Search results for: autoclave
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 53

Search results for: autoclave

23 Preparation and Characterization of Titania-Coated Glass Fibrous Filters Using Aqueous Peroxotitanium Acid Solution

Authors: Ueda Honoka, Yasuo Hasegawa, Fumihiro Nishimura, Jae-Ho Kim, Susumu Yonezawa

Abstract:

Aqueous peroxotitanium acid solution prepared from the TiO₂ fluorinated by F₂ gas was used for the TiO₂ coating on glass fibrous filters in this study. The coating of TiO₂ on the surface of glass fibers was carried out at 120℃ and for 15 min ~ 24 h with aqueous peroxotitanium acid solution using a hydrothermal synthesis autoclave reactor. The morphology TiO₂ coating layer was largely dependent on the reaction time, as shown in the results of scanning electron microscopy and energy dispersive X-ray spectroscopy. Increasing the reaction times, the TiO₂ layer on the glass expanded uniformly. Moreover, the surface fluorination of glass fibers can promote the formation of the TiO₂ layer on the surface. The photocatalytic activity of prepared titania-coated glass fibrous filters was investigated by both the degradation test of methylene blue (MB) and the decomposition test of gaseous acetaldehyde. The MB decomposition ratio with fluorinated samples was about 95% for 30 min of UV irradiation time, and it was much higher than that (70%) with the untreated thing. The decomposition ratio (50%) of gaseous acetaldehyde with fluorinated samples was also higher than that (30%) with the untreated thing. Consequently, photocatalytic activity is enhanced by surface fluorination.

Keywords: aqueous peroxotitanium acid solution, titania-coated glass fibrous filters, photocatalytic activity, surface fluorination

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22 Carbon Coated Silicon Nanoparticles Embedded MWCNT/Graphene Matrix Anode Material for Li-Ion Batteries

Authors: Ubeyd Toçoğlu, Miraç Alaf, Hatem Akbulut

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We present a work which was conducted in order to improve the cycle life of silicon based lithium ion battery anodes by utilizing novel composite structure. In this study, carbon coated nano sized (50-100 nm) silicon particles were embedded into Graphene/MWCNT silicon matrix to produce free standing silicon based electrodes. Also, conventional Si powder anodes were produced from Si powder slurry on copper current collectors in order to make comparison of composite and conventional anode structures. Free –standing composite anodes (binder-free) were produced via vacuum filtration from a well dispersion of Graphene, MWCNT and carbon coated silicon powders. Carbon coating process of silicon powders was carried out via microwave reaction system. The certain amount of silicon powder and glucose was mixed under ultrasonication and then coating was conducted at 200 °C for two hours in Teflon lined autoclave reaction chamber. Graphene which was used in this study was synthesized from well-known Hummers method and hydrazine reduction of graphene oxide. X-Ray diffraction analysis and RAMAN spectroscopy techniques were used for phase characterization of anodes. Scanning electron microscopy analyses were conducted for morphological characterization. The electrochemical performance tests were carried out by means of galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy.

Keywords: graphene, Li-Ion, MWCNT, silicon

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21 Non-Burn Treatment of Health Care Risk Waste

Authors: Jefrey Pilusa, Tumisang Seodigeng

Abstract:

This research discusses a South African case study for the potential of utilizing refuse-derived fuel (RDF) obtained from non-burn treatment of health care risk waste (HCRW) as potential feedstock for green energy production. This specific waste stream can be destroyed via non-burn treatment technology involving high-speed mechanical shredding followed by steam or chemical injection to disinfect the final product. The RDF obtained from this process is characterised by a low moisture, low ash, and high calorific value which means it can be potentially used as high-value solid fuel. Due to the raw feed of this RDF being classified as hazardous, the final RDF has been reported to be non-infectious and can blend with other combustible wastes such as rubber and plastic for waste to energy applications. This study evaluated non-burn treatment technology as a possible solution for on-site destruction of HCRW in South African private and public health care centres. Waste generation quantities were estimated based on the number of registered patient beds, theoretical bed occupancy. Time and motion study was conducted to evaluate the logistics viability of on-site treatment. Non-burn treatment technology for HCRW is a promising option for South Africa, and successful implementation of this method depends upon the initial capital investment, operational cost and environmental permitting of such technology; there are other influencing factors such as the size of the waste stream, product off-take price as well as product demand.

Keywords: autoclave, disposal, fuel, incineration, medical waste

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20 Avoiding Gas Hydrate Problems in Qatar Oil and Gas Industry: Environmentally Friendly Solvents for Gas Hydrate Inhibition

Authors: Nabila Mohamed, Santiago Aparicio, Bahman Tohidi, Mert Atilhan

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Qatar's one of the biggest problem in processing its natural resource, which is natural gas, is the often occurring blockage in the pipelines caused due to uncontrolled gas hydrate formation in the pipelines. Several millions of dollars are being spent at the process site to dehydrate the blockage safely by using chemical inhibitors. We aim to establish national database, which addresses the physical conditions that promotes Qatari natural gas to form gas hydrates in the pipelines. Moreover, we aim to design and test novel hydrate inhibitors that are suitable for Qatari natural gas and its processing facilities. From these perspectives we are aiming to provide more effective and sustainable reservoir utilization and processing of Qatari natural gas. In this work, we present the initial findings of a QNRF funded project, which deals with the natural gas hydrate formation characteristics of Qatari type gas in both experimental (PVTx) and computational (molecular simulations) methods. We present the data from the two fully automated apparatus: a gas hydrate autoclave and a rocking cell. Hydrate equilibrium curves including growth/dissociation conditions for multi-component systems for several gas mixtures that represent Qatari type natural gas with and without the presence of well known kinetic and thermodynamic hydrate inhibitors. Ionic liquids were designed and used for testing their inhibition performance and their DFT and molecular modeling simulation results were also obtained and compared with the experimental results. Results showed significant performance of ionic liquids with up to 0.5 % in volume with up to 2 to 4 0C inhibition at high pressures.

Keywords: gas hydrates, natural gas, ionic liquids, inhibition, thermodynamic inhibitors, kinetic inhibitors

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19 Design and Development of Constant Stress Composite Cantilever Beam

Authors: Vinod B. Suryawanshi, Ajit D. Kelkar

Abstract:

Glass fiber reinforced composites materials, due their unique properties such as high mechanical strength to weight ratio, corrosion resistance, and impact resistance have huge potential as structural materials in automotive, construction and transportation applications. However, these properties often come at higher cost owing to complex design methods, difficult manufacturing processes and raw material cost. In this paper, a cost effective design and manufacturing approach for a composite cantilever beam structure is presented. A constant stress (variable cross section) beam concept has been used to design and optimize the shape of composite cantilever beam and thus obtain the reduction in material used. The variable cross section beam was fabricated from the glass epoxy prepregs using cost effective out of autoclave process. The drop ply technique has been successfully used to obtain the variation in the cross section along the span of the beam. In order to test the beam and validate the design, the beam was subjected to different end loads. Strain gauges were mounted along the length of the beam to obtain strains in the beam at different sections and loads. The strain values were used to calculate the flexural strength and bending stresses in the beam. The stresses obtained through strain measurements from the experiment were found to be uniform along the span of the beam, and thus validates the design. Finally, the finite element model for the constant stress beam was developed using commercial finite element simulation software. It was observed that the simulation results agreed very well with the experimental results.

Keywords: beams, composites, constant cross-section, structures

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18 Fabrication and Characterization of Ceramic Matrix Composite

Authors: Yahya Asanoglu, Celaletdin Ergun

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Ceramic-matrix composites (CMC) have significant prominence in various engineering applications because of their heat resistance associated with an ability to withstand the brittle type of catastrophic failure. In this study, specific raw materials have been chosen for the purpose of having suitable CMC material for high-temperature dielectric applications. CMC material will be manufactured through the polymer infiltration and pyrolysis (PIP) method. During the manufacturing process, vacuum infiltration and autoclave will be applied so as to decrease porosity and obtain higher mechanical properties, although this advantage leads to a decrease in the electrical performance of the material. Time and temperature adjustment in pyrolysis parameters provide a significant difference in the properties of the resulting material. The mechanical and thermal properties will be investigated in addition to the measurement of dielectric constant and tangent loss values within the spectrum of Ku-band (12 to 18 GHz). Also, XRD, TGA/PTA analyses will be employed to prove the transition of precursor to ceramic phases and to detect critical transition temperatures. Additionally, SEM analysis on the fracture surfaces will be performed to see failure mechanism whether there is fiber pull-out, crack deflection and others which lead to ductility and toughness in the material. In this research, the cost-effectiveness and applicability of the PIP method will be proven in the manufacture of CMC materials while optimization of pyrolysis time, temperature and cycle for specific materials is detected by experiment. Also, several resins will be shown to be a potential raw material for CMC radome and antenna applications. This research will be distinguished from previous related papers due to the fact that in this research, the combination of different precursors and fabrics will be experimented with to specify the unique cons and pros of each combination. In this way, this is an experimental sum of previous works with unique PIP parameters and a guide to the manufacture of CMC radome and antenna.

Keywords: CMC, PIP, precursor, quartz

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17 Subcritical and Supercritical Water Gasification of Xylose

Authors: Shyh-Ming Chern, Te-Hsiu Tang

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Hemicellulose is one of the major constituents of all plant cell walls, making up 15-25% of dry wood. It is a biopolymer from many different sugar monomers, including pentoses, like xylose, and hexoses, like mannose. In an effort to gasify real biomass in subcritical and supercritical water in a single process, it is necessary to understand the gasification of hemicellulose, in addition to cellulose and lignin, in subcritical and supercritical water. In the present study, xylose is chosen as the model compound for hemicellulose, since it has the largest amount in most hardwoods. Xylose is gasified in subcritical and supercritical water for the production of higher-valued gaseous products. Experiments were conducted with a 16-ml autoclave batch-type reactor. Hydrogen peroxide is adopted as the oxidant in an attempt to promote the gasification yield. The major operating parameters for the gasification include reaction temperature (400 - 600°C), reaction pressure (5 - 25 MPa), the concentration of xylose (0.05 and 0.30 M), and level of oxidant added (0 and 0.25 chemical oxygen demand). 102 experimental runs were completed out of 46 different set of experimental conditions. Product gases were analyzed with a GC-TCD and determined to be mainly composed of H₂ (10 – 74 mol. %), CO (1 – 56 mol. %), CH₄ (1 – 27 mol. %), CO₂ (10 – 50 mol. %), and C₂H₆ (0 – 8 mol. %). It has been found that the gas yield (amount of gas produced per gram of xylose gasified), higher heating value (HHV) of the dry product gas, and energy yield (energy stored in the product gas divided by the energy stored in xylose) all increase significantly with rising temperature and moderately with reducing pressure. The overall best operating condition occurred at 873 K and 10 MPa, with a gas yield of 54 mmol/g of xylose, a gas HHV of 440 kJ/mol, and an energy yield of 1.3. A seemingly unreasonably energy yield of greater than unity resulted from the external heating employed in the experiments to drive the gasification process. It is concluded that xylose can be completely gasified in subcritical and supercritical water under proper operating conditions. The addition of oxidant does not promote the gasification of xylose.

Keywords: gasification, subcritical water, supercritical water, xylose

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16 The Effect of Carbon Nanotubes in Copolyamide Nonwovens on the Properties of CFRP Laminates

Authors: Kamil Dydek, Anna Boczkowska, Paulina Latko-Duralek, Rafal Kozera, Michal Salacinski

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In recent years there has been increasing interest in many industries, such as the aviation, automotive, and military industries, in Carbon Fibre Reinforced Polymers (CFRP). This is because of the excellent properties of CFRP, which are characterized by very high strength and stiffness in relation to their mass, low density (almost twice as low as aluminum and more than five times as low as steel), and corrosion resistance. However, they do not have sufficient electrical conductivity, which is required in some applications. Therefore, work is underway to improve their electrical conductivity, for example, by incorporating carbon nanotubes (CNTs) into the CFRP structure. CNTs possess excellent properties, such as high electrical conductivity, high aspect ratio, high Young’s modulus, and high tensile strength. An idea developed by our team is a modification of CFRP by the use of thermoplastic nonwovens containing CNTs. Nanocomposite fibers were made from three different masterbatches differing in the content of multi-wall carbon nanotubes, and then nonwovens that differed in areal weight were produced using a thermo-press. The out of autoclave method was used to fabricate the laminates from commercial carbon-epoxy prepreg dedicated to aviation applications - one without the nonwovens (reference) and five containing nonwovens placed between each prepreg layer. The volume of electrical conductivity of the manufactured laminates was measured in three directions. In order to investigate the adhesion between carbon fibers and nonwovens, the microstructure of the produced laminates was observed. The mechanical properties of the CFRP composites were measured in a short-beam shear test. In addition, the influence of thermoplastic nonwovens on the thermos-mechanical properties of laminates was analyzed by Dynamic Mechanical Analysis. The studies were carried out within grant no. DOB-1-3/1/PS/2014 financed by the National Centre for Research and Development in Poland.

Keywords: CFRP, thermoplastic nonwovens, carbon nanotubes, electrical conductivity

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15 Thermosonic Devulcanization of Waste Ground Rubber Tires by Quaternary Ammonium-Based Ternary Deep Eutectic Solvents and the Effect of α-Hydrogen

Authors: Ricky Saputra, Rashmi Walvekar, Mohammad Khalid

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Landfills, water contamination, and toxic gas emission are a few impacts faced by the environment due to the increasing number of αof waste rubber tires (WRT). In spite of such concerning issue, only minimal efforts are taken to reclaim or recycle these wastes as their products are generally not-profitable for companies. Unlike the typical reclamation process, devulcanization is a method to selectively cleave sulfidic bonds within vulcanizates to avoid polymeric scissions that compromise elastomer’s mechanical and tensile properties. The process also produces devulcanizates that are re-processable similar to virgin rubber. Often, a devulcanizing agent is needed. In the current study, novel and sustainable ammonium chloride-based ternary deep eutectic solvents (TDES), with a different number of α-hydrogens, were utilised to devulcanize ground rubber tire (GRT) as an effort to implement green chemistry to tackle such issue. 40-mesh GRT were soaked for 1 day with different TDESs and sonicated at 37-80 kHz for 60-120 mins and heated at 100-140oC for 30-90 mins. Devulcanizates were then filtered, dried, and evaluated based on the percentage of by means of Flory-Rehner calculation and swelling index. The result shows that an increasing number of α-Hs increases the degree of devulcanization, and the value achieved was around eighty-percent, thirty percent higher than the typical industrial-autoclave method. Resulting bondages of devulcanizates were also analysed by Fourier transform infrared spectrometer (FTIR), Horikx fitting, and thermogravimetric analyser (TGA). The earlier two confirms only sulfidic scissions were experienced by GRT through the treatment, while the latter proves the absence or negligibility of carbon-chains scission.

Keywords: ammonium, sustainable, deep eutectic solvent, α-hydrogen, waste rubber tire

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14 Comparison of Catalyst Support for High Pressure Reductive Amination

Authors: Tz-Bang Du, Cheng-Han Hsieh, Li-Ping Ju, Hung-Jie Liou

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Polyether amines synthesize by secondary hydroxyl polyether diol play an important role in epoxy hardener. The low molecular weight product is used in low viscosity and high transparent polyamine product for the logo, ground cover, especially for wind turbine blade, while the high molecular weight products are used in advanced agricultures such as a high-speed railway. High-pressure reductive amination process is required for producing these amines. In the condition of higher than 150 atm pressure and 200 degrees Celsius temperature, supercritical ammonia is used as a reactant and also a solvent. It would be a great challenge to select a catalyst support for such high-temperature alkaline circumstance. In this study, we have established a six-autoclave-type (SAT) high-pressure reactor for amination catalyst screening, which six experiment conditions with different temperature and pressure could be examined at the same time. We synthesized copper-nickel catalyst on different shaped alumina catalyst support and evaluated the catalyst activity for high-pressure reductive amination of polypropylene glycol (PPG) by SAT reactor. Ball type gamma alumina, ball type activated alumina and pellet type gamma alumina catalyst supports are evaluated in this study. Gamma alumina supports have shown better activity on PPG reductive amination than activated alumina support. In addition, the catalysts are evaluated in fixed bed reactor. The diamine product was successfully synthesized via this catalyst and the strength of the catalysts is measured. The crush strength of blank supports is about 13.5 lb for both gamma alumina and activated alumina. The strength increases to 20.3 lb after synthesized to be copper-nickel catalyst. After test in the fixed bed high-pressure reductive amination process for 100 hours, the crush strength of the used catalyst is 3.7 lb for activated alumina support, 12.0 lb for gamma alumina support. The gamma alumina is better than activated alumina to use as catalyst support in high-pressure reductive amination process.

Keywords: high pressure reductive amination, copper nickel catalyst, polyether amine, alumina

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13 Designing the Management Plan for Health Care (Medical) Wastes in the Cities of Semnan, Mahdishahr and Shahmirzad

Authors: Rasouli Divkalaee Zeinab, Kalteh Safa, Roudbari Aliakbar

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Introduction: Medical waste can lead to the generation and transmission of many infectious and contagious diseases due to the presence of pathogenic agents, thereby necessitating the need for special management to collect, decontaminate, and finally dispose of such products. This study aimed to design a centralized health care (medical) waste management program for the cities of Semnan, Mahdishahr, and Shahmirzad. Methods: This descriptive-analytical study was conducted for six months in the cities of Semnan, Mahdishahr, and Shahmirzad. In this study, the quantitative and qualitative characteristics of the generated wastes were determined by taking samples from all medical waste production centers. Then, the equipment, devices, and machines required for separate collection of the waste from the production centers and for their subsequent decontamination were estimated. Next, the investment costs, current costs, and working capital required for collection, decontamination, and final disposal of the wastes were determined. Finally, the payment for proper waste management of each category of medical waste-producing centers was determined. Results: 1021 kilograms of medical waste are produced daily in the cities of Semnan, Mahdishahr, and Shahmirzad. It was estimated that a 1000-liter autoclave, a machine for collecting medical waste, four 60-liter bins, four 120-liter bins, and four 1200-liter bins were required for implementing the study plan. Also, the estimated total annual medical waste management costs for Semnan City were determined (23,283,903,720 Iranian Rials). Conclusion: The study results showed that establishing a proper management system for medical wastes generated in the three studied cities will cost between 334,280 and 1,253,715 Iranian Rials in fees for the medical centers. The findings of this study provided comprehensive data regarding medical wastes from the generation point to the landfill site, which is vital for the government and the private sector.

Keywords: clinics, decontamination, management, medical waste

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12 Modeling of Void Formation in 3D Woven Fabric During Resin Transfer Moulding

Authors: Debabrata Adhikari, Mikhail Matveev, Louise Brown, Jan Kočí, Andy Long

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Resin transfer molding (RTM) is increasingly used for manufacturing high-quality composite structures due to its additional advantages over prepregs of low-cost out-of-autoclave processing. However, to retain the advantages, it is critical to reduce the void content during the injection. Reinforcements commonly used in RTM, such as woven fabrics, have dual-scale porosity with mesoscale pores between the yarns and the micro-scale pores within the yarns. Due to the fabric geometry and the nature of the dual-scale flow, the flow front during injection creates a complicated fingering formation which leads to void formation. Analytical modeling of void formation for woven fabrics has been widely studied elsewhere. However, there is scope for improvement to the reduction in void formation in 3D fabrics wherein the in-plane yarn layers are confined by additional through-thickness binder yarns. In the present study, the structural morphology of the tortuous pore spaces in the 3D fabric has been studied and implemented using open-source software TexGen. An analytical model for the void and the fingering formation has been implemented based on an idealized unit cell model of the 3D fabric. Since the pore spaces between the yarns are free domains, the region is treated as flow-through connected channels, whereas intra-yarn flow has been modeled using Darcy’s law with an additional term to account for capillary pressure. Later the void fraction has been characterised using the criterion of void formation by comparing the fill time for inter and intra yarn flow. Moreover, the dual-scale two-phase flow of resin with air has been simulated in the commercial CFD solver OpenFOAM/ANSYS to predict the probable location of voids and validate the analytical model. The use of an idealised unit cell model will give the insight to optimise the mesoscale geometry of the reinforcement and injection parameters to minimise the void content during the LCM process.

Keywords: 3D fiber, void formation, RTM, process modelling

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11 High Heating Value Bio-Chars from a Bio-Oil Upgrading Process

Authors: Julius K. Gane, Mohamad N. Nahil, Paul T. Williams

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In today’s world of rapid population growth and a changing climate, one way to mitigate various negative effects is via renewable energy solutions. Energy and power as basic requirements in almost all human endeavours are also the banes of the changing climate and the impacts thereof. Thus it is crucial to develop innovative and environmentally friendly energy options to ameliorate various negative repercussions. Upgrading of fast pyrolysis bio-oil via hydro-treatment offers such opportunities, as quality renewable liquid transportation fuels can be produced. The process, however, is typically accompanied by bio-char formation as a by-product. The goal of this work was to study the yield and some properties of bio-chars formed from a hydrotreatment process, with an overall aim to promote the valuable utilization of wastes or by-products from renewable energy technologies. It is assumed that bio-chars that have comparable energy contents with coals will be more desirable as solid energy materials due to renewability and environmental friendliness. Therefore, the analytical work in this study focused mainly on determining the higher heating value (HHV) of the chars. The method involved the reaction of bio-oil in an autoclave supplied by the Parr Instrument Company, IL, USA. Two main parameters (different temperatures and resident times) were investigated. The chars were characterized using a Thermo EA2000 CHNS analyser, then oxygen contents and HHVs computed based on the literature. From the results, these bio-chars can readily serve as feedstocks for the production of renewable solid fuels. Their HHVs ranged between 29.26-39.18 MJ/kg, affected by different temperatures and retention times. There was an inverse relationship between the oxygen content and the HHVs of the chars. It can, therefore, be concluded that it is possible to optimize the process efficiency of the hydrotreatment process used through the production of renewable energy materials from the 'waste’ char by-products. Future work should consider developing a suitable balance between the primary objective of bio-oil upgrading processes (which is to improve the quality of the liquid fuels) and the conversion of its solid wastes into value-added products such as smokeless briquettes.

Keywords: bio-char, renewable solid biofuels, valorisation, waste-to-energy

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10 CO2 Capture in Porous Silica Assisted by Lithium

Authors: Lucero Gonzalez, Salvador Alfaro

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Carbon dioxide (CO2) and methane (CH4) are considered as the compounds with higher abundance among the greenhouse gases (CO2, NOx, SOx, CxHx, etc.), due to its higher concentration, this two gases have a greater impact in the environment pollution and provokes global warming. So, recovery, disposal and subsequent reuse, are of great interest, especially from the ecological and health perspective. By one hand, porous inorganic materials are good candidates to capture gases, because these type of materials are higher stability from the point view of thermal, chemical and mechanical under adsorption gas processes. By another hand, during the design and the synthetic preparation of the porous materials is possible add other intrinsic properties (physicochemical and structural) by adding chemical compounds as dopants or using structured directed agents or surfactants to improve the porous structure, the above features allow to have alternative materials for separation, capture and storage of greenhouse gases. In this work, ordered mesoporous materials base silica were prepared using Surfynol as surfactant. The surfactant micelles are commonly used as self-assembly templates for the development of new structure porous silica’s, adding a variety of textures and structures. By another hand, the Surfynol is a commercial surfactant, is non-ionic, for that is necessary determine its critical micelles concentration (cmc) by the pyrene I1/I3 ratio method, before to prepare silica particles. One time known the CMC, a precursor gel was prepared via sol-gel process at room temperature using TEOS as silica precursor, NH4OH as catalyst, Surfynol as template and H2O as solvent. Then, the gel precursor was treatment hydrothermally in a Teflon-lined stainless steel autoclave with a volume of 100 mL and kept at 100 ºC for 24 h under static conditions in a convection oven. After that, the porous silica particles obtained were impregnated with lithium to improve the CO2 adsorption capacity. Then the silica particles were characterized physicochemical, morphology and structurally, by XRD, FTIR, BET and SEM techniques. The thermal stability and the CO2 adsorption capacity was evaluated by thermogravimetric analysis (TGA). According the results, we found that the Surfynol is a good candidate to prepare silica particles with an ordered structure. Also the TGA analysis shown that the particles has a good thermal stability in the range of 250 °C and 800 °C. The best materials had, the capacity to adsorbing 70 and 90 mg per gram of silica particles and its CO2 adsorption capacity depends on the way to thermal pretreatment of the porous silica before of the adsorption experiments and of the concentration of surfactant used during the synthesis of silica particles. Acknowledgments: This work was supported by SIP-IPN through project SIP-20161862.

Keywords: CO2 adsorption, lithium as dopant, porous silica, surfynol as surfactant, thermogravimetric analysis

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9 Predicting Polyethylene Processing Properties Based on Reaction Conditions via a Coupled Kinetic, Stochastic and Rheological Modelling Approach

Authors: Kristina Pflug, Markus Busch

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Being able to predict polymer properties and processing behavior based on the applied operating reaction conditions in one of the key challenges in modern polymer reaction engineering. Especially, for cost-intensive processes such as the high-pressure polymerization of low-density polyethylene (LDPE) with high safety-requirements, the need for simulation-based process optimization and product design is high. A multi-scale modelling approach was set-up and validated via a series of high-pressure mini-plant autoclave reactor experiments. The approach starts with the numerical modelling of the complex reaction network of the LDPE polymerization taking into consideration the actual reaction conditions. While this gives average product properties, the complex polymeric microstructure including random short- and long-chain branching is calculated via a hybrid Monte Carlo-approach. Finally, the processing behavior of LDPE -its melt flow behavior- is determined in dependence of the previously determined polymeric microstructure using the branch on branch algorithm for randomly branched polymer systems. All three steps of the multi-scale modelling approach can be independently validated against analytical data. A triple-detector GPC containing an IR, viscosimetry and multi-angle light scattering detector is applied. It serves to determine molecular weight distributions as well as chain-length dependent short- and long-chain branching frequencies. 13C-NMR measurements give average branching frequencies, and rheological measurements in shear and extension serve to characterize the polymeric flow behavior. The accordance of experimental and modelled results was found to be extraordinary, especially taking into consideration that the applied multi-scale modelling approach does not contain parameter fitting of the data. This validates the suggested approach and proves its universality at the same time. In the next step, the modelling approach can be applied to other reactor types, such as tubular reactors or industrial scale. Moreover, sensitivity analysis for systematically varying process conditions is easily feasible. The developed multi-scale modelling approach finally gives the opportunity to predict and design LDPE processing behavior simply based on process conditions such as feed streams and inlet temperatures and pressures.

Keywords: low-density polyethylene, multi-scale modelling, polymer properties, reaction engineering, rheology

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8 Impact of Boundary Conditions on the Behavior of Thin-Walled Laminated Column with L-Profile under Uniform Shortening

Authors: Jaroslaw Gawryluk, Andrzej Teter

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Simply supported angle columns subjected to uniform shortening are tested. The experimental studies are conducted on a testing machine using additional Aramis and the acoustic emission system. The laminate samples are subjected to axial uniform shortening. The tested columns are loaded with the force values from zero to the maximal load destroying the L-shaped column, which allowed one to observe the column post-buckling behavior until its collapse. Laboratory tests are performed at a constant velocity of the cross-bar equal to 1 mm/min. In order to eliminate stress concentrations between sample and support, flexible pads are used. Analyzed samples are made with carbon-epoxy laminate using the autoclave method. The configurations of laminate layers are: [60,0₂,-60₂,60₃,-60₂,0₃,-60₂,0,60₂]T, where direction 0 is along the length of the profile. Material parameters of laminate are: Young’s modulus along the fiber direction - 170GPa, Young’s modulus along the fiber transverse direction - 7.6GPa, shear modulus in-plane - 3.52GPa, Poisson’s ratio in-plane - 0.36. The dimensions of all columns are: length-300 mm, thickness-0.81mm, width of the flanges-40mm. Next, two numerical models of the column with and without flexible pads are developed using the finite element method in Abaqus software. The L-profile laminate column is modeled using the S8R shell elements. The layup-ply technique is used to define the sequence of the laminate layers. However, the model of grips is made of the R3D4 discrete rigid elements. The flexible pad is consists of the C3D20R type solid elements. In order to estimate the moment of the first laminate layer damage, the following initiation criteria were applied: maximum stress criterion, Tsai-Hill, Tsai-Wu, Azzi-Tsai-Hill, and Hashin criteria. The best compliance of results was observed for the Hashin criterion. It was found that the use of the pad in the numerical model significantly influences the damage mechanism. The model without pads characterized a much more stiffness, as evidenced by a greater bifurcation load and damage initiation load in all analyzed criteria, lower shortening, and less deflection of the column in its center than the model with flexible pads. Acknowledgment: The project/research was financed in the framework of the project Lublin University of Technology-Regional Excellence Initiative, funded by the Polish Ministry of Science and Higher Education (contract no. 030/RID/2018/19).

Keywords: angle column, compression, experiment, FEM

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7 Corrosion Protection and Failure Mechanism of ZrO₂ Coating on Zirconium Alloy Zry-4 under Varied LiOH Concentrations in Lithiated Water at 360°C and 18.5 MPa

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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6 Selective Conversion of Biodiesel Derived Glycerol to 1,2-Propanediol over Highly Efficient γ-Al2O3 Supported Bimetallic Cu-Ni Catalyst

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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5 Structural and Morphological Characterization of the Biomass of Aquatics Macrophyte (Egeria densa) Submitted to Thermal Pretreatment

Authors: Joyce Cruz Ferraz Dutra, Marcele Fonseca Passos, Rubens Maciel Filho, Douglas Fernandes Barbin, Gustavo Mockaitis

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The search for alternatives to control hunger in the world, generated a major environmental problem. Intensive systems of fish production can cause an imbalance in the aquatic environment, triggering the phenomenon of eutrophication. Currently, there are many forms of growth control aquatic plants, such as mechanical withdrawal, however some difficulties arise for their final destination. The Egeria densa is a species of submerged aquatic macrophyte-rich in cellulose and low concentrations of lignin. By applying the concept of second generation energy, which uses lignocellulose for energy production, the reuse of these aquatic macrophytes (Egeria densa) in the biofuels production can turn an interesting alternative. In order to make lignocellulose sugars available for effective fermentation, it is important to use pre-treatments in order to separate the components and modify the structure of the cellulose and thus facilitate the attack of the microorganisms responsible for the fermentation. Therefore, the objective of this research work was to evaluate the structural and morphological transformations occurring in the biomass of aquatic macrophytes (E.densa) submitted to a thermal pretreatment. The samples were collected in an intensive fish growing farm, in the low São Francisco dam, in the northeastern region of Brazil. After collection, the samples were dried in a 65 0C ventilation oven and milled in a 5mm micron knife mill. A duplicate assay was carried, comparing the in natural biomass with the pretreated biomass with heat (MT). The sample (MT) was submitted to an autoclave with a temperature of 1210C and a pressure of 1.1 atm, for 30 minutes. After this procedure, the biomass was characterized in terms of degree of crystallinity and morphology, using X-ray diffraction (XRD) techniques and scanning electron microscopy (SEM), respectively. The results showed that there was a decrease of 11% in the crystallinity index (% CI) of the pretreated biomass, leading to the structural modification in the cellulose and greater presence of amorphous structures. Increases in porosity and surface roughness of the samples were also observed. These results suggest that biomass may become more accessible to the hydrolytic enzymes of fermenting microorganisms. Therefore, the morphological transformations caused by the thermal pretreatment may be favorable for a subsequent fermentation and, consequently, a higher yield of biofuels. Thus, the use of thermally pretreated aquatic macrophytes (E.densa) can be an environmentally, financially and socially sustainable alternative. In addition, it represents a measure of control for the aquatic environment, which can generate income (biogas production) and maintenance of fish farming activities in local communities.

Keywords: aquatics macrophyte, biofuels, crystallinity, morphology, pretreatment thermal

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4 3D Nanostructured Assembly of 2D Transition Metal Chalcogenide/Graphene as High Performance Electrocatalysts

Authors: Sunil P. Lonkar, Vishnu V. Pillai, Saeed Alhassan

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Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

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3 Upgrading of Bio-Oil by Bio-Pd Catalyst

Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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2 Affordable and Environmental Friendly Small Commuter Aircraft Improving European Mobility

Authors: Diego Giuseppe Romano, Gianvito Apuleo, Jiri Duda

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Mobility is one of the most important societal needs for amusement, business activities and health. Thus, transport needs are continuously increasing, with the consequent traffic congestion and pollution increase. Aeronautic effort aims at smarter infrastructures use and in introducing greener concepts. A possible solution to address the abovementioned topics is the development of Small Air Transport (SAT) system, able to guarantee operability from today underused airfields in an affordable and green way, helping meanwhile travel time reduction, too. In the framework of Horizon2020, EU (European Union) has funded the Clean Sky 2 SAT TA (Transverse Activity) initiative to address market innovations able to reduce SAT operational cost and environmental impact, ensuring good levels of operational safety. Nowadays, most of the key technologies to improve passenger comfort and to reduce community noise, DOC (Direct Operating Costs) and pilot workload for SAT have reached an intermediate level of maturity TRL (Technology Readiness Level) 3/4. Thus, the key technologies must be developed, validated and integrated on dedicated ground and flying aircraft demonstrators to reach higher TRL levels (5/6). Particularly, SAT TA focuses on the integration at aircraft level of the following technologies [1]: 1)    Low-cost composite wing box and engine nacelle using OoA (Out of Autoclave) technology, LRI (Liquid Resin Infusion) and advance automation process. 2) Innovative high lift devices, allowing aircraft operations from short airfields (< 800 m). 3) Affordable small aircraft manufacturing of metallic fuselage using FSW (Friction Stir Welding) and LMD (Laser Metal Deposition). 4)       Affordable fly-by-wire architecture for small aircraft (CS23 certification rules). 5) More electric systems replacing pneumatic and hydraulic systems (high voltage EPGDS -Electrical Power Generation and Distribution System-, hybrid de-ice system, landing gear and brakes). 6) Advanced avionics for small aircraft, reducing pilot workload. 7) Advanced cabin comfort with new interiors materials and more comfortable seats. 8) New generation of turboprop engine with reduced fuel consumption, emissions, noise and maintenance costs for 19 seats aircraft. (9) Alternative diesel engine for 9 seats commuter aircraft. To address abovementioned market innovations, two different platforms have been designed: Reference and Green aircraft. Reference aircraft is a virtual aircraft designed considering 2014 technologies with an existing engine assuring requested take-off power; Green aircraft is designed integrating the technologies addressed in Clean Sky 2. Preliminary integration of the proposed technologies shows an encouraging reduction of emissions and operational costs of small: about 20% CO2 reduction, about 24% NOx reduction, about 10 db (A) noise reduction at measurement point and about 25% DOC reduction. Detailed description of the performed studies, analyses and validations for each technology as well as the expected benefit at aircraft level are reported in the present paper.

Keywords: affordable, European, green, mobility, technologies development, travel time reduction

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1 Intensification of Wet Air Oxidation of Landfill Leachate Reverse Osmosis Concentrates

Authors: Emilie Gout, Mathias Monnot, Olivier Boutin, Pierre Vanloot, Philippe Moulin

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Water is a precious resource. Treating industrial wastewater remains a considerable technical challenge of our century. The effluent considered for this study is landfill leachate treated by reverse osmosis (RO). Nowadays, in most developed countries, sanitary landfilling is the main method to deal with municipal solid waste. Rainwater percolates through solid waste, generating leachates mostly comprised of organic and inorganic matter. Whilst leachate ages, its composition varies, becoming more and more bio-refractory. RO is already used for landfill leachates as it generates good quality permeate. However, its mains drawback is the production of highly polluted concentrates that cannot be discharged in the environment or reused, which is an important industrial issue. It is against this background that the study of coupling RO with wet air oxidation (WAO) was set to intensify and optimize processes to meet current regulations for water discharge in the environment. WAO is widely studied for effluents containing bio-refractory compounds. Oxidation consists of a destruction reaction capable of mineralizing the recalcitrant organic fraction of pollution into carbon dioxide and water when complete. WAO process in subcritical conditions requires a high-energy consumption, but it can be autothermic in a certain range of chemical oxygen demand (COD) concentrations (10-100 g.L⁻¹). Appropriate COD concentrations are reached in landfill leachate RO concentrates. Therefore, the purpose of this work is to report the performances of mineralization during WAO on RO concentrates. The coupling of RO/WAO has shown promising results in previous works on both synthetic and real effluents in terms of organic carbon (TOC) reduction by WAO and retention by RO. Non-catalytic WAO with air as oxidizer was performed in a lab-scale stirred autoclave (1 L) on landfill leachates RO concentrates collected in different seasons in a sanitary landfill in southern France. The yield of WAO depends on operating parameters such as total pressure, temperature, and time. Compositions of the effluent are also important aspects for process intensification. An experimental design methodology was used to minimize the number of experiments whilst finding the operating conditions achieving the best pollution reduction. The simulation led to a set of 18 experiments, and the responses to highlight process efficiency are pH, conductivity, turbidity, COD, TOC, and inorganic carbon. A 70% oxygen excess was chosen for all the experiments. First experiments showed that COD and TOC abatements of at least 70% were obtained after 90 min at 300°C and 20 MPa, which attested the possibility to treat RO leachate concentrates with WAO. In order to meet French regulations and validate process intensification with industrial effluents, some continuous experiments in a bubble column are foreseen, and some further analyses will be performed, such as biological oxygen demand and study of gas composition. Meanwhile, other industrial effluents are treated to compare RO-WAO performances. These effluents, coming from pharmaceutical, petrochemical, and tertiary wastewater industries, present different specific pollutants that will provide a better comprehension of the hybrid process and prove the intensification and feasibility of the process at an industrial scale. Acknowledgments: This work has been supported by the French National Research Agency (ANR) for the Project TEMPO under the reference number ANR-19-CE04-0002-01.

Keywords: hybrid process, landfill leachates, process intensification, reverse osmosis, wet air oxidation

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