Search results for: K-M reactor

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

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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

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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

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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

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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

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Authors: A. Kesraoui, M. Seffen

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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

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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

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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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Authors: Thomas S. Abia II

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Intel Chandler Site has internally developed its first-of-kind (FOK) facility-scale wastewater treatment system to achieve multi-metal ion exchange. The process was carried out using a serial process train of carbon filtration, pH / ORP adjustment, and cationic exchange purification to treat dilute metal wastewater (DMW) discharged from a substrate packaging factory. Spanning a trial period of 10 months, a total of 3,271 samples were collected and statistically analyzed (average baseline + standard deviation) to evaluate the performance of a 95-gpm, multi-reactor continuous copper ion exchange treatment system that was consequently retrofitted for manganese ion exchange to meet environmental regulations. The system is also equipped with an inline acid and hot caustic regeneration system to rejuvenate exhausted IX resins and occasionally remove surface crud. Data generated from lab-scale studies was transferred to system operating modifications following multiple trial-and-error experiments. Despite the DMW treatment system failing to meet internal performance specifications for manganese output, it was observed to remove the cation notwithstanding the prevalence of copper in the waste stream. Accordingly, the average manganese output declined from 6.5 + 5.6 mg¹L⁻¹ at pre-pilot to 1.1 + 1.2 mg¹L⁻¹ post-pilot (83% baseline reduction). This milestone was achieved regardless of the average influent manganese to DMW increasing from 1.0 + 13.7 mg¹L⁻¹ at pre-pilot to 2.1 + 0.2 mg¹L⁻¹ post-pilot (110% baseline uptick). Likewise, the pre-trial and post-trial average influent copper values to DMW were 22.4 + 10.2 mg¹L⁻¹ and 32.1 + 39.1 mg¹L⁻¹, respectively (43% baseline increase). As a result, the pre-trial and post-trial average copper output values were 0.1 + 0.5 mg¹L⁻¹ and 0.4 + 1.2 mg¹L⁻¹, respectively (300% baseline uptick). Conclusively, the operating pH range upstream of treatment (between 3.5 and 5) was shown to be the largest single point of influence for optimizing manganese uptake during multi-metal ion exchange. However, the high variability of the influent copper-to-manganese ratio was observed to adversely impact the system functionality. The journal herein intends to discuss the operating parameters such as pH and oxidation-reduction potential (ORP) that were shown to influence the functional versatility of the ion exchange system significantly. The literature also proposes to discuss limitations of the treatment system such as influent copper-to-manganese ratio variations, operational configuration, waste by-product management, and system recovery requirements to provide a balanced assessment of the multi-metal ion exchange process. The take-away from this literature is intended to analyze the overall feasibility of ion exchange for metals manufacturing facilities that lack the capability to expand hardware due to real estate restrictions, aggressive schedules, or budgetary constraints.

Keywords: copper, industrial wastewater treatment, multi-metal ion exchange, manganese

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Authors: Johan Buermans, Kristel Crombé, Niek Desmet, Laura Dittrich, Andrei Goriaev, Yurii Kovtun, Daniel López-Rodriguez, Sören Möller, Per Petersson, Maja Verstraeten

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The International Thermonuclear Experimental Reactor (ITER) will rely on three sources of external heating to produce and sustain a plasma; Neutral Beam Injection (NBI), Ion Cyclotron Resonance Heating (ICRH), and Electron Cyclotron Resonance Heating (ECRH). ECRH is a way to heat the electrons in a plasma by resonant absorption of electromagnetic waves. The energy of the electrons is transferred indirectly to the ions by collisions. The electron cyclotron heating system can be directed to deposit heat in particular regions in the plasma (https://www.iter.org/mach/Heating). Electron Cyclotron Resonance Heating (ECRH) at the fundamental resonance in X-mode is limited by a low cut-off density. Electromagnetic waves cannot propagate in the region between this cut-off and the Upper Hybrid Resonance (UHR) and cannot reach the Electron Cyclotron Resonance (ECR) position. Higher harmonic heating is hence preferred in heating scenarios nowadays to overcome this problem. Additional power deposition mechanisms can occur above this threshold to increase the plasma density. This includes collisional losses in the evanescent region, resonant power coupling at the UHR, tunneling of the X-wave with resonant coupling at the ECR, and conversion to the Electron Bernstein Wave (EBW) with resonant coupling at the ECR. A more profound knowledge of these deposition mechanisms can help determine the optimal plasma production scenarios. Several ECRH experiments are performed on the TOroidally MAgnetized System (TOMAS) to identify the conditions for Electron Bernstein Wave (EBW) heating. Density and temperature profiles are measured with movable Triple Langmuir Probes in the horizontal and vertical directions. Measurements of the forwarded and reflected power allow evaluation of the coupling efficiency. Optical emission spectroscopy and camera images also contribute to plasma characterization. The influence of the injected power, magnetic field, gas pressure, and wave polarization on the different deposition mechanisms is studied, and the contribution of the Electron Bernstein Wave is evaluated. The TOMATOR 1D hydrogen-helium plasma simulator numerically describes the evolution of current less magnetized Radio Frequency plasmas in a tokamak based on Braginskii’s legal continuity and heat balance equations. This code was initially benchmarked with experimental data from TCV to determine the transport coefficients. The code is used to model the plasma parameters and the power deposition profiles. The modeling is compared with the data from the experiments.

Keywords: electron Bernstein wave, Langmuir probe, plasma characterization, TOMAS

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Authors: Alessio Varotto, Lorenzo Freschi, Umberto Pasqual Laverdura, Anastasia Moschovi, Davide Pumiglia, Iakovos Yakoumis, Marta Feroci, Maria Luisa Grilli

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Dry reforming of Methane (DRM) is considered one of the most valuable technologies for green-house gas valorization thanks to the fact that through this reaction, it is possible to obtain syngas, a mixture of H₂ and CO in an H₂/CO ratio suitable for utilization in the Fischer-Tropsch process of high value-added chemicals and fuels. Challenges of the DRM process are the reduction of costs due to the high temperature of the process and the high cost of precious metals of the catalyst, the metal particles sintering, and carbon deposition on the catalysts’ surface. The aim of this study is to demonstrate the feasibility of the synthesis of catalysts using a leachate solution containing Pt coming directly from the recovery of spent diesel oxidation catalysts (DOCs) without further purification. An unusual perovskite support for DRM, the BaCe₁₋ₓ₋ᵧZrₓGdᵧO₃ (BCZG) perovskite, has been chosen as the catalyst support because of its high thermal stability and capability to produce oxygen vacancies, which suppress the carbon deposition and enhance the catalytic activity of the catalyst. BCZG perovskite has been synthesized by a sol-gel modified Pechini process and calcinated in air at 1100 °C. BCZG supports have been impregnated with a Pt-containing leachate solution of DOC, obtained by a mild hydrometallurgical recovery process, as reported elsewhere by some of the authors of this manuscript. For comparison reasons, a synthetic solution obtained by digesting commercial Pt-black powder in aqua regia was used for BCZG support impregnation. Pt nominal content was 2% in both BCZG-based catalysts formed by real and synthetic solutions. The structure and morphology of catalysts were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Thermogravimetric Analysis (TGA) was used to study the thermal stability of the catalyst’s samples. Brunauer-Emmett-Teller (BET) analysis provided a high surface area of the catalysts. H₂-TPR (Temperature Programmed Reduction) analysis was used to study the consumption of hydrogen for reducibility, and it was associated with H₂-TPD characterization to study the dispersion of Pt on the surface of the support and calculate the number of active sites used by the precious metal. Dry reforming of methane (DRM) reaction, carried out in a fixed bed reactor, showed a high conversion efficiency of CO₂ and CH4. At 850°C, CO₂ and CH₄ conversion were close to 100% for the catalyst obtained with the aqua regia-based solution of commercial Pt-black, and ~70% (for CH₄) and ~80 % (for CO₂) in the case of real HCl-based leachate solution. H₂/CO ratios were ~0.9 and ~0.70 in the first and latter cases, respectively. As far as we know, this is the first pioneering work in which a BCGZ catalyst and a real Pt-containing leachate solution were successfully employed for DRM reaction.

Keywords: dry reforming of methane, perovskite, PGM, recycled Pt, syngas

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

Procedia PDF Downloads 69

Authors: Valerii Levshakov, Olga Fedorova

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Specific features of ship structures, made from composites, i.e. simultaneous shaping of material and structure, large sizes, complicated outlines and tapered thickness have defined leading role of technology, integrating test results from material science, designing and structural analysis. Main procedures of composite shipbuilding are contact molding, vacuum molding and winding. Now, the most demanded composite shipbuilding technology is the manufacture of structures from fiberglass and multilayer hybrid composites by means of vacuum molding. This technology enables the manufacture of products with improved strength properties (in comparison with contact molding), reduction of production duration, weight and secures better environmental conditions in production area. Mechanized winding is applied for the manufacture of parts, shaped as rotary bodies – i.e. parts of ship, oil and other pipelines, deep-submergence vehicles hulls, bottles, reservoirs and other structures. This procedure involves processing of reinforcing fiberglass, carbon and polyaramide fibers. Polyaramide fibers have tensile strength of 5000 MPa, elastic modulus value of 130 MPa and rigidity of the same can be compared with rigidity of fiberglass, however, the weight of polyaramide fiber is 30% less than weight of fiberglass. The same enables to the manufacture different structures, including that, using both – fiberglass and organic composites. Organic composites are widely used for the manufacture of parts with size and weight limitations. High price of polyaramide fiber restricts the use of organic composites. Perspective area of winding technology development is the manufacture of carbon fiber shafts and couplings for ships. JSC ‘Shipbuilding & Shiprepair Technology Center’ (JSC SSTC) developed technology of dielectric uncouplers for cryogenic lines, cooled by gaseous or liquid cryogenic agents (helium, nitrogen, etc.) for temperature range 4.2-300 K and pressure up to 30 MPa – the same is used for separating components of electro physical equipment with different electrical potentials. Dielectric uncouplers were developed, the manufactured and tested in accordance with International Thermonuclear Experimental Reactor (ITER) Technical specification. Spiral uncouplers withstand operating voltage of 30 kV, direct-flow uncoupler – 4 kV. Application of spiral channel instead of rectilinear enables increasing of breakdown potential and reduction of uncouplers sizes. 95 uncouplers were successfully the manufactured and tested. At the present time, Russian the manufacturers of ship composite structures have started absorption of technology of manufacturing the same using automated prepreg laminating; this technology enables the manufacture of structures with improved operational specifications.

Keywords: fiberglass, infusion, polymeric composites, winding

Procedia PDF Downloads 238

Authors: Anaelle Gabet, Helene Metivier, Christine De Brauer, Gilles Mailhot, Marcello Brigante

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The presence of micropollutants in surface waters has been widely reported around the world, particularly downstream from wastewater treatment plants (WWTPs). Rural WWTPs constitute more than 90 % of the total WWTPs in France. Like conventional ones, they are not able to fully remove micropollutants. Estrogens are excreted by human beings every day and several studies have highlighted their endocrine disruption properties on river wildlife. They are mainly estrone (E1), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2). Rural WWTPs require cheap and robust tertiary processes. UVC activation of H₂O₂ for HO· generation, a very reactive molecule, has demonstrated its effectiveness. However, UVC rays are dangerous to manipulate and energy-consuming. This is why the ability of UVA rays was investigated in this study. Moreover, the use of S₂O₈²⁻ for SO₄·- generation as an alternative to HO· has emerged in the last few years. Such processes have been widely studied on a lab scale. However, pilot-scale works constitute fewer studies. This study was carried out on a 20-L pilot composed of a 1.12-L UV reactor equipped with a polychromatic UVA lamp or a monochromatic (254 nm) UVC lamp fed in recirculation. Degradation rates of a mixture of spiked E1, E2 and EE2 (5 µM each) were followed by HPLC-UV. Results are expressed in UV dose (mJ.cm-2) received by the compounds of interest to compare UVC and UVA. In every system, estrogen degradation rates followed pseudo-first-order rates. First, experiments were carried out in tap water. All estrogens underwent photolysis under UVC rays, although E1 photolysis is higher. However, only very weak photolysis was observed under UVA rays. Preliminary studies on both oxidants have shown that S₂O₈²⁻ photolysis constants are higher than H₂O₂ under both UVA and UVC rays. Therefore, estrogen degradation rates are about ten times higher in the presence of 1 mM of S₂O₈²⁻ than with one mM of H₂O₂ under both radiations. In the same conditions, the mixture of interest required about 40 times higher UV dose when using UVA rays compared to UVC. However, the UVA/S₂O₈²⁻ system only requires four times more UV dose than the conventional UVC/H₂O₂ system. Further studies were carried out in WWTP effluent with the UVC lamp. When comparing these results to the tap water ones, estrogen degradation rates were more inhibited in the S₂O₈²⁻ system than with H₂O₂. It seems that SO₄·- undergo higher quenching by a real effluent than HO·. Preliminary experiments have shown that natural organic matter is mainly responsible for the radical quenching and that HO and SO₄ both had similar second-order reaction rate constants with dissolved organic matter. However, E1, E2 and EE2 second-order reaction rate constants are about ten times lower with SO₄ than with HO. In conclusion, the UVA/S₂O₈²⁻ system showed encouraging results for the use of UVA rays but further studies in WWTP effluent have to be carried out to confirm this interest. The efficiency of other pollutants in the real matrix also needs to be investigated.

Keywords: AOPs, decontamination, estrogens, radicals, wastewater

Procedia PDF Downloads 191

Authors: C. Fúnez Guerra, B. Nieto Calderón, M. Jaén Caparrós, L. Reyes-Bozo, A. Godoy-Faúndez, E. Vyhmeister

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The global energy system is experiencing a change of scenery. Unstable energy markets, an increasing focus on climate change and its sustainable development is forcing businesses to pursue new solutions in order to ensure future economic growth. This has led to the interest in using hydrogen as an energy carrier in transportation and industrial applications. As an energy carrier, hydrogen is accessible and holds a high gravimetric energy density. Abundant in hydrocarbons, hydrogen can play an important role in the shift towards low-emission fossil value chains. By combining hydrogen production by natural gas reforming with carbon capture and storage, the overall CO2 emissions are significantly reduced. In addition, the flexibility of hydrogen as an energy storage makes it applicable as a stabilizer in the renewable energy mix. The recent development in hydrogen fuel cells is also raising the expectations for a hydrogen powered transportation sector. Hydrogen value chains exist to a large extent in the industry today. The global hydrogen consumption was approximately 50 million tonnes (7.2 EJ) in 2013, where refineries, ammonia, methanol production and metal processing were main consumers. Natural gas reforming produced 48% of this hydrogen, but without carbon capture and storage (CCS). The total emissions from the production reached 500 million tonnes of CO2, hence alternative production methods with lower emissions will be necessary in future value chains. Hydrogen from electrolysis is used for a wide range of industrial chemical reactions for many years. Possibly, the earliest use was for the production of ammonia-based fertilisers by Norsk Hydro, with a test reactor set up in Notodden, Norway, in 1927. This application also claims one of the world’s largest electrolyser installations, at Sable Chemicals in Zimbabwe. Its array of 28 electrolysers consumes 80 MW per hour, producing around 21,000 Nm3/h of hydrogen. These electrolysers can compete if cheap sources of electricity are available and natural gas for steam reforming is relatively expensive. Because electrolysis of water produces oxygen as a by-product, a system of Autothermal Reforming (ATR) utilizing this oxygen has been analyzed. Replacing the air separation unit with electrolysers produces the required amount of oxygen to the ATR as well as additional hydrogen. The aim of this paper is to evaluate the technical and economic potential of large-scale production of hydrogen for oil refining industry. Sensitivity analysis of parameters such as investment costs, plant operating hours, electricity price and sale price of hydrogen and oxygen are performed.

Keywords: autothermal reforming, electrolyser, hydrogen, natural gas, steam methane reforming

Procedia PDF Downloads 211

Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

Procedia PDF Downloads 303

Authors: Nabila Ihaddadene, Razika Ihaddadene, Abdelwahaab Betka

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1973 energy crisis (rising oil prices) pushed the world to consider other alternative energy resources to existing conventional energies consisting predominantly of hydrocarbons. Renewable energies such as solar, the wind and geothermal have received renewed interest, especially to preserve nature ( the low-temperature rise of global environmental problems). Solar energy as an available, cheap and environmental friendly alternative source has various applications such as heating, cooling, drying, power generation, etc. In short, there is no life on earth without this enormous nuclear reactor, called the sun. Among available solar collector designs, flat plate collector (FPC) is low-temperature applications (heating water, space heating, etc.) due to its simple design and ease of manufacturing. Flat plate collectors are permanently fixed in position and do not track the sun (non-concentrating collectors). They operate by converting solar radiation into heat and transferring that heat to a working fluid (usually air, water, water plus antifreeze additive) flowing through them. An FPC generally consists of the main following components: glazing, absorber plate of high absorptivity, fluid tubes welded to or can be an integral part of the absorber plate, insulation and container or casing of the above-mentioned components. Insulation is of prime importance in thermal applications. There are three main families of insulation: mineral insulation; vegetal insulation and synthetic organic insulation. The old houses of the inhabitants of North Africa were built of brick made of composite material that is clay and straw. These homes are characterized by their thermal comfort; i.e. the air inside these houses is cool in summer and warm in winter. So, the material composed from clay and straw act as a thermal insulation. In this research document, the polystyrene used as insulation in the ET200 flat plate solar collector is replaced by the cheapest natural material which is clay and straw. Trials were carried out on a solar energy demonstration system (ET 200). This system contains a solar collector, water storage tank, a high power lamp simulating solar energy and a control and command cabinet. In the experimental device, the polystyrene is placed under the absorber plate and in the edges of the casing containing the components of the solar collector. In this work, we have replaced the polystyrene of the edges by the composite material. The use of the clay and straw as insulation instead of the polystyrene increases temperature difference (T2-T1) between the inlet and the outlet of the absorber by 0.9°C; thus increases the useful power transmitted to water in the solar collector. Tank Water is well heated when using the clay and straw as insulation. However, it is less heated when using the polystyrene as insulation. Clay and straw material improves also the performance of the solar collector by 5.77%. Thus, it is recommended to use this cheapest non-polluting material instead of synthetic insulation to improve the performance of the solar collector.

Keywords: clay, insulation material, polystyrene, solar collector, straw

Procedia PDF Downloads 461

Authors: Magdalena Wilk-Kozubek, Magdalena Rowińska, Krzysztof Rola, Joanna Cybińska

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Leuco dye-based thermochromic systems are classified as intelligent materials because they exhibit thermally induced color changes. Thanks to this feature, they are mainly used as temperature sensors in many industrial sectors. For example, placing a thermochromic material on a chemical reactor may warn about exceeding the maximum permitted temperature for a chemical process. Usually two components, a color former and a developer are needed to produce a system with irreversible color change. The color former is an electron donating (proton accepting) compound such as fluoran leuco dye. The developer is an electron accepting (proton donating) compound such as organic carboxylic acid. When the developer melts, the color former - developer complex is created and the termochromic system becomes colored. Typically, the melting point of the applied developer determines the temperature at which the color change occurs. When the lactone ring of the color former is closed, then the dye is in its colorless state. The ring opening, induced by the addition of a proton, causes the dye to turn into its colored state. Since the color former and the developer are often solid, they can be incorporated into polymer films to facilitate their practical use in industry. The objective of this research was to fabricate a leuco dye-based termochromic system that will irreversibly change color after reaching the temperature of 100°C. For this purpose, benzofluoran leuco dye (as color former) and phenoxyacetic acid (as developer with a melting point of 100°C) were introduced into the polymer films during the drop casting process. The film preparation process was optimized in order to obtain thin films with appropriate properties such as transparency, flexibility and homogeneity. Among the optimized factors were the concentration of benzofluoran leuco dye and phenoxyacetic acid, the type, average molecular weight and concentration of the polymer, and the type and concentration of the surfactant. The selected films, containing benzofluoran leuco dye and phenoxyacetic acid, were combined by mild heat treatment. Structural characterization of single and combined films was carried out by FTIR spectroscopy, morphological analysis was performed by optical microscopy and SEM, phase transitions were examined by DSC, color changes were investigated by digital photography and UV-Vis spectroscopy, while emission changes were studied by photoluminescence spectroscopy. The resulting thermochromic system is colorless at room temperature, but after reaching 100°C the developer melts and it turns irreversibly pink. Therefore, it could be used as an additional sensor to warn against boiling of water in power plants using water cooling. Currently used electronic temperature indicators are prone to faults and unwanted third-party actions. The sensor constructed in this work is transparent, thanks to which it can be unnoticed by an outsider and constitute a reliable reference for the person responsible for the apparatus.

Keywords: color developer, leuco dye, thin film, thermochromism

Procedia PDF Downloads 101

Authors: Amirhosein Moonesi Shabestary, Eckhard Krepper, Dirk Lucas

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The current PhD project comprises CFD-modeling and simulation of condensation and heat transfer inside horizontal pipes. Condensation plays an important role in emergency cooling systems of reactors. The emergency cooling system consists of inclined horizontal pipes which are immersed in a tank of subcooled water. In the case of an accident the water level in the core is decreasing, steam comes in the emergency pipes, and due to the subcooled water around the pipe, this steam will start to condense. These horizontal pipes act as a strong heat sink which is responsible for a quick depressurization of the reactor core when any accident happens. This project is defined in order to model all these processes which happening in the emergency cooling systems. The most focus of the project is on detection of different morphologies such as annular flow, stratified flow, slug flow and plug flow. This project is an ongoing project which has been started 1 year ago in Helmholtz Zentrum Dresden Rossendorf (HZDR), Fluid Dynamics department. In HZDR most in cooperation with ANSYS different models are developed for modeling multiphase flows. Inhomogeneous MUSIG model considers the bubble size distribution and is used for modeling small-scaled dispersed gas phase. AIAD (Algebraic Interfacial Area Density Model) is developed for detection of the local morphology and corresponding switch between them. The recent model is GENTOP combines both concepts. GENTOP is able to simulate co-existing large-scaled (continuous) and small-scaled (polydispersed) structures. All these models are validated for adiabatic cases without any phase change. Therefore, the start point of the current PhD project is using the available models and trying to integrate phase transition and wall condensing models into them. In order to simplify the idea of condensation inside horizontal tubes, 3 steps have been defined. The first step is the investigation of condensation inside a horizontal tube by considering only direct contact condensation (DCC) and neglect wall condensation. Therefore, the inlet of the pipe is considered to be annular flow. In this step, AIAD model is used in order to detect the interface. The second step is the extension of the model to consider wall condensation as well which is closer to the reality. In this step, the inlet is pure steam, and due to the wall condensation, a liquid film occurs near the wall which leads to annular flow. The last step will be modeling of different morphologies which are occurring inside the tube during the condensation via using GENTOP model. By using GENTOP, the dispersed phase is able to be considered and simulated. Finally, the results of the simulations will be validated by experimental data which will be available also in HZDR.

Keywords: wall condensation, direct contact condensation, AIAD model, morphology detection

Procedia PDF Downloads 307

Authors: Ching Shya Lee, Mohamed Kheireddine Aroua, Wan Mohd Ashri Wan Daud, Patrick Cognet, Yolande Peres, Mohammed Ajeel

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In recent years, with the decreasing supply of fossil fuel, renewable energy has received a significant demand. Biodiesel which is well known as vegetable oil based fatty acid methyl ester is an alternative fuel for diesel. It can be produced from transesterification of vegetable oils, such as palm oil, sunflower oil, rapeseed oil, etc., with methanol. During the transesterification process, crude glycerol is formed as a by-product, resulting in 10% wt of the total biodiesel production. To date, due to the fast growing of biodiesel production in worldwide, the crude glycerol supply has also increased rapidly and resulted in a significant price drop for glycerol. Therefore, extensive research has been developed to use glycerol as feedstock to produce various added-value chemicals, such as tartronic acid, mesoxalic acid, glycolic acid, glyceric acid, propanediol, acrolein etc. The industrial processes that usually involved are selective oxidation, biofermentation, esterification, and hydrolysis. However, the conversion of glycerol into added-value compounds by electrochemical approach is rarely discussed. Currently, the approach is mainly focused on the electro-oxidation study of glycerol under potentiostatic mode for cogenerating energy with other chemicals. The electro-organic synthesis study from glycerol under galvanostatic mode is seldom reviewed. In this study, the glycerol was converted into various added-value compounds by electrochemical method under galvanostatic mode. This work aimed to study the possible compounds produced from glycerol by electrochemical technique in a one-pot electrolysis cell. The electro-organic synthesis study from glycerol was carried out in a single compartment reactor for 8 hours, over the platinum cathode and anode electrodes under acidic condition. Various parameters such as electric current (1.0 A to 3.0 A) and reaction temperature (27 °C to 80 °C) were evaluated. The products obtained were characterized by using gas chromatography-mass spectroscopy equipped with an aqueous-stable polyethylene glycol stationary phase column. Under the optimized reaction condition, the glycerol conversion achieved as high as 95%. The glycerol was successfully converted into various added-value chemicals such as ethylene glycol, glycolic acid, glyceric acid, acetaldehyde, formic acid, and glyceraldehyde; given the yield of 1%, 45%, 27%, 4%, 0.7% and 5%, respectively. Based on the products obtained from this study, the reaction mechanism of this process is proposed. In conclusion, this study has successfully converted glycerol into a wide variety of added-value compounds. These chemicals are found to have high market value; they can be used in the pharmaceutical, food and cosmetic industries. This study effectively opens a new approach for the electrochemical conversion of glycerol. For further enhancement on the product selectivity, electrode material is an important parameter to be considered.

Keywords: biodiesel, glycerol, electrochemical conversion, galvanostatic mode

Procedia PDF Downloads 194

Authors: Tomasz Borowski, Dawid Sołoducha, Agata Markowska-Szczupak, Aneta Wesołowska, Marian Kordas, Rafał Rakoczy

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Essential oils (EOs) are fragrant volatile oils obtained from plants. These are used for cooking (for flavor and aroma), cleaning, beauty (e.g., rosemary essential oil is used to promote hair growth), health (e.g. thyme essential oil cures arthritis, normalizes blood pressure, reduces stress on the heart, cures chest infection and cough) and in the food industry as preservatives and antioxidants. Rosemary and thyme essential oils are considered the most eminent herbs based on their history and medicinal properties. They possess a wide range of activity against different types of bacteria and fungi compared with the other oils in both in vitro and in vivo studies. However, traditional uses of EOs are limited due to rosemary and thyme oils in high concentrations can be toxic. In light of the accessible data, the following hypothesis was put forward: Low frequency rotating magnetic field (RMF) increases the antimicrobial potential of EOs. The aim of this work was to investigate the antimicrobial activity of commercial Salvia Rosmarinus L. and Thymus vulgaris L. essential oil from Polish company Avicenna-Oil under Rotating Magnetic Field (RMF) at f = 25 Hz. The self-constructed reactor (MAP) was applied for this study. The chemical composition of oils was determined by gas chromatography coupled with mass spectrometry (GC-MS). Model bacteria Escherichia coli K12 (ATCC 25922) was used. Minimum inhibitory concentrations (MIC) against E. coli were determined for the essential oils. Tested oils in very small concentrations were prepared (from 1 to 3 drops of essential oils per 3 mL working suspensions). From the results of disc diffusion assay and MIC tests, it can be concluded that thyme oil had the highest antibacterial activity against E. coli. Moreover, the study indicates the exposition to the RMF, as compared to the unexposed controls causing an increase in the efficacy of antibacterial properties of tested oils. The extended radiation exposure to RMF at the frequency f= 25 Hz beyond 160 minutes resulted in a significant increase in antibacterial potential against E. coli. Bacteria were killed within 40 minutes in thyme oil in lower tested concentration (1 drop of essential oils per 3 mL working suspension). Rapid decrease (>3 log) of bacteria number was observed with rosemary oil within 100 minutes (in concentration 3 drops of essential oils per 3 mL working suspension). Thus, a method for improving the antimicrobial performance of essential oil in low concentrations was developed. However, it still remains to be investigated how bacteria get killed by the EOs treated by an electromagnetic field. The possible mechanisms relies on alteration in the permeability of ionic channels in ionic channels in the bacterial cell walls that transport in the cells was proposed. For further studies, it is proposed to examine other types of essential oils and other antibiotic-resistant bacteria (ARB), which are causing a serious concern throughout the world.

Keywords: rotating magnetic field, rosemary, thyme, essential oils, Escherichia coli

Procedia PDF Downloads 157

Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

Procedia PDF Downloads 61

Authors: Harshvardhan Soni, Anil Kumar Dikshit, R. K. Pathak

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Nowadays, a large amount of wastewater is being generated from cities and travels very long distances from their point of generation to their point of treatment, i.e., conventional centralized wastewater treatment plants (CCWTPs) which in turn results in several operational troubles due to heavy mechanized systems, also the large CCWTPs are sometimes even unable to handle these large volumes of wastewater being generated and the wastewater is either partially treated or sometimes may be even disposed of directly without any treatment into the water bodies, thus causing environmental problems. To overcome these operational troubles of heavily mechanized centralized treatment systems, there is a need for on-spot safe and complete treatment of wastewater being generated from various residential areas and areas such as holiday homes, industries, resorts, etc. These days, it is being felt, and in fact, several municipal corporations have already started requiring the proposed residential/commercial/industrial projects (i.e., where a conventional CCWTP is not there or not working or does not function properly or where there is a scarcity of freshwater supply) to take care of their wastewater within their premises, so that the effluent can be reused for a variety of non-potable uses including agriculture, irrigation, landscaping, surface storages, domestic uses, commercial uses, urban uses, environmental and recreational uses and industrial applications, and hence the freshwater demand of the area can be reduced. So, there's a need to design some specific units for some specific social needs and assess them and verify that they are capable of not only treating the sewage but also recycling the associated resources. Hence, there is a scope for decentralized/on-site treatment of sewage, which forms the basis for the research/innovation being proposed in this study. In view of that and considering the above requirements, for residential areas, a decentralized wastewater treatment plant (DWTP) (completely based on natural treatment technology to avoid heavy mechanized systems as in CCWTPs) was developed and deployed at the Indian Institute of Technology Bombay (IIT Bombay) campus, Mumbai, Maharashtra, India, to assess and evaluate its efficacy in long run. The system was deployed at the sewage pumping station of the campus for having a continuous 24 hours sewage flow into the system. The reactor configuration consists of an aerobic, facultative, and anaerobic tank as a pre-treatment unit followed by a planted gravel bed as a post-treatment unit in series. Results of the start-up period indicated that the system was very efficient/effective in the treatment of wastewater. The COD of the final effluent was found to be 29.7 mg/l; BOD was 0.7 mg/l, turbidity was 1.7 NTU, nitrate concentration was 1 mg/l, while the phosphorous concentration was 4.6 mg/l, and nearly all the parameters have very well complied with the reuse standards as per the Indian Standards. If seen on a daily basis also, turbidity has met the reuse standards around 92% of the time, COD around 84% of the time, and BOD and nitrates at all times.

Keywords: centralized wastewater treatment systems, decentralized wastewater treatment systems, reuse, effluent

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Authors: A. V. Samokhin, A. A. Fadeev, M. A. Sinaiskii, N. V. Alekseev, A. V. Kolesnikov

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Composite materials where metal matrix is reinforced by ceramic or metal particles are of great interest for use in the manufacturing of electrical contacts. Significant improvement of the composite physical and mechanical properties as well as increase of the performance parameters of composite-based products can be achieved if the nanoscale structure in the composite materials is obtained by using nanosized powders as starting components. The results of nanosized composite powders synthesis (Ag-SnO2, W-Cu and Cu-C) in the DC thermal plasma flows are presented in this paper. The investigations included the following processes: - Recondensation of micron powder mixture Ag + SnO2 in a nitrogen plasma; - The reduction of the oxide powders mixture (WO3 + CuO) in a hydrogen-nitrogen plasma; - Decomposition of the copper formate and copper acetate powders in nitrogen plasma. The calculations of equilibrium compositions of multicomponent systems Ag-Sn-O-N, W-Cu-O-H-N and Cu-O-C-H-N in the temperature range of 400-5000 K were carried to estimate basic process characteristics. Experimental studies of the processes were performed using a plasma reactor with a confined jet flow. The plasma jet net power was in the range of 2 - 13 kW, and the feedstock flow rate was up to 0.35 kg/h. The obtained powders were characterized by TEM, HR-TEM, SEM, EDS, ED-XRF, XRD, BET and QEA methods. Nanocomposite Ag-SnO2 (12 wt. %). Processing of the initial powder mixture (Ag-SnO2) in nitrogen thermal plasma stream allowed to produce nanopowders with a specific surface area up to 24 m2/g, consisting predominantly of particles with size less than 100 nm. According to XRD results, tin was present in the obtained products as SnO2 phase, and also as intermetallic phases AgxSn. Nanocomposite W-Cu (20 wt .%). Reduction of (WO3+CuO) mixture in the hydrogen-nitrogen plasma provides W-Cu nanopowder with particle sizes in the range of 10-150 nm. The particles have mainly spherical shape and structure tungsten core - copper shell. The thickness of the shell is about several nanometers, the shell is composed of copper and its oxides (Cu2O, CuO). The nanopowders had 1.5 wt. % oxygen impurity. Heat treatment in a hydrogen atmosphere allows to reduce the oxygen content to less than 0.1 wt. %. Nanocomposite Cu-C. Copper nanopowders were found as products of the starting copper compounds decomposition. The nanopowders primarily had a spherical shape with a particle size of less than 100 nm. The main phase was copper, with small amount of Cu2O and CuO oxides. Copper formate decomposition products had a specific surface area 2.5-7 m2/g and contained 0.15 - 4 wt. % carbon; and copper acetate decomposition products had the specific surface area 5-35 m2/g, and carbon content of 0.3 - 5 wt. %. Compacting of nanocomposites (sintering in hydrogen for Ag-SnO2 and electric spark sintering (SPS) for W-Cu) showed that the samples having a relative density of 97-98 % can be obtained with a submicron structure. The studies indicate the possibility of using high-intensity plasma processes to create new technologies to produce nanocomposite materials for electric contacts.

Keywords: electrical contact, material, nanocomposite, plasma, synthesis

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Authors: Zhihao Peng, Qiong Zhang, Xiyao Li, Yongzhen Peng

Abstract:

Nowadays, conventional nitrogen removal process (nitrification and denitrification) was adopted in most wastewater treatment plants, but many problems have occurred, such as: high aeration energy consumption, extra carbon sources dosage and high sludge treatment costs. The emergence of anammox has bring about the great revolution to the nitrogen removal technology, and only the ammonia and nitrite were required to remove nitrogen autotrophically, no demand for aeration and sludge treatment. However, there existed many challenges in anammox applications: difficulty of biomass retention, insufficiency of nitrite substrate, damage from complex organic etc. Much effort was put into the research in overcoming the above challenges, and the payment was rewarded. It was also imperative to establish an innovative process that can settle the above problems synchronously, after all any obstacle above mentioned can cause the collapse of anammox system. Therefore, in this study, a two-stage process was established that the sequencing batch reactor (SBR) and upflow anaerobic sludge blanket (UASB) were used in the pre-stage and post-stage, respectively. The domestic wastewater entered into the SBR first and went through anaerobic/aerobic/anoxic (An/O/A) mode, and the draining at the aerobic end of SBR was mixed with domestic wastewater, the mixture then entering to the UASB. In the long term, organic and nitrogen removal performance was evaluated. All along the operation, most COD was removed in pre-stage (COD removal efficiency > 64.1%), including some macromolecular organic matter, like: tryptophan, tyrosinase and fulvic acid, which could weaken the damage of organic matter to anammox. And the An/O/A operating mode of SBR was beneficial to the achievement and maintenance of partial nitrification (PN). Hence, sufficient and steady nitrite supply was another favorable condition to anammox enhancement. Besides, the flexible mixing ratio helped to gain a substrate ratio appropriate to anammox (1.32-1.46), which further enhance the anammox. Further, the UASB was used and gas recirculation strategy was adopted in the post-stage, aiming to achieve granulation by the selection pressure. As expected, the granules formed rapidly during 38 days, which increased from 153.3 to 354.3 μm. Based on bioactivity and gene measurement, the anammox metabolism and abundance level rose evidently, by 2.35 mgN/gVss·h and 5.3 x109. The anammox bacteria mainly distributed in the large granules (>1000 μm), while the biomass in the flocs (<200 μm) and microgranules (200-500 μm) barely displayed anammox bioactivity. Enhanced anammox promoted the advanced autotrophic nitrogen removal, which increased from 71.9% to 93.4%, even when the temperature was only 12.9 ℃. Therefore, it was feasible to enhance anammox in the multiple favorable conditions created, and the strategy extended the application of anammox to the full-scale mainstream, enhanced the understanding of anammox in the aspects of culturing conditions.

Keywords: anammox, granules, nitrite accumulation, nitrogen removal efficiency

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Authors: Sara Camino, Fernando Vega, Mercedes Cano, Benito Navarrete, José A. Camino

Abstract:

Carbon capture and storage (CCS) technologies should play a relevant role towards low-carbon systems in the European Union by 2030. Partial oxy-combustion emerges as a promising CCS approach to mitigate anthropogenic CO₂ emissions. Its advantages respect to other CCS technologies rely on the production of a higher CO₂ concentrated flue gas than these provided by conventional air-firing processes. The presence of more CO₂ in the flue gas increases the driving force in the separation process and hence it might lead to further reductions of the energy requirements of the overall CO₂ capture process. A higher CO₂ concentrated flue gas should enhance the CO₂ capture by chemical absorption in solvent kinetic and CO₂ cyclic capacity. They have impact on the performance of the overall CO₂ absorption process by reducing the solvent flow-rate required for a specific CO₂ removal efficiency. Lower solvent flow-rates decreases the reboiler duty during the regeneration stage and also reduces the equipment size and pumping costs. Moreover, R&D activities in this field are focused on novel solvents and blends that provide lower CO₂ absorption enthalpies and therefore lower energy penalties associated to the solvent regeneration. In this respect, sterically hindered amines are considered potential solvents for CO₂ capture. They provide a low energy requirement during the regeneration process due to its molecular structure. However, its absorption kinetics are slow and they must be promoted by blending with faster solvents such as monoethanolamine (MEA) and piperazine (PZ). In this work, the kinetic behavior of two sterically hindered amines were studied under partial oxy-combustion conditions and compared with MEA. A lab-scale semi-batch reactor was used. The CO₂ composition of the synthetic flue gas varied from 15%v/v – conventional coal combustion – to 60%v/v – maximum CO₂ concentration allowable for an optimal partial oxy-combustion operation. Firstly, 2-amino-2-methyl-1-propanol (AMP) showed a hybrid behavior with fast kinetics and a low enthalpy of CO₂ absorption. The second solvent was Isophrondiamine (IF), which has a steric hindrance in one of the amino groups. Its free amino group increases its cyclic capacity. In general, the presence of higher CO₂ concentration in the flue gas accelerated the CO₂ absorption phenomena, producing higher CO₂ absorption rates. In addition, the evolution of the CO2 loading also exhibited higher values in the experiments using higher CO₂ concentrated flue gas. The steric hindrance causes a hybrid behavior in this solvent, between both fast and slow kinetic solvents. The kinetics rates observed in all the experiments carried out using AMP were higher than MEA, but lower than the IF. The kinetic enhancement experienced by AMP at a high CO2 concentration is slightly over 60%, instead of 70% – 80% for IF. AMP also improved its CO₂ absorption capacity by 24.7%, from 15%v/v to 60%v/v, almost double the improvements achieved by MEA. In IF experiments, the CO₂ loading increased around 10% from 15%v/v to 60%v/v CO₂ and it changed from 1.10 to 1.34 mole CO₂ per mole solvent, more than 20% of increase. This hybrid kinetic behavior makes AMP and IF promising solvents for partial oxy–combustion applications.

Keywords: absorption, carbon capture, partial oxy-combustion, solvent

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Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

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Authors: Alexia Wu, Joel Ribis, Jean-Christophe Brachet, Emmanuel Clouet, Benoit Arnal, Elodie Rouesne, Stéphane Urvoy, Justine Roubaud, Yves Serruys, Frederic Lepretre

Abstract:

To enhance the safety of Light Water Reactor, accident tolerant fuel (ATF) claddings materials are under development. In the framework of CEA-AREVA-EDF collaborative program on ATF cladding materials, CEA has engaged specific studies on chromium coated zirconium alloys. Especially for Loss-of-Coolant-Accident situations, chromium coated claddings have shown some additional 'coping' time before achieving full embrittlement of the oxidized cladding, when compared to uncoated references – both tested in steam environment up to 1300°C. Nevertheless, the behavior of chromium coatings and the stability of the Zr-Cr interface under neutron irradiation remain unknown. Two main points are addressed: 1. Bulk Cr behavior under irradiation: Due to its BCC crystallographic structure, Cr is prone to Ductile-to-Brittle-Transition at quite high temperature. Irradiation could be responsible for a significant additional DBTT shift towards higher temperatures. 2. Zircaloy/Cr interface behavior under irradiation: Preliminary TEM examinations of un-irradiated samples revealed a singular Zircaloy-4/Cr interface with nanometric intermetallic phase layers. Such particular interfaces highlight questions of how they would behave under irradiation - intermetallic zirconium phases are known to be more or less stable under irradiations. Another concern is a potential enhancement of chromium diffusion into the zirconium-alpha based substrate. The purpose of this study is then to determine the behavior of such coatings after ion irradiations, as a surrogate to neutron irradiation. Ion irradiations were performed at the Jannus-Saclay facility (France). 20 MeV Kr8+ ions at 400°C with a flux of 2.8x1011 ions.cm-2.s-1 were used to irradiate chromium coatings of 1-2 µm thick on Zircaloy-4 sheets substrate. At the interface, the calculated damage is close to 10 dpa (SRIM, Quick Calculation Damage mode). Thin foil samples were prepared with FIB for both as-received and irradiated coated samples. Transmission Electron Microscopy (TEM) and in-situ tensile tests in a Scanning Electron Microscope are being used to characterize the un-irradiated and irradiated materials. High Resolution TEM highlights a great complexity of the interface before irradiation since it is formed of an alternation of intermetallic phases – C14 and C15. The interfaces formed by these intermetallic phases with chromium and zirconium show semi-coherency. Chemical analysis performed before irradiation shows some iron enrichment at the interface. The chromium coating bulk microstructures and properties are also studied before and after irradiation. On-going in-situ tensile tests focus on the capacity of chromium coatings to sustain some plastic deformation when tested up to 350°C. The stability of the Cr/Zr interface is shown after ion irradiation up to 10 dpa. This observation constitutes the first result after irradiation on these new coated claddings materials.

Keywords: accident tolerant fuel, HRTEM, interface, ion-irradiation

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Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

Procedia PDF Downloads 155