome phenomenon such as corrosion and explosion have been developed and there is a prospect of their decomposition in the facility by simple method. And solidification of aqueous or organic liquid wastes after the decomposition has been studied by adding cement or coagulants. Furthermore, we treated experimental tools of various materials with making an effort to stabilize and to compact them before the package into the waste container. It is expected to decrease the number of transportation of the solid waste and widen the operation space. Some achievements of these studies will be shown in this paper. The project is expected to contribute beneficial waste management outcome that can be shared world widely.

Keywords: chemical processing facility, medium- and long-term management plan of JAEA facilities, STRAD project, treatment of radioactive waste

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Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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Authors: Vikas Teotia, Sanjay Malhotra, Elina Mishra, Prashant Kumar, R. R. Singh, Priti Ukarde, P. P. Marathe, Y. S. Mayya

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Bhabha Atomic Research Centre, Trombay is developing low energy high intensity Proton Accelerator (LEHIPA) as pre-injector for 1 GeV proton accelerator for accelerator driven sub-critical reactor system (ADSS). LEHIPA consists of RFQ (Radio Frequency Quadrupole) and DTL (Drift Tube Linac) as major accelerating structures. DTL is RF resonator operating in TM010 mode and provides longitudinal E-field for acceleration of charged particles. The RF design of drift tubes of DTL was carried out to maximize the shunt impedance; this demands the diameter of drift tubes (DTs) to be as low as possible. The width of the DT is however determined by the particle β and trade-off between a transit time factor and effective accelerating voltage in the DT gap. The array of Drift Tubes inside DTL shields the accelerating particle from decelerating RF phase and provides transverse focusing to the charged particles which otherwise tends to diverge due to Columbic repulsions and due to transverse e-field at entry of DTs. The magnetic lenses housed inside DTS controls the transverse emittance of the beam. Quadrupole magnets are preferred over solenoid magnets due to relative high focusing strength of former over later. The availability of small volume inside DTs for housing magnetic quadrupoles has motivated the usage of permanent magnet quadrupoles rather than Electromagnetic Quadrupoles (EMQ). This provides another advantage as joule heating is avoided which would have added thermal loaded in the continuous cycle accelerator. The beam dynamics requires uniformity of integral magnetic gradient to be better than ±0.5% with the nominal value of 2.05 tesla. The paper describes the magnetic design of the PMQ using Sm2Co17 rare earth permanent magnets. The paper discusses the results of five pre-series prototype fabrications and qualification of their prototype permanent magnet quadrupoles and a full scale DT developed with embedded PMQs. The paper discusses the magnetic pole design for optimizing integral Gdl uniformity and the value of higher order multipoles. A novel but simple method of tuning the integral Gdl is discussed.

Keywords: DTL, focusing, PMQ, proton, rate earth magnets

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Authors: Rong Li, Brian D. Wirth, Bing Liu

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Graphite is the matrix, and structural material in the high temperature gas-cooled reactor exhibits an irradiation response. It is of significant importance to analyze the defect production and evaluate the role of graphite under irradiation. A vast experimental literature exists for graphite on the dimensional change, mechanical properties, and thermal behavior. However, simulations have not been applied to the atomistic perspective. Remarkably few molecular dynamics simulations have been performed to study the irradiation response in graphite. In this paper, irradiation-induced damage cascades in graphite were investigated with molecular dynamics simulation. Statistical results of the graphite defects were obtained by sampling a wide energy range (1–30 KeV) and 10 different runs for every cascade simulation with different random number generator seeds to the velocity scaling thermostat function. The chemical bonding in carbon was described using the adaptive intermolecular reactive empirical bond-order potential (AIREBO) potential coupled with the standard Ziegler–Biersack–Littmack (ZBL) potential to describe close-range pair interactions. This study focused on analyzing the number of defects, the final cascade morphology and the distribution of defect clusters in space, the length-scale cascade properties such as the cascade length and the range of primary knock-on atom (PKA), and graphite mechanical properties’ variation. It can be concluded that the number of surviving Frenkel pairs increased remarkably with the increasing initial PKA energy but did not exhibit a thermal spike at slightly lower energies in this paper. The PKA range and cascade length approximately linearly with energy which indicated that increasing the PKA initial energy will come at expensive computation cost such as 30KeV in this study. The cascade morphology and the distribution of defect clusters in space mainly related to the PKA energy meanwhile the temperature effect was relatively negligible. The simulations are in agreement with known experimental results and the Kinchin-Pease model, which can help to understand the graphite damage cascades and lifetime span under irradiation and provide a direction to the designs of these kinds of structural materials in the future reactors.

Keywords: graphite damage cascade, molecular dynamics, cascade morphology, cascade distribution

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Authors: Moses Kolade Ogun, Ina Korner

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To improve on the sustainable resource management in the wastepaper recycling industry, studies into the valorization of wastes generated by the industry are necessary. The industry produces different residues, among which is the deinking sludge (DS). The DS is generated from the deinking process and constitutes a major fraction of the residues generated by the European pulp and paper industry. The traditional treatment of DS by incineration is capital intensive due to energy requirement for dewatering and the need for complementary fuel source due to DS low calorific value. This could be replaced by a biotechnological approach. This study, therefore, investigated the biogas potential of different DS streams (different dewatering degrees) and the influence of the high calcium carbonate content of DS on its biogas potential. Dewatered DS (solid fraction) sample from filter press and the filtrate (liquid fraction) were collected from a partner wastepaper recycling company in Germany. The solid fraction and the liquid fraction were mixed in proportion to realize DS with different water content (55–91% fresh mass). Spiked samples of DS using deionized water, cellulose and calcium carbonate were prepared to simulate DS with varying calcium carbonate content (0– 40% dry matter). Seeding sludge was collected from an existing biogas plant treating sewage sludge in Germany. Biogas potential was studied using a 1-liter batch test system under the mesophilic condition and ran for 21 days. Specific biogas potential in the range 133- 230 NL/kg-organic dry matter was observed for DS samples investigated. It was found out that an increase in the liquid fraction leads to an increase in the specific biogas potential and a reduction in the absolute biogas potential (NL-biogas/ fresh mass). By comparing the absolute biogas potential curve and the specific biogas potential curve, an optimal dewatering degree corresponding to a water content of about 70% fresh mass was identified. This degree of dewatering is a compromise when factors such as biogas yield, reactor size, energy required for dewatering and operation cost are considered. No inhibitory influence was observed in the biogas potential of DS due to the reported high calcium carbonate content of DS. This study confirms that DS is a potential bioresource for biogas production. Further optimization such as nitrogen supplementation due to DS high C/N ratio can increase biogas yield.

Keywords: biogas, calcium carbonate, deinking sludge, dewatering, water content

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Authors: Marius Sebastian Secula, Mihaela Darie, Gabriela Carja

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Ibuprofen is a non-steroidal anti-inflammatory drug (NSAIDs) and is among the most frequently detected pharmaceuticals in environmental samples and among the most widespread drug in the world. Its concentration in the environment is reported to be between 10 and 160 ng L-1. In order to improve the abatement efficiency of this compound for water source prevention and reclamation, the development of innovative technologies is mandatory. AOPs (advanced oxidation processes) are known as highly efficient towards the oxidation of organic pollutants. Among the promising combined treatments, photo-Fenton processes using layered double hydroxides (LDHs) attracted significant consideration especially due to their composition flexibility, high surface area and tailored redox features. This work presents the self-supported Fe, Mn or Ti on ZnFeAl LDHs obtained by co-precipitation followed by reconstruction method as novel efficient photo-catalysts for Fenton-like catalysis. Fe, Mn or Ti/ZnFeAl LDHs nano-hybrids were tested for the degradation of a model pharmaceutical agent, the anti-inflammatory agent ibuprofen, by photocatalysis and photo-Fenton catalysis, respectively, by means of a lab-scale system consisting of a batch reactor equipped with an UV lamp (17 W). The present study presents comparatively the degradation of Ibuprofen in aqueous solution UV light irradiation using four different types of LDHs. The newly prepared Ti/ZnFeAl 4:1 catalyst results in the best degradation performance. After 60 minutes of light irradiation, the Ibuprofen removal efficiency reaches 95%. The slowest degradation of Ibuprofen solution occurs in case of Fe/ZnFeAl 4:1 LDH, (67% removal efficiency after 60 minutes of process). Evolution of Ibuprofen degradation during the photo Fenton process is also studied using Ti/ZnFeAl 2:1 and 4:1 LDHs in the presence and absence of H2O2. It is found that after 60 min the use of Ti/ZnFeAl 4:1 LDH in presence of 100 mg/L H2O2 leads to the fastest degradation of Ibuprofen molecule. After 120 min, both catalysts Ti/ZnFeAl 4:1 and 2:1 result in the same value of removal efficiency (98%). In the absence of H2O2, Ibuprofen degradation reaches only 73% removal efficiency after 120 min of degradation process. Acknowledgements: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: layered double hydroxide, advanced oxidation process, micropollutant, heterogeneous Fenton

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Authors: Hernan Arturo Blas López, Gustavo Henndel Lopes, Antonio Carlos Silva Costa Teixeira, Carmen Elena Flores Barreda, Patricia Araujo Pantoja

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Phenols are toxic for life and the environment and may come from many sources. Uncured phenolic monomers present in phenolic resins used as binders in grinding wheels and emery paper can contaminate industrial wastewaters in abrasives manufacture plants. Furthermore, vestiges of resol and novolacs resins generated by wear and tear of abrasives are also possible sources of water contamination by phenolics in these facilities. Fortunately, advanced oxidation by dark Fenton and photo-Fenton techniques are capable of oxidizing phenols and their degradation products up to their mineralization into H₂O and CO₂. The maximal allowable concentrations for phenols in Peruvian waterbodies is very low, such that insufficiently treated effluents from the abrasives industry are a potential environmental noncompliance. The current case study highlights findings obtained during the lab-scale application of Fenton’s and photo-assisted Fenton’s chemistries to real industrial wastewater samples from an abrasives manufacture plant in Peru. The goal was to reduce the phenolic content and sample toxicity. For this purpose, two independent variables-reaction time and effect of ultraviolet radiation–were studied as for their impacts on the concentration of total phenols, total organic carbon (TOC), biological oxygen demand (BOD) and chemical oxygen demand (COD). In this study, diluted samples (1 L) of the industrial effluent were treated with Fenton’s reagent (H₂O₂ and Fe²⁺ from FeSO₄.H₂O) during 10 min in a photochemical batch reactor (Alphatec RFS-500, Brazil) at pH 2.92. In the case of photo-Fenton tests with ultraviolet lamps of 9 W, UV-A, UV-B and UV-C lamps were evaluated. All process conditions achieved 100% of phenols degraded within 5 minutes. TOC, BOD and COD decreased by 49%, 52% and 86% respectively (all processes together). However, Fenton treatment was not capable of reducing BOD, COD and TOC below a certain value even after 10 minutes, contrarily to photo-Fenton. It was also possible to conclude that the processes here studied degrade other compounds in addition to phenols, what is an advantage. In all cases, elevated effluent dilution factors and high amounts of oxidant agent impact negatively the overall economy of the processes here investigated.

Keywords: fenton oxidation, wastewater treatment, phenols, abrasives industry

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Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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The CO2 emitted from anthropic activities is perceived as a constraint in industrial activity due to taxes, stringent environmental regulations, impact on global warming… To limit these CO2 emissions, reuse of CO2 represents a promising alternative, with important applications in chemical industry and for power generation. However, CO2 valorization process requires a gas as pure as possible Oxyfuel-combustion that enables obtaining a CO2 rich stream, with water vapor (10%) is then interesting. Nevertheless to decrease the amount of the by-products found with the CO2 (especially CO and NOx which are harmful to the environment) a catalytic treatment must be applied. Nowadays three-way catalysts are well-developed material for simultaneous conversion of unburned hydrocarbons, carbon monoxide (CO) and nitrogen oxides (NOx). The use of Pd attracted considerable attention on the basis of economic factors (the high cost and scarcity of Pt and Rh). This explains the large number of studies concerning the CO-NO reaction on Pd in the recent years. In the present study, we will compare a series of Pd materials supported on different oxides for CO2 purification from the oxyfuel combustion system, by reducing NO with CO in an oxidizing environment containing CO2 rich stream and presence of 8.2% of water. Al2O3, CeO2, MgO, SiO2 and TiO2 were used as support materials of the catalysts. 1wt% Pd/Support catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2]. The obtained samples were subsequently characterized by H2 chemisorption, BET surface area and TEM. Finally, their catalytic performances were evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200mL.min−1, in the same GHSV. The catalytic performance of the Pd catalysts for CO2 purification revealed that: -The support material has a strong influence on the catalytic activity of 1wt.% Pd supported catalysts. depending of the nature of support, the Pd-based catalysts activity changes. -The highest reduction of NO with CO is obtained in the following ranking: TiO2>CeO2>Al2O3. -The supports SiO2 and MgO should be avoided for this reaction, -Total oxidation of CO occurred over different materials, -CO2 purification can reach 97%, -The presence of H2O has a positive effect on the NO reduction due to the production of the reductant H2 from WGS reaction H2O+CO → H2+CO2

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis, oxyfuel combustion

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Authors: Agnieszka Feliczak-Guzik, Paulina Szczyglewska, Izabela Nowak

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A catalyst-assisted oxidation reaction is one of the key reactions exploited by various industries. Their conductivity yields essential compounds and intermediates, such as alcohols, epoxides, aldehydes, ketones, and organic acids. Researchers are devoting more and more attention to developing active and selective materials that find application in many catalytic reactions, such as cyclohexene epoxidation. This reaction yields 1,2-epoxycyclohexane and 1,2-diols as the main products. These compounds are widely used as intermediates in the perfume industry and synthesizing drugs and lubricants. Hence, our research aimed to use hierarchical zeolites modified with transition metal ions, e.g., Nb, V, and Ta, in the epoxidation reaction of cyclohexene using microwaveheating. Hierarchical zeolites are materials with secondary porosity, mainly in the mesoporous range, compared to microporous zeolites. In the course of the research, materials based on two commercial zeolites, with Faujasite (FAU) and Zeolite Socony Mobil-5 (ZSM-5) structures, were synthesized and characterized by various techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and low-temperature nitrogen adsorption/desorption isotherms. The materials obtained were then used in a cyclohexene epoxidation reaction, which was carried out as follows: catalyst (0.02 g), cyclohexene (0.1 cm3), acetonitrile (5 cm3) and dihydrogen peroxide (0.085 cm3) were placed in a suitable glass reaction vessel with a magnetic stirrer inside in a microwave reactor. Reactions were carried out at 45° C for 6 h (samples were taken every 1 h). The reaction mixtures were filtered to separate the liquid products from the solid catalyst and then transferred to 1.5 cm3 vials for chromatographic analysis. The test techniques confirmed the acquisition of additional secondary porosity while preserving the structure of the commercial zeolite (XRD and low-temperature nitrogen adsorption/desorption isotherms). The results of the activity of the hierarchical catalyst modified with niobium in the cyclohexene epoxidation reaction indicate that the conversion of cyclohexene, after 6 h of running the process, is about 70%. As the main product of the reaction, 2-cyclohexanediol was obtained (selectivity > 80%). In addition to the mentioned product, adipic acid, cyclohexanol, cyclohex-2-en-1-one, and 1,2-epoxycyclohexane were also obtained. Furthermore, in a blank test, no cyclohexene conversion was obtained after 6 h of reaction. Acknowledgments The work was carried out within the project “Advanced biocomposites for tomorrow’s economy BIOG-NET,” funded by the Foundation for Polish Science from the European Regional Development Fund (POIR.04.04.00-00-1792/18-00.

Keywords: epoxidation, oxidation reactions, hierarchical zeolites, synthesis

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Authors: Chikang Wang, Jhongjheng Jian, Poming Huang

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Among a wide variety of pharmaceutical compounds, tetracycline antibiotics are one of the largest groups of pharmaceutical compounds extensively used in human and veterinary medicine to treat and prevent bacterial infections. Because it is water soluble, biologically active, stable and bio-refractory, release to the environment threatens aquatic life and increases the risk posed by antibiotic-resistant pathogens. In practice, due to its antibacterial nature, tetracycline cannot be effectively destructed by traditional biological methods. Hence, in this study, two advanced oxidation processes such as ozonation and sono-Fenton processes were conducted individually to degrade the tetracycline for investigating their feasibility on tetracycline degradation. Effect of operational variables on tetracycline degradation, release of nitrogen and change of toxicity were also proposed. Initial tetracycline concentration was 50 mg/L. To evaluate the efficiency of tetracycline degradation by ozonation, the ozone gas was produced by an ozone generator (Model LAB2B, Ozonia) and introduced into the reactor with different flows (25 - 500 mL/min) at varying pH levels (pH 3 - pH 11) and reaction temperatures (15 - 55°C). In sono-Fenton system, an ultrasonic transducer (Microson VCX 750, USA) operated at 20 kHz combined with H₂O₂ (2 mM) and Fe²⁺ (0.2 mM) were carried out at different pH levels (pH 3 - pH 11), aeration gas and flows (air and oxygen; 0.2 - 1.0 L/min), tetracycline concentrations (10 - 200 mg/L), reaction temperatures (15 - 55°C) and ultrasonic powers (25 - 200 Watts), respectively. Sole ultrasound was ineffective on tetracycline degradation, where the degradation efficiencies were lower than 10% with 60 min reaction. Contribution of Fe²⁺ and H₂O₂ on the degradation of tetracycline was significant, where the maximum tetracycline degradation efficiency in sono-Fenton process was as high as 91.3% followed by 45.8% mineralization. Effect of initial pH level on tetracycline degradation was insignificant from pH 3 to pH 6 but significantly decreased as the pH was greater than pH 7. Increase of the ultrasonic power was slightly increased the degradation efficiency of tetracycline, which indicated that the hydroxyl radicals dominated the oxidation of tetracycline. Effects of aeration of air or oxygen with different flows and reaction temperatures were insignificant. Ozonation showed better efficiencies in tetracycline degradation, where the optimum reaction condition was found at pH 3, 100 mL O₃/min and 25°C with 94% degradation and 60% mineralization. The toxicity of tetracycline was significantly decreased due to the mineralization of tetracycline. In addition, less than 10% of nitrogen content was released to solution phase as NH₃-N, and the most degraded tetracycline cannot be full mineralized to CO₂. The results shown in this study indicated that both the sono-Fenton process and ozonation can effectively degrade the tetracycline and reduce its toxicity at profitable condition. The costs of two systems needed to be further investigated to understand the feasibility in tetracycline degradation.

Keywords: degradation, detoxification, mineralization, ozonation, sono-Fenton process, tetracycline

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Authors: Pauline Bredy, Yves Schuurman, David Farrusseng

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To fulfill climate objectives, the production of synthetic e-fuels using CO₂ as a raw material appears as part of the solution. In particular, Power-to-Liquid (PtL) concept combines CO₂ with hydrogen supplied from water electrolysis, powered by renewable sources, which is currently gaining interest as it allows the production of sustainable fossil-free liquid fuels. The proposed process discussed here is an upgrading of the well-known Fischer-Tropsch synthesis. The concept deals with two cascade reactions in one pot, with first the conversion of CO₂ into CO via the reverse water gas shift (RWGS) reaction, which is then followed by the Fischer-Tropsch Synthesis (FTS). Instead of using a Fe-based catalyst, which can carry out both reactions, we have chosen the strategy to decouple the two functions (RWGS and FT) on two different catalysts within the same reactor. The FTS shall shift the equilibrium of the RWGS reaction (which alone would be limited to 15-20% of conversion at 250°C) by converting the CO into hydrocarbons. This strategy shall enable optimization of the catalyst pair and thus lower the temperature of the reaction thanks to the equilibrium shift to gain selectivity in the liquid fraction. The challenge lies in maximizing the activity of the RWGS catalyst but also in the ability of the FT catalyst to be highly selective. Methane production is the main concern as the energetic barrier of CH₄ formation is generally lower than that of the RWGS reaction, so the goal will be to minimize methane selectivity. Here we report the study of different combinations of copper-based RWGS catalysts with different cobalt-based FTS catalysts. We investigated their behaviors under mild process conditions by the use of high-throughput experimentation. Our results show that at 250°C and 20 bars, Cobalt catalysts mainly act as methanation catalysts. Indeed, CH₄ selectivity never drops under 80% despite the addition of various protomers (Nb, K, Pt, Cu) on the catalyst and its coupling with active RWGS catalysts. However, we show that the activity of the RWGS catalyst has an impact and can lead to longer hydrocarbons chains selectivities (C₂⁺) of about 10%. We studied the influence of the reduction temperature on the activity and selectivity of the tandem catalyst system. Similar selectivity and conversion were obtained at reduction temperatures between 250-400°C. This leads to the question of the active phase of the cobalt catalysts, which is currently investigated by magnetic measurements and DRIFTS. Thus, in coupling it with a more selective FT catalyst, better results are expected. This was achieved using a cobalt/iron FTS catalyst. The CH₄ selectivity dropped to 62% at 265°C, 20 bars, and a GHSV of 2500ml/h/gcat. We propose that the conditions used for the cobalt catalysts could have generated this methanation because these catalysts are known to have their best performance around 210°C in classical FTS, whereas the iron catalysts are more flexible but are also known to have an RWGS activity.

Keywords: cobalt-copper catalytic systems, CO₂-hydrogenation, Fischer-Tropsch synthesis, hydrocarbons, low-temperature process

Procedia PDF Downloads 32

Authors: Radek Novotny, Michal Novak, Daniela Marusakova, Monika Sipova, Hugo Fuentes, Peter Borst

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This research has been conducted within the European HORIZON 2020 project ECC-SMART. The main objective is to assess whether it is feasible to design and develop a small modular reactor (SMR) that would be cooled by supercritical water (SCW). One of the main objectives for material research concerns the corrosion of the candidate cladding materials. The experimental part has been conducted in support of the qualification procedure of the future SCW-SMR constructional materials. The last objective was to identify the gaps in current norms and guidelines. Apart from corrosion, resistance testing of candidate materials stresses corrosion cracking susceptibility tests have been performed in supercritical water. This paper describes part of these tests, in particular, those slow strain rate tensile loading applied for tangential ring shape specimens of two candidate materials, Alloy 800H and 310S stainless steel. These ring tensile tests are one the methods used for tensile testing of nuclear cladding. Here full circular heads with dimensions roughly equal to the inner diameter of the sample and the gage sections are placed in the parallel direction to the applied load. Slow strain rate tensile tests have been conducted in 380 or 500oC supercritical water applying two different elongation rates, 1x10-6 and 1x10-7 s-1. The effect of temperature and dissolved oxygen content on the SCC susceptibility of Alloy 800H and 310S stainless steel was investigated when two different temperatures and concentrations of dissolved oxygen were applied in supercritical water. The post-fracture analysis includes fractographic analysis of the fracture surfaces using SEM as well as cross-sectional analysis on the occurrence of secondary cracks. Assessment of the effect of environment and dissolved oxygen content was by comparing to the results of the reference tests performed in air and N2 gas overpressure. The effect of high temperature on creep and its role in the initiation of SCC was assessed as well. It has been concluded that the applied test method could be very useful for the investigation of stress corrosion cracking susceptibility of candidate cladding materials in supercritical water.

Keywords: stress corrosion cracking, ring tensile tests, super-critical water, alloy 800H, 310S stainless steel

Procedia PDF Downloads 57

Authors: Luz Stella Cadavid-Rodriguez, Viviana E. Castro-Lopez

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Fish waste (FW) has a high content of potentially biodegradable components, so it is amenable to be digested anaerobically. In this line, anaerobic digestion (AD) of FW has been studied for biogas production. Nevertheless, intermediate products such as volatile fatty acids (VFA), generated during the acidogenic stage, have been scarce investigated, even though they have a high potential as a renewable source of carbon. In the literature, there are few studies about the Inoculum-Substrate (I/S) ratio on acidogenesis. On the other hand, it is well known that pH is a critical factor in the production of VFA. The optimum pH for the production of VFA seems to change depending on the substrate and can vary in a range between 5.25 and 11. Nonetheless, the literature about VFA production from protein-rich waste, such as FW, is scarce. In this context, it is necessary to deepen on the determination of the optimal operating conditions of acidogenic fermentation for VFA production from protein-rich waste. Therefore, the aim of this research was to optimize the volatile fatty acid production from artisanal fishing waste, studying the effect of pH and the I/S ratio on the acidogenic process. For this research, the inoculum used was a methanogenic sludge (MS) obtained from a UASB reactor treating wastewater of a slaughterhouse plant, and the FW was collected in the port of Tumaco (Colombia) from the local artisanal fishers. The acidogenic fermentation experiments were conducted in batch mode, in 500 mL glass bottles as anaerobic reactors, equipped with rubber stoppers provided with a valve to release biogas. The effective volume used was 300 mL. The experiments were carried out for 15 days at a mesophilic temperature of 37± 2 °C and constant agitation of 200 rpm. The effect of 3 pH levels: 5, 7, 9, coupled with five I/S ratios, corresponding to 0.20, 0.15, 0.10, 0.05, 0.00 was evaluated taking as a response variable the production of VFA. A complete randomized block design was selected for the experiments in a 5x3 factorial arrangement, with two repetitions per treatment. At the beginning and during the process, pH in the experimental reactors was adjusted to the corresponding values of 5, 7, and 9 using 1M NaOH or 1M H2SO4, as was appropriated. In addition, once the optimum I/S ratio was determined, the process was evaluated at this condition without pH control. The results indicated that pH is the main factor in the production of VFA, obtaining the highest concentration with neutral pH. By reducing the I/S ratio, as low as 0.05, it was possible to maximize VFA production. Thus, the optimum conditions found were natural pH (6.6-7.7) and I/S ratio of 0.05, with which it was possible to reach a maximum total VFA concentration of 70.3 g Ac/L, whose major components were acetic acid (35%) and butyric acid (32%). The findings showed that the acidogenic fermentation of FW is an efficient way of producing VFA and that the operating conditions can be simple and economical.

Keywords: acidogenesis, artisanal fishing waste, inoculum to substrate ratio, volatile fatty acids

Procedia PDF Downloads 88

Authors: Nicole Virgili, Marco Utili

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The design of the Breeding Blanket in Tokamak fusion energy systems has to guarantee sufficient availability in addition to its functions, that are, tritium breeding self-sufficiency, power extraction and shielding (the magnets and the VV). All these function in the presence of extremely harsh operating conditions in terms of heat flux and neutron dose as well as chemical environment of the coolant and breeder that challenge structural materials (structural resistance and corrosion resistance). The movement and activation of fluids from the BB to the Ex-vessel components in a fusion power plant have an important radiological consideration because flowing material can carry radioactivity to safety-critical areas. This includes gamma-ray emission from activated fluid and activated corrosion products, and secondary activation resulting from neutron emission, with implication for the safety of maintenance personnel and damage to electrical and electronic equipment. In addition to the PbLi breeder activation, it is important to evaluate the contribution due to the activated corrosion products (ACPs) dissolved in the lead-lithium eutectic alloy, at different concentration levels. Therefore, the purpose of the study project is to evaluate the PbLi activity utilizing the FISPACT II inventory code. Emphasis is given on how the design of the EU-DEMO WCLL, and potential recycling of the breeder material will be impacted by the activation of PbLi and the associated active corrosion products (ACPs). For this scope the following Computational Tools, Data and Geometry have been considered: • Neutron source: EU-DEMO neutron flux < 1014/cm2/s • Neutron flux distribution in equatorial breeding blanket module (BBM) #13 in the WCLL BB outboard central zone, which is the most activated zone, with the aim to introduce a conservative component utilizing MNCP6. • The recommended geometry model: 2017 EU DEMO CAD model. • Blanket Module Material Specifications (Composition) • Activation calculations for different ACP concentration levels in the PbLi breeder, with a given chemistry in stationary equilibrium conditions, using FISPACT II code. Results suggest that there should be a waiting time of about 10 years from the shut-down (SD) to be able to safely manipulate the PbLi for recycling operations with simple shielding requirements. The dose rate is mainly given by the PbLi and the ACP concentration (x1 or x 100) does not shift the result. In conclusion, the results show that there is no impact on PbLi activation due to ACPs levels.

Keywords: activation, corrosion products, recycling, WCLL BB., PbLi

Procedia PDF Downloads 80

Authors: Hellen L. De Castro e Silva, Ana A. Robles Aguilar, Erik Meers

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Digestates are residual by-products, rich in nutrients and trace elements, which can be used as organic fertilisers on soils. However, due to the non-digestibility of these elements and reduced dry matter during the anaerobic digestion process, metal concentrations are higher in digestates than in feedstocks, which might hamper their use as fertilisers according to the threshold values of some country policies. Furthermore, there is uncertainty regarding the required assimilated amount of these elements by some crops, which might result in their bioaccumulation. Therefore, further processing of the digestate to obtain safe fertilizing products has been recommended. This research aims to analyze the effect of applying the hydrothermal carbonization process to manure-derived digestates as a thermal treatment to reduce the bioavailability of heavy metals in mono and co-digestates derived from pig manure and maize from contaminated land in France. This study examined pig manure collected from a novel stable system (VeDoWs, province of East Flanders, Belgium) that separates the collection of pig urine and feces, resulting in a solid fraction of manure with high up-concentration of heavy metals and nutrients. Mono-digestion and co-digestion processes were conducted in semi-continuous reactors for 45 days at mesophilic conditions, in which the digestates were dried at 105 °C for 24 hours. Then, hydrothermal carbonization was applied to a 1:10 solid/water ratio to guarantee controlled experimental conditions in different temperatures (180, 200, and 220 °C) and residence times (2 h and 4 h). During the process, the pressure was generated autogenously, and the reactor was cooled down after completing the treatments. The solid and liquid phases were separated through vacuum filtration, in which the solid phase of each treatment -hydrochar- was dried and ground for chemical characterization. Different fractions (exchangeable / adsorbed fraction - F1, carbonates-bound fraction - F2, organic matter-bound fraction - F3, and residual fraction – F4) of some heavy metals (Cd, Cr, Ni, and Cr) have been determined in digestates and derived hydrochars using the modified Community Bureau of Reference (BCR) sequential extraction procedure. The main results indicated a difference in the heavy metals fractionation between digestates and their derived hydrochars; however, the hydrothermal carbonization operating conditions didn’t have remarkable effects on heavy metals partitioning between the hydrochars of the proposed treatments. Based on the estimated potential ecological risk assessment, there was one level decrease (considerate to moderate) when comparing the HMs partitioning in digestates and derived hydrochars.

Keywords: heavy metals, bioavailability, hydrothermal treatment, bio-based fertilisers, agriculture

Procedia PDF Downloads 66

Authors: Muhammad Zaman Shakir, Mingfa Yao, Zohaib Iqbal

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This study proposed four Jet fuel surrogate (S1, S2 S3, and 4) with careful selection of seven large hydrocarbon fuel components, ranging from C₉-C₁₆ of higher molecular weight and higher boiling point, adapting the standard molecular distribution size of the actual jet fuel. The surrogate was composed of seven components, including n-propyl cyclohexane (C₉H₁₈), n- propylbenzene (C₉H₁₂), n-undecane (C₁₁H₂₄), n- dodecane (C₁₂H₂₆), n-tetradecane (C₁₄H₃₀), n-hexadecane (C₁₆H₃₄) and iso-cetane (iC₁₆H₃₄). The skeletal jet fuel surrogate reaction mechanism was developed by two approaches, firstly based on a decoupling methodology by describing the C₄ -C₁₆ skeletal mechanism for the oxidation of heavy hydrocarbons and a detailed H₂ /CO/C₁ mechanism for prediction of oxidation of small hydrocarbons. The combined skeletal jet fuel surrogate mechanism was compressed into 128 species, and 355 reactions and thereby can be used in computational fluid dynamics (CFD) simulation. The extensive validation was performed for individual single-component including ignition delay time, species concentrations profile and laminar flame speed based on various fundamental experiments under wide operating conditions, and for their blended mixture, among all the surrogate, S1 has been extensively validated against the experimental data in a shock tube, rapid compression machine, jet-stirred reactor, counterflow flame, and premixed laminar flame over wide ranges of temperature (700-1700 K), pressure (8-50 atm), and equivalence ratio (0.5-2.0) to capture the properties target fuel Jet-A, while the rest of three surrogate S2, S3 and S4 has been validated for Shock Tube ignition delay time only to capture the ignition characteristic of target fuel S-8 & GTL, IPK and RP-3 respectively. Based on the newly proposed HyChem model, another four surrogate with similar components and composition, was developed and parallel validations data was used as followed for previously developed surrogate but at high-temperature condition only. After testing the mechanism prediction performance of surrogates developed by the decoupling methodology, the comparison was done with the results of surrogates developed by the HyChem model. It was observed that all of four proposed surrogates in this study showed good agreement with the experimental measurements and the study comes to this conclusion that like the decoupling methodology HyChem model also has a great potential for the development of oxidation mechanism for heavy alkanes because of applicability, simplicity, and compactness.

Keywords: computational fluid dynamics, decoupling methodology Hychem, jet fuel, surrogate, skeletal mechanism

Procedia PDF Downloads 103

Authors: Viviane P. Romani, Bradley D. Olsen, Vilásia G. Martins

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Biodegradable films for food packaging have gained growing attention due to environmental pollution caused by synthetic films and the interest in the better use of resources from nature. Important research advances were made in the development of materials from proteins, polysaccharides, and lipids. However, the commercial use of these new generation of sustainable materials for food packaging is still limited due to their low mechanical and barrier properties that could compromise the food quality and safety. Thus, strategies to improve the performance of these materials have been tested, such as chemical modifications, incorporation of reinforcing structures and others. Cold plasma is a versatile, fast and environmentally friendly technology. It consists of a partially ionized gas containing free electrons, ions, and radicals and neutral particles able to react with polymers and start different reactions, leading to the polymer degradation, functionalization, etching and/or cross-linking. In the present study, biodegradable films from fish protein prepared through the casting technique were plasma treated using an AC glow discharge equipment. The reactor was preliminary evacuated to ~7 Pa and the films were exposed to air plasma for 2, 5 and 8 min. The films were evaluated by their mechanical and water vapor permeability (WVP) properties and changes in the protein structure were observed using Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD). Potential cross-links and elimination of surface defects by etching might be the reason for the increase in tensile strength and decrease in the elongation at break observed. Among the times of plasma application tested, no differences were observed when higher times of exposure were used. The X-ray pattern showed a broad peak at 2θ = 19.51º that corresponds to the distance of 4.6Å by applying the Bragg’s law. This distance corresponds to the average backbone distance within the α-helix. Thus, the changes observed in the films might indicate that the helical configuration of fish protein was disturbed by plasma treatment. SEM images showed surface damage in the films with 5 and 8 min of plasma treatment, indicating that 2 min was the most adequate time of treatment. It was verified that plasma removes water from the films once weight loss of 4.45% was registered for films treated during 2 min. However, after 24 h in 50% of relative humidity, the water lost was recovered. WVP increased from 0.53 to 0.65 g.mm/h.m².kPa after plasma treatment during 2 min, that is desired for some foods applications which require water passage through the packaging. In general, the plasma technology affects the properties and structure of fish protein films. Since this technology changes the surface of polymers, these films might be used to develop multilayer materials, as well as to incorporate active substances in the surface to obtain active packaging.

Keywords: fish protein films, food packaging, improvement of properties, plasma treatment

Procedia PDF Downloads 139

Authors: S. Agarwal, A. Rani

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Catechol is a natural polyphenolic compound that widely exists in higher plants such as teas, vegetables, fruits, tobaccos, and some traditional Chinese medicines. The fly ash-based zeolites are capable of absorbing a wide range of pollutants. But the process of zeolite synthesis is time-consuming and requires technical setups by the industries. The marketed costs of zeolites are quite high restricting its use by small-scale industries for the removal of phenolic compounds. The present research proposes a simple method of alkaline treatment of FA to produce an effective adsorbent for catechol removal from wastewater. The experimental parameter such as pH, temperature, initial concentration and adsorbent dose on the removal of catechol were studied in batch reactor. For this purpose the adsorbent materials were mixed with aqueous solutions containing catechol ranging in 50 – 200 mg/L initial concentrations and then shaken continuously in a thermostatic Orbital Incubator Shaker at 30 ± 0.1 °C for 24 h. The samples were withdrawn from the shaker at predetermined time interval and separated by centrifugation (Centrifuge machine MBL-20) at 2000 rpm for 4 min. to yield a clear supernatant for analysis of the equilibrium concentrations of the solutes. The concentrations were measured with Double Beam UV/Visible spectrophotometer (model Spectrscan UV 2600/02) at the wavelength of 275 nm for catechol. In the present study, the use of low-cost adsorbent (BTFA) derived from coal fly ash (FA), has been investigated as a substitute of expensive methods for the sequestration of catechol. The FA and BTFA adsorbents were well characterized by XRF, FE-SEM with EDX, FTIR, and surface area and porosity measurement which proves the chemical constituents, functional groups and morphology of the adsorbents. The catechol adsorption capacities of synthesized BTFA and native material were determined. The adsorption was slightly increased with an increase in pH value. The monolayer adsorption capacities of FA and BTFA for catechol were 100 mg g⁻¹ and 333.33 mg g⁻¹ respectively, and maximum adsorption occurs within 60 minutes for both adsorbents used in this test. The equilibrium data are fitted by Freundlich isotherm found on the basis of error analysis (RMSE, SSE, and χ²). Adsorption was found to be spontaneous and exothermic on the basis of thermodynamic parameters (ΔG°, ΔS°, and ΔH°). Pseudo-second-order kinetic model better fitted the data for both FA and BTFA. BTFA showed large adsorptive characteristics, high separation selectivity, and excellent recyclability than FA. These findings indicate that BTFA could be employed as an effective and inexpensive adsorbent for the removal of catechol from wastewater.

Keywords: catechol, fly ash, isotherms, kinetics, thermodynamic parameters

Procedia PDF Downloads 99

Authors: Haseen Siddiqui, Sanjay M. Mahajani

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Various important reactions in chemical and metallurgical industries fall in the category of gas-solid reactions. These reactions can be categorized as catalytic and non-catalytic gas-solid reactions. In gas-solid reaction systems, heat and mass transfer limitations put an appreciable influence on the rate of the reaction. The consequences can be unavoidable for overlooking such effects while collecting the reaction rate data for the design of the reactor. Pyrolysis reaction comes in this category that involves the production of gases due to the interaction of heat and solid substance. Pyrolysis is also an important step in the gasification process and therefore, the gasification reactivity majorly influenced by the pyrolysis process that produces the char, as a feed for the gasification process. Therefore, in the present study, a non-isothermal transient 1-D model is developed for a single biomass pellet to investigate the effect of heat and mass transfer limitations on the rate of pyrolysis reaction. The obtained set of partial differential equations are firstly discretized using the concept of ‘method of lines’ to obtain a set of ordinary differential equation with respect to time. These equations are solved, then, using MATLAB ode solver ode15s. The model is capable of incorporating structural changes, porosity variation, variation in various thermal properties and various pellet shapes. The model is used to analyze the effectiveness factor for different values of Lewis number and heat of reaction (G factor). Lewis number includes the effect of thermal conductivity of the solid pellet. Higher the Lewis number, the higher will be the thermal conductivity of the solid. The effectiveness factor was found to be decreasing with decreasing Lewis number due to the fact that smaller Lewis numbers retard the rate of heat transfer inside the pellet owing to a lower rate of pyrolysis reaction. G factor includes the effect of the heat of reaction. Since the pyrolysis reaction is endothermic in nature, the G factor takes negative values. The more the negative value higher will be endothermic nature of the pyrolysis reaction. The effectiveness factor was found to be decreasing with more negative values of the G factor. This behavior can be attributed to the fact that more negative value of G factor would result in more energy consumption by the reaction owing to a larger temperature gradient inside the pellet. Further, the analytical expressions are also derived for gas and solid concentrations and effectiveness factor for two limiting cases of the general model developed. The two limiting cases of the model are categorized as the homogeneous model and unreacted shrinking core model.

Keywords: effectiveness factor, G-factor, homogeneous model, lewis number, non-catalytic, shrinking core model

Procedia PDF Downloads 99

Authors: masmoudi Jabri Khaoula, Zitouni Hana, Bousselmi Latifa, Akrout Hanen

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Mathematical modeling has become an essential tool for sustainable wastewater management, particularly for the simulation and the optimization of complex processes involved in activated sludge systems. In this context, the activated sludge model (ASM3h) was used for the simulation of a Biological Membrane Reactor (MBR) as it includes the integration of biological wastewater treatment and physical separation by membrane filtration. In this study, the MBR with a useful volume of 12.5 L was fed continuously with poultry slaughterhouse wastewater (PSWW) for 50 days at a feed rate of 2 L/h and for a hydraulic retention time (HRT) of 6.25h. Throughout its operation, High removal efficiency was observed for the removal of organic pollutants in terms of COD with 84% of efficiency. Moreover, the MBR has generated a treated effluent which fits with the limits of discharge into the public sewer according to the Tunisian standards which were set in March 2018. In fact, for the nitrogenous compounds, average concentrations of nitrate and nitrite in the permeat reached 0.26±0.3 mg. L-1 and 2.2±2.53 mg. L-1, respectively. The simulation of the MBR process was performed using SIMBA software v 5.0. The state variables employed in the steady state calibration of the ASM3h were determined using physical and respirometric methods. The model calibration was performed using experimental data obtained during the first 20 days of the MBR operation. Afterwards, kinetic parameters of the model were adjusted and the simulated values of COD, N-NH4+and N- NOx were compared with those reported from the experiment. A good prediction was observed for the COD, N-NH4+and N- NOx concentrations with 467 g COD/m³, 110.2 g N/m³, 3.2 g N/m³ compared to the experimental data which were 436.4 g COD/m³, 114.7 g N/m³ and 3 g N/m³, respectively. For the validation of the model under dynamic simulation, the results of the experiments obtained during the second treatment phase of 30 days were used. It was demonstrated that the model simulated the conditions accurately by yielding a similar pattern on the variation of the COD concentration. On the other hand, an underestimation of the N-NH4+ concentration was observed during the simulation compared to the experimental results and the measured N-NO3 concentrations were lower than the predicted ones, this difference could be explained by the fact that the ASM models were mainly designed for the simulation of biological processes in the activated sludge systems. In addition, more treatment time could be required by the autotrophic bacteria to achieve a complete and stable nitrification. Overall, this study demonstrated the effectiveness of mathematical modeling in the prediction of the performance of the MBR systems with respect to organic pollution, the model can be further improved for the simulation of nutrients removal for a longer treatment period.

Keywords: activated sludge model (ASM3h), membrane bioreactor (MBR), poultry slaughter wastewater (PSWW), reuse

Procedia PDF Downloads 18

Authors: Danish Laidin, Peter Gostomski, Aaron Marshall, Carlo Carere

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Groundwater contamination of nitrate (NO3-) is becoming more prevalent in regions of intensive and extensive agricultural activities. Household nitrate removal involves using ion exchange membranes and reverse osmosis (RO) systems, whereas industrial nitrate removal may use organic carbon substrates (e.g. methanol) for heterotrophic microbial denitrification. However, these approaches both require high capital investment and operating costs. In this study, denitrification was demonstrated using bio-electrochemical systems (BESs) inoculated from sediments and microbial enrichment cultures. The BES reactors were operated continuously as microbial electrolytic cells (MECs) with a poised potential of -0.7V and -1.1V vs Ag/AgCl. Three parallel MECs were inoculated using hydrogen-driven denitrifying enrichments, stream sediments, and biofilm harvested from a denitrifying biotrickling filter, respectively. These reactors were continuously operated for over a year as various operating conditions were investigated to determine the optimal conditions for electroactive denitrification. The mass loading rate of nitrate was varied between 10 – 70 mg NO3-/d, and the maximum observed nitrate removal rate was 22 mg NO3- /(cm2∙d) with a current of 2.1 mA. For volumetric load experiments, the dilution rate of 1 mM NO3- feed was varied between 0.01 – 0.1 hr-1 to achieve a nitrate loading rate similar to the mass loading rate experiments. Under these conditions, the maximum rate of denitrification observed was 15.8 mg NO3- /(cm2∙d) with a current of 1.7mA. Hydrogen (H2) was supplied intermittently to investigate the hydrogenotrophic potential of the denitrifying biofilm electrodes. H2 supplementation at 0.1 mL/min resulted in an increase of nitrate removal from 0.3 mg NO3- /(cm2∙d) to 3.4 mg NO3- /(cm2∙d) in the hydrogenotrophically subcultured reactor but had no impact on the reactors which exhibited direct electron transfer properties. Results from this study depict the denitrification performance of the immobilized biofilm electrodes, either by direct electron transfer or hydrogen-driven denitrification, and the contribution of the planktonic cells present in the growth medium. Other results will include the microbial community analysis via 16s rDNA amplicon sequencing, varying the effect of poising cathodic potential from 0.7V to 1.3V vs Ag/AgCl, investigating the potential of using in-situ electrochemically produced hydrogen for autotrophic denitrification and adjusting the conductivity of the feed solution to mimic groundwater conditions. These findings highlight the overall performance of sediment inoculated MECs in removing nitrate and will be used for the future development of sustainable solutions for the treatment of nitrate polluted groundwater.

Keywords: bio-electrochemical systems, groundwater, electroactive denitrification, microbial electrolytic cell

Procedia PDF Downloads 41

Authors: I. Nitoi, P. Oancea, M. Raileanu, M. Crisan, L. Constantin, I. Cristea

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Hazardous organic compounds like nitroaromatics are frequently found in chemical and petroleum industries discharged effluents. Due to their bio-refractory character and high chemical stability cannot be efficiently removed by classical biological or physical-chemical treatment processes. In the past decades, semiconductor photocatalysis has been frequently applied for the advanced degradation of toxic pollutants. Among various semiconductors titania was a widely studied photocatalyst, due to its chemical inertness, low cost, photostability and nontoxicity. In order to improve optical absorption and photocatalytic activity of TiO2 many attempts have been made, one feasible approach consists of doping oxide semiconductor with metal. The degradation of dinitrobenzene (DNB) and dinitrotoluene (DNT) from aqueous solution under UVA-VIS irradiation using heavy metal (0.5% Fe, 1%Co, 1%Ni ) doped titania was investigated. The photodegradation experiments were carried out using a Heraeus laboratory scale UV-VIS reactor equipped with a medium-pressure mercury lamp which emits in the range: 320-500 nm. Solutions with (0.34-3.14) x 10-4 M pollutant content were photo-oxidized in the following working conditions: pH = 5-9; photocatalyst dose = 200 mg/L; irradiation time = 30 – 240 minutes. Prior to irradiation, the photocatalyst powder was added to the samples, and solutions were bubbled with air (50 L/hour), in the dark, for 30 min. Dopant type, pH, structure and initial pollutant concentration influence on the degradation efficiency were evaluated in order to set up the optimal working conditions which assure substrate advanced degradation. The kinetics of nitroaromatics degradation and organic nitrogen mineralization was assessed and pseudo-first order rate constants were calculated. Fe doped photocatalyst with lowest metal content (0.5 wt.%) showed a considerable better behaviour in respect to pollutant degradation than Co and Ni (1wt.%) doped titania catalysts. For the same working conditions, degradation efficiency was higher for DNT than DNB in accordance with their calculated adsobance constants (Kad), taking into account that degradation process occurs on catalyst surface following a Langmuir-Hinshalwood model. The presence of methyl group in the structure of DNT allows its degradation by oxidative and reductive pathways, while DNB is converted only by reductive route, which also explain the highest DNT degradation efficiency. For highest pollutant concentration tested (3 x 10-4 M), optimum working conditions (0.5 wt.% Fe doped –TiO2 loading of 200 mg/L, pH=7 and 240 min. irradiation time) assures advanced nitroaromatics degradation (ηDNB=89%, ηDNT=94%) and organic nitrogen mineralization (ηDNB=44%, ηDNT=47%).

Keywords: hazardous organic compounds, irradiation, nitroaromatics, photocatalysis

Procedia PDF Downloads 282

Authors: Debalina Ghoshal

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Nuclear security is the ‘prevention and detection of, and response to unauthorised removal, sabotage, unauthorised access, illegal transfer or other malicious acts involving nuclear or radiological material or their associated facilities.’ Ever since the end of Cold War, nuclear materials security has remained a concern for global security. However, with the increase in terrorist attacks not just in India especially, security of nuclear materials remains a priority. Therefore, India has made continued efforts to tighten its security on nuclear materials to prevent nuclear theft and radiological terrorism. Nuclear security is different from nuclear safety. Physical security is also a serious concern and India had been careful of the physical security of its nuclear materials. This is more so important since India is expanding its nuclear power capability to generate electricity for economic development. As India targets 60,000 MW of electricity production by 2030, it has a range of reactors to help it achieve its goal. These include indigenous Pressurised Heavy Water Reactors, now standardized at 700 MW per reactor Light Water Reactors, and the indigenous Fast Breeder Reactors that can generate more fuel for the future and enable the country to utilise its abundant thorium resource. Nuclear materials security can be enhanced through two important ways. One is through proliferation resistant technologies and diplomatic efforts to take non proliferation initiatives. The other is by developing technical means to prevent any leakage in nuclear materials in the hands of asymmetric organisations. New Delhi has already implemented IAEA Safeguards on their civilian nuclear installations. Moreover, the IAEA Additional Protocol has also been ratified by India in order to enhance its transparency of nuclear material and strengthen nuclear security. India is a party to the IAEA Conventions on Nuclear Safety and Security, and in particular the 1980 Convention on the Physical Protection of Nuclear Material and its amendment in 2005, Code of Conduct in Safety and Security of Radioactive Sources, 2006 which enables the country to provide for the highest international standards on nuclear and radiological safety and security. India's nuclear security approach is driven by five key components: Governance, Nuclear Security Practice and Culture, Institutions, Technology and International Cooperation. However, there is still scope for further improvements to strengthen nuclear materials and nuclear security. The NTI Report, ‘India’s improvement reflects its first contribution to the IAEA Nuclear Security Fund etc. in the future, India’s nuclear materials security conditions could be further improved by strengthening its laws and regulations for security and control of materials, particularly for control and accounting of materials, mitigating the insider threat, and for the physical security of materials during transport. India’s nuclear materials security conditions also remain adversely affected due to its continued increase in its quantities of nuclear material, and high levels of corruption among public officials.’ This paper would study briefly the progress made by India in nuclear and nuclear material security and the step ahead for India to further strengthen this.

Keywords: India, nuclear security, nuclear materials, non proliferation

Procedia PDF Downloads 320

Authors: A. Kesraoui, M. Seffen

Abstract:

Applications of adsorption onto activated carbon for water treatment are well known. The process has been demonstrated to be widely effective for removing dissolved organic substances from wastewaters, but this treatment has a major drawback is the high operating cost. The main goal of our research work is to improve the retention capacity of Tunisian biomass for the depollution of industrial wastewater and retention of pollutants considered toxic. The biosorption process is based on the retention of molecules and ions onto a solid surface composed of biological materials. The evaluation of the potential use of these materials is important to propose as an alternative to the adsorption process generally expensive, used to remove organic compounds. Indeed, these materials are very abundant in nature and are low cost. Certainly, the biosorption process is effective to remove the pollutants, but it presents a slow kinetics. The improvement of the biosorption rates is a challenge to make this process competitive with respect to oxidation and adsorption onto lignocellulosic fibers. In this context, the alternating current appears as a new alternative, original and a very interesting phenomenon in the acceleration of chemical reactions. Our main goal is to increase the retention acceleration of dyes (indigo carmine, methylene blue) and phenol by using a new alternative: alternating current. The adsorption experiments have been performed in a batch reactor by adding some of the adsorbents in 150 mL of pollutants solution with the desired concentration and pH. The electrical part of the mounting comprises a current source which delivers an alternating current voltage of 2 to 15 V. It is connected to a voltmeter that allows us to read the voltage. In a 150 mL capacity cell, we plunged two zinc electrodes and the distance between two Zinc electrodes has been 4 cm. Thanks to alternating current, we have succeeded to improve the performance of activated carbon by increasing the speed of the indigo carmine adsorption process and reducing the treatment time. On the other hand, we have studied the influence of the alternating current on the biosorption rate of methylene blue onto Luffa cylindrica fibers and the hybrid material (Luffa cylindrica-ZnO). The results showed that the alternating current accelerated the biosorption rate of methylene blue onto the Luffa cylindrica and the Luffa cylindrica-ZnO hybrid material and increased the adsorbed amount of methylene blue on both adsorbents. In order to improve the removal of phenol, we performed the coupling between the alternating current and the biosorption onto two adsorbents: Luffa cylindrica and the hybrid material (Luffa cylindrica-ZnO). In fact, the alternating current has succeeded to improve the performance of adsorbents by increasing the speed of the adsorption process and the adsorption capacity and reduce the processing time.

Keywords: adsorption, alternating current, dyes, modeling

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Authors: Guanyu Jiang, Donghai Xu, Huanteng Liu

Abstract:

After the Fukushima-Daiichi accident, the development of accident tolerant fuel cladding materials to improve reactor safety has become a hot topic in the field of nuclear industry. ZrO₂ has a satisfactory neutron economy and can guarantee the fission chain reaction process, which enables it to be a promising coating for zirconium alloy cladding. Maintaining a good corrosion resistance in primary coolant loop during normal operations of Pressurized Water Reactors is a prerequisite for ZrO₂ as a protective coating on zirconium alloy cladding. Research on the corrosion performance of ZrO₂ coating in nuclear water chemistry is relatively scarce, and existing reports failed to provide an in-depth explanation for the failure causes of ZrO₂ coating. Herein, a detailed corrosion process of ZrO₂ coating in lithiated water at 360 °C and 18.5 MPa was proposed based on experimental research and molecular dynamics simulation. Lithiated water with different LiOH solutions in the present work was deaerated and had a dissolved oxygen concentration of < 10 ppb. The concentration of Li (as LiOH) was determined to be 2.3 ppm, 70 ppm, and 500 ppm, respectively. Corrosion tests were conducted in a static autoclave. Modeling and corresponding calculations were operated on Materials Studio software. The calculation of adsorption energy and dynamics parameters were undertaken by the Energy task and Dynamics task of the Forcite module, respectively. The protective effect and failure mechanism of ZrO₂ coating on Zry-4 under varied LiOH concentrations was further revealed by comparison with the coating corrosion performance in pure water (namely 0 ppm Li). ZrO₂ coating provided a favorable corrosion protection with the occurrence of localized corrosion at low LiOH concentrations. Factors influencing corrosion resistance mainly include pitting corrosion extension, enhanced Li+ permeation, short-circuit diffusion of O²⁻ and ZrO₂ phase transformation. In highly-concentrated LiOH solutions, intergranular corrosion, internal oxidation, and perforation resulted in coating failure. Zr ions were released to coating surface to form flocculent ZrO₂ and ZrO₂ clusters due to the strong diffusion and dissolution tendency of α-Zr in the Zry-4 substrate. Considering that primary water of Pressurized Water Reactors usually includes 2.3 ppm Li, the stability of ZrO₂ make itself a candidate fuel cladding coating material. Under unfavorable conditions with high Li concentrations, more boric acid should be added to alleviate caustic corrosion of ZrO₂ coating once it is used. This work can provide some references to understand the service behavior of nuclear coatings under variable water chemistry conditions and promote the in-pile application of ZrO₂ coating.

Keywords: ZrO₂ coating, Zry-4, corrosion behavior, failure mechanism, LiOH concentration

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Authors: Smita Mondal, Dinesh Kumar Pandey, Prakash Biswas

Abstract:

During past two decades, considerable attention has been given to the value addition of biodiesel derived glycerol (~10wt.%) to make the biodiesel industry economically viable. Among the various glycerol value-addition methods, hydrogenolysis of glycerol to 1,2-propanediol is one of the attractive and promising routes. In this study, highly active and selective γ-Al₂O₃ supported bimetallic Cu-Ni catalyst was developed for selective hydrogenolysis of glycerol to 1,2-propanediol in the liquid phase. The catalytic performance was evaluated in a high-pressure autoclave reactor. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. Experimental results demonstrated that bimetallic copper-nickel catalyst was more active and selective to 1,2-PDO as compared to monometallic catalysts due to bifunctional behavior. To verify the effect of calcination temperature on the formation of Cu-Ni mixed oxide phase, the calcination temperature of 20wt.% Cu:Ni(1:1)/Al₂O₃ catalyst was varied from 300°C-550°C. The physicochemical properties of the catalysts were characterized by various techniques such as specific surface area (BET), X-ray diffraction study (XRD), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). The BET surface area and pore volume of the catalysts were in the range of 71-78 m²g⁻¹, and 0.12-0.15 cm³g⁻¹, respectively. The peaks at the 2θ range of 43.3°-45.5° and 50.4°-52°, was corresponded to the copper-nickel mixed oxidephase [JCPDS: 78-1602]. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. The crystallite size decreased with increasing the calcination temperature up to 450°C. Further, the crystallite size was increased due to agglomeration. Smaller crystallite size of 16.5 nm was obtained for the catalyst calcined at 400°C. Total acidic sites of the catalysts were determined by NH₃-TPD, and the maximum total acidic of 0.609 mmol NH₃ gcat⁻¹ was obtained over the catalyst calcined at 400°C. TPR data suggested the maximum of 75% degree of reduction of catalyst calcined at 400°C among all others. Further, 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst calcined at 400°C exhibited highest catalytic activity ( > 70%) and 1,2-PDO selectivity ( > 85%) at mild reaction condition due to highest acidity, highest degree of reduction, smallest crystallite size. Further, the modified Power law kinetic model was developed to understand the true kinetic behaviour of hydrogenolysis of glycerol over 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst. Rate equations obtained from the model was solved by ode23 using MATLAB coupled with Genetic Algorithm. Results demonstrated that the model predicted data were very well fitted with the experimental data. The activation energy of the formation of 1,2-PDO was found to be 45 kJ mol⁻¹.

Keywords: glycerol, 1, 2-PDO, calcination, kinetic

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