Search results for: supercritical methanol

Authors: Velid Demir, Mesut Akgün

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The lanthanum and zinc oxide were synthesized and then loaded with 6 wt% over γ-Al₂O₃ using the wet impregnation method. The samples were calcined at 900 °C to ensure a coherent structure with high catalytic performance. Characterization of the catalysts was verified by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). The effect of catalysts on biodiesel content from jatropha oil was studied under supercritical conditions. The results showed that ZnO/γ-Al₂O₃ was the superior catalyst for jatropha oil with 98.05% biodiesel under reaction conditions of 7 min reaction time, 1:40 oil to methanol molar ratio, 6 wt% of catalyst loading, 90 bar of reaction pressure, and 300 °C of reaction temperature, compared to 95.50% with La₂O₃/γ-Al₂O₃ at the same parameters. For this study, ZnO/γ-Al₂O₃ was the most suitable catalyst due to performance and cost considerations.

Keywords: biodiesel, heterogeneous catalyst, jatropha oil, supercritical methanol, transesterification

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Authors: M. Kustyawati, F. Pratama, D. Saputra, A. Wijaya

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Tempe composes of not only molds but also bacteria and yeasts. The structure of microorganisms needs to be in balance number in order the tempe to be an acceptable quality for an extended time. Sub supercritical carbon dioxide can be a promising preservation method for tempe as it induces microbial inactivation avoiding alterations of its quality attributes. Fresh tempe were processed using supercritical and sub supercritical CO2 for a defined holding times, then the growth ability of molds and bacteria were analyzed. The results showed that the supercritical CO2 processing for 5 minutes reduced the number of bacteria and molds to 0.30 log cycle and 1.17 log cycles, respectively. In addition, sub supercritical CO2 processing for 20 minutes had fungicidal effect against mold tempe; whereas, the sub supercritical CO2 for 10 minutes had reducing effect against bacteria tempe, and had fungistatic affect against mold tempe. It suggested that sub-supercritical CO2 processing for 10 min could be useful alternative technique for preservation of tempe.

Keywords: tempe, sub supercritical CO2, fungistatic effect, preservation

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Authors: Sui Yan Wong, Keat Ping Yeoh, Chi Wai Hui

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In this study, supercritical steam is introduced to Combined Cycle Power Plant (CCPP) in an attempt to further optimize energy recovery. Subcritical steam is commonly used in the CCPP, operating at maximum pressures around 150-160 bar. Supercritical steam is an alternative to increase heat recovery during vaporization period of water. The idea of improvement using supercritical steam is further examined with the use of exergy, pinch analysis and Aspen Plus simulation.

Keywords: exergy, pinch, combined cycle power plant, supercritical steam

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Authors: M. Bougamouza, M. Bouhadef, T. Zitoun

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The aim of this study is to examine, through experimentation in the laboratory, the supercritical flow in the presence of an obstacle in a rectangular channel. The supercritical regime in the whole hydraulic channel is achieved by adding a convergent. We will observe the influence of the obstacle shape and dimension on the characteristics of the supercritical flow, mainly the free-surface elevation and the velocity profile. The velocity measurements have been conducted with the one dimension laser anemometry technique.

Keywords: experiments, free-surface flow, hydraulic channel, uneven bottom, laser anemometry, supercritical regime

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Authors: Boy Arief Fachri

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Even its content is rich in antioxidants ϒ-oryzanol, rice bran is not used properly as functional food. This research aims to (1) extract ϒ-oryzanol; (2) determine the solubility of ϒ-oryzanol in supercritical CO₂ based on phase equilibrium theory; and (3) study the effect of process variables on solubility. Extraction experiments were carried out for rice bran (5 g) at various extraction pressures, temperatures and reaction times. The flowrate of supercritical fluid through the extraction vessel was 25 g/min. The extracts were collected and analysed with high-pressure liquid chromatography (HPLC). The conclusion based on the experiments are as: (1) The highest experimental solubility was 0.303 mcg/mL RBO at T= 60°C, P= 90 atm, t= 30 min; (2) Solubility of ϒ-oryzanol was influenced by pressure and temperature. As the pressure and temperature increase, the solubility increases; (3) The solubility data of supercritical extraction can be successfully determined using phase equilibrium theory. Meanwhile, tocopherol was found and slightly investigated in this work.

Keywords: rice bran, solubility, supercritical CO2, ϒ-orizanol

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Authors: M. Azadi, N. Tahouni, M. H. Panjeshahi

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A techno-economic evaluation for efficient use of energy in a large scale industrial plant of methanol is carried out. This assessment is based on integration of a gas turbine with an existing plant of methanol in which the outlet gas products of exothermic reactor is expanded to power generation. Also, it is decided that methanol production rate is constant through addition of power generation system to the existing methanol plant. Having incorporated a gas turbine with the existing plant, the economic results showed total investment of MUSD 16.9, energy saving of 3.6 MUSD/yr with payback period of approximately 4.7 years.

Keywords: energy saving, methanol, gas turbine, power generation

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Authors: Hanifa Taher, Sulaiman Al-Zuhair, Ali H. Al-Marzouqi, Yousef Haik, Mohammed Farid

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Biodiesel, as an alternative renewable fuel, has been receiving increasing attention due to the limited supply of fossil fuels and the increasing need for energy. Microalgae is a promising source for lipids, which can be converted to biodiesel. The biodiesel production from microalgae lipids using lipase catalyzed reaction in supercritical CO2 medium has several advantages over conventional production processes. However, identifying the optimum microalgae lipid extraction and transesterification conditions is still a challenge. In this study, the lipids extracted from Scenedesmus sp. and their enzymatic transesterification using supercritical carbon dioxide have been investigated. The effect of extraction variables (temperature, pressure and solvent flow rate) and reaction variables (enzyme loading, incubation time, methanol to lipids molar ratio and temperature) were considered. Process parameters and their effects were studied using a full factorial analysis of both. Response Surface Methodology (RSM) and was used to determine the optimum conditions for the extraction and reaction steps. For extraction, the optimum conditions were 53 °C and 500 bar, whereas for the reaction the optimum conditions were 35% enzyme loading, 4 h reaction, 9:1 molar ratio and 50 oC. At these optimum conditions, the highest biodiesel production yield was found to be 82 %. The fuel properties of the produced biodiesel, at optimum reaction condition, were determined and compared to ASTM standards. The properties were found to comply with the limits, and showed a low glycerol content, without any separation step.

Keywords: biodiesel, lipase, supercritical CO2, standards

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Authors: Hamidreza Bagheri, Alireza Shariati

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There are many difficulties in the purification of raw components and products. However, researchers are seeking better ways for purification. One of the recent methods is extraction using supercritical fluids. In this study, the phase equilibria of benzoic acid-supercritical carbon dioxide system were investigated. Regarding the phase equilibria of this system, the modeling of solid-supercritical fluid behavior was performed using the Perturbed-Chain Statistical Association Fluid Theory (PC-SAFT) and Peng-Robinson equations of state (PR EoS). For this purpose, five PC-SAFT EoS parameters for pure benzoic acid were obtained using its experimental vapor pressure. Benzoic acid has association sites and the behavior of the benzoic acid-supercritical fluid system was well-predicted using both equations of state, while the binary interaction parameter values for PR EoS were negative. Genetic algorithm, which is one of the most accurate global optimization algorithms, was also used to optimize the pure benzoic acid parameters and the binary interaction parameters. The AAD% value for the PC-SAFT EoS, were 0.22 for the carbon dioxide-benzoic acid system.

Keywords: supercritical fluids, solubility, solid, PC-SAFT EoS, genetic algorithm

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Authors: Parvaneh Hajeb, Shahram Shakibazadeh, Md. Zaidul Islam Sarker

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High-quality fish oil for human consumption requires low levels of toxic elements. The aim of this study was to develop a method to extract oil from fish wastes with the least toxic elements contamination. Supercritical fluid extraction (SFE) was applied to detoxify fish oils from toxic elements. The SFE unit used consisted of an intelligent HPLC pump equipped with a cooling jacket to deliver CO2. The freeze-dried fish waste sample was extracted by heating in a column oven. Under supercritical conditions, the oil dissolved in CO2 was separated from the supercritical phase using pressure reduction. The SFE parameters (pressure, temperature, CO2 flow rate, and extraction time) were optimized using response surface methodology (RSM) to extract the highest levels of toxic elements. The results showed that toxic elements in fish oil can be reduced using supercritical CO2 at optimum pressure 40 MPa, temperature 61 ºC, CO2 flow rate 3.8 MPa, and extraction time 4.25 hr. There were significant reductions in the mercury (98.2%), cadmium (98.9%), arsenic (96%), and lead contents (99.2%) of the fish oil. The fish oil extracted using this method contained elements at levels that were much lower than the accepted limits of 0.1 μg/g. The reduction of toxic elements using the SFE method was more efficient than that of the conventional methods due to the high selectivity of supercritical CO2 for non-polar compounds.

Keywords: food safety, toxic elements, fish oil, supercritical carbon dioxide

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Authors: Huirui Han, Chao Zhang

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The rod bundle is used in the fuel assembly of the supercritical water-cooled nuclear reactor. In the rod bundle, the coolant absorbs the heat contributed by the fission process. Because of the dramatic variations in the thermophysical properties of water at supercritical conditions, it is essential to investigate the heat transfer characteristics of supercritical water in the rod bundle to ensure the safety of the nuclear power plant. In this study, the effects of the flow direction, including horizontal, upward, and downward, on the fluid flow and heat transfer of the supercritical water in the rod bundle were studied numerically. The results show the possibility of gap vortices in the flow subchannels of the rod bundle. In addition, the distributions of the circumferential wall temperature show differences in different flow direction conditions. It was also found that the circumferential cladding surface temperature distribution in the upward flow condition is extremely non-uniform, and there is a large difference between the maximum wall temperatures for different fuel rods.

Keywords: heat transfer, rod bundle, supercritical water, wall temperature

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Authors: Espinoza S. Clara, Gamarra Q. Flor, Marianela F. Ramos Quispe S. Miguel, Flores R. Omar

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Tropaeolum majus L. is a native plant to South and Central America, used since ancient times by our ancestors to combat different diseases. Glucotropaeolonin is one of its main components, which when hydrolyzed, forms benzyl isothiocyanate (BIT) that promotes cellular apoptosis (programmed cell death in cancer cells). Therefore, the present research aims to evaluate the effect of the pressure and temperature of BIT extraction by supercritical CO₂ from Tropaeolum majus L. The extraction was carried out in a supercritical fluid extractor equipment Speed SFE BASIC Brand: Poly science, the leaves of Tropaeolum majus L. were ground for one hour and lyophilized until obtaining a humidity of 6%. The extraction with supercritical CO₂ was carried out with pressures of 200 bar and 300 bar, temperatures of 50°C, 60°C and 70°C, obtained by the conjugation of these six treatments. BIT was identified by thin layer chromatography using 98% BIT as the standard, and as the mobile phase hexane: dichloromethane (4:2). Subsequently, BIT quantification was performed by high performance liquid chromatography (HPLC). The highest yield of oleoresin by supercritical CO₂ extraction was obtained pressure 300 bar and temperature at 60°C; and the higher content of BIT at pressure 200 bar and 70°C for 30 minutes to obtain 113.615 ± 0.03 mg BIT/100 g dry matter was obtained.

Keywords: solvent extraction, Tropaeolum majus L., supercritical fluids, benzyl isothiocyanate

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Authors: Shyh-Ming Chern, Kai-Ting Hsieh

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Organic solvents find various applications in many industrial sectors and laboratories as dilution solvents, dispersion solvents, cleaners and even lubricants. Millions of tons of Spent Organic Solvents (SOS) are generated each year worldwide, prompting the need for more efficient, cleaner and safer methods for the treatment and resource recovery of SOS. As a result, acetone, selected as a model compound for SOS, was gasified in supercritical water to assess the feasibility of resource recovery of SOS by means of supercritical water processes. Experiments were conducted with an autoclave reactor. Gaseous product is mainly consists of H2, CO, CO2 and CH4. The effects of three major operating parameters, the reaction temperature, from 673 to 773K, the dosage of oxidizing agent, from 0.3 to 0.5 stoichiometric oxygen, and the concentration of acetone in the feed, 0.1 and 0.2M, on the product gas composition, yield and heating value were evaluated with the water density fixed at about 0.188g/ml.

Keywords: acetone, gasification, SCW, supercritical water

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Authors: D. M. Reddy Prasad, Nur Sabrina Binti Rahmat, Huei Ruey Ong, Chin Kui Cheng, Maksudur Rahman Khan, D. Sathiyamoorthy

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Carbon dioxide (CO₂) emission to the environment is inevitable which is responsible for global warming. Photocatalytic reduction of CO₂ to fuel, such as methanol, methane etc. is a promising way to reduce greenhouse gas CO₂ emission. In the present work, Bi₂S₃/CdS was synthesized as an effective visible light responsive photocatalyst for CO₂ reduction into methanol. The Bi₂S₃/CdS photocatalyst was prepared by hydrothermal reaction. The catalyst was characterized by X-ray diffraction (XRD) instrument. The photocatalytic activity of the catalyst has been investigated for methanol production as a function of time. Gas chromatograph flame ionization detector (GC-FID) was employed to analyze the product. The yield of methanol was found to increase with higher CdS concentration in Bi₂S₃/CdS and the maximum yield was obtained for 45 wt% of Bi₂S₃/CdS under visible light irradiation was 20 μmole/g. The result establishes that Bi₂S₃/CdS is favorable catalyst to reduce CO₂ to methanol.

Keywords: photocatalyst, CO2 reduction, methanol, visible light, XRD, GC-FID

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Authors: Jakub Zágora, Daniela Plachá, Karla Čech Barabaszová, Sylva Holešová, Roman Gábor, Alexandra Muñoz Bonilla, Marta Fernández García

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The development of new antimicrobial materials that are not toxic to higher living organisms is a major challenge today. Newly developed materials can have high application potential in biomedicine, coatings, packaging, etc. A combination of commonly used biopolymer polylactide with cationic polymers seems to be very successful in the fight against antimicrobial resistance [1].PLA will play a key role in fulfilling the intention set out in the New Deal announced by the EU commission, as it is a bioplastic that is easily degradable, recyclable, and mass-produced. Also, the development of 3D printing in the context of this initiative, and the actual use of PLA as one of the main materials used for this printing, make the technology around the preparation and modification of PLA quite logical. Moreover, theenvironmentally friendly and energy saving technology like supercritical fluid process (SFP) will be used for their preparation. In a first approach, polylactide nano- and microparticles and structures were prepared by supercritical fluid extraction. The RESS (rapid expansion supercritical fluid solution) method is easier to optimize and shows better particle size control. On the contrary, a highly porous structure was obtained using the SAS (supercritical antisolvent) method. In a second part, the antimicrobial biobased polymer was introduced by SFP.

Keywords: polylactide, antimicrobial polymers, supercritical fluid technology, micronization

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Authors: Shyh-Ming Chern, H. Y. Cheng

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Biomass is renewable and sustainable. As an energy source, it will not release extra carbon dioxide into the atmosphere. Hence, tremendous efforts have been made to develop technologies capable of transforming biomass into suitable forms of bio-fuel. One of the viable technologies is gasifying biomass in supercritical water (SCW), a green medium for reactions. While previous studies overwhelmingly selected glucose as a model compound for biomass, the present study adopted fructose for the sake of comparison. The gasification of fructose in SCW was investigated experimentally to evaluate the applicability of supercritical water processes to biomass gasification. Experiments were conducted with an autoclave reactor. Gaseous product mainly consists of H2, CO, CO2, CH4 and C2H6. The effect of two major operating parameters, the reaction temperature (673-873 K) and the dosage of oxidizing agent (0-0.5 stoichiometric oxygen), on the product gas composition, yield and heating value was also examined, with the reaction pressure fixed at 25 MPa.

Keywords: biomass, fructose, gasification, supercritical water

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Authors: Antaram Sarve, Mahesh Varma, Shriram Sonawane

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Conventional route of producing biodiesel with alcohol produces glycerol as side product which leads to oversupply and devaluation in the world market. Supercritical methyl acetate (SCMA) has been proven to convert triglycerides into fatty acid methyl esters (FAMEs) and triacetin, which is a valuable biodiesel additive as side product rather than glycerol. However, due to the low reactivity of supercritical methyl acetate on triglycerides, high reaction conditions are required to obtained maximum yields. The present study describes the renewable approach for the production of biodiesel from low-cost, high acid value mahua oil under supercritical methyl acetate condition using carbon dioxide (CO2) as a co-solvent. CO2 was employed to decrease high reaction conditions required for supercritical methyl acetate transesterification. The influence of process parameters such as temperature, oil to methyl acetate molar ratio, reaction time, and the CO2 pressure was evaluated. The properties of biodiesel produced were found to be superior compared to conventional biodiesel method. Furthermore, SCMA has a high tolerance towards free fatty acids (FFAs) which is crucial to allow the utilization of inexpensive waste oils as a biodiesel feedstock.

Keywords: supercritical methyl acetate, CO2, biodiesel, fuel properties

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Authors: Chia-Yu Lin, Chun-Ying Lee, Chih-Jer Lin

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Lemongrass (Cymbopogon citratus), grown in tropical and subtropical regions over the world, has many potential uses in pharmaceutical, cosmetics, food and flavor, and agriculture industries. In this study, because of its affinity to human body and friendliness to the environment, lemongrass extract was prepared from different processes to evaluate its effectiveness as mosquito repellent. Moreover, the supercritical fluid extraction method has been widely used as an effective and environmental friendly process in the preparation of a variety of compounds. Thus, both the extracts from lemongrass by the conventional hydrodistillation method and the supercritical CO₂ assisted method were compared. The effects of pressure, temperature and time duration on the supercritical CO₂ extraction were also investigated. The compositions of different extracts were examined using mass spectrometer. As for the experiment of mosquito repellence, the extract was placed inside a mosquito trap along with syrup. The mosquito counts in each trap with extracts prepared from different processes were employed in the quantitative evaluation. It was found that the extract from the supercritical CO₂ assisted process contained higher citronellol content than the conventional hydrodistillation method. The extract with higher citronellol content also demonstrated more effective as a mosquito repellent.

Keywords: lemongrass (Cymbopogon citratus), hydrodistillation, supercritical fluid extraction, mosquito repellent

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Authors: Haifa El-Sadi, Maria Elektorowicz, Reed Rushing, Ammar Badawieh, Asif Chaudry

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Clay soils have particular properties that affect the assessment and remediation of contaminated sites. In clay soils, electro-kinetic transport of heavy metals has been carried out. The transport of these metals is predicated on maintaining a low pH throughout the cell, which, in turn, keeps the metals in the pore water phase where they are accessible to electro-kinetic transport. Supercritical fluid extraction and acid digestion were used for the analysis of heavy metals concentrations after the completion of electro-kinetic experimentation. Supercritical fluid (carbon dioxide) extraction is a new technique used to extract the heavy metal (lead, nickel, calcium and potassium) from clayey soil. The comparison between supercritical extraction and acid digestion of different metals was carried out. Supercritical fluid extraction, using ethylenediaminetetraacetic acid (EDTA) as a modifier, proved to be efficient and a safer technique than acid digestion technique in extracting metals from clayey soil. Mixing time of soil with EDTA before extracting heavy metals from clayey soil was investigated. The optimum and most practical shaking time for the extraction of lead, nickel, calcium and potassium was two hours.

Keywords: clay soil, heavy metals, supercritical fluid extraction, acid digestion

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Authors: Suresh Sahu, Abhijeet M. Vaidya, Naresh K. Maheshwari

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The efforts to understand the heat transfer behavior of supercritical water in supercritical water cooled reactor (SCWR) are ongoing worldwide to fulfill the future energy demand. The higher thermal efficiency of these reactors compared to a conventional nuclear reactor is one of the driving forces for attracting the attention of nuclear scientists. In this work, a solution procedure has been described for solving supercritical fluid flow problems in complex geometries. The solution procedure is based on non-staggered grid. All governing equations are discretized by finite volume method (FVM) in curvilinear coordinate system. Convective terms are discretized by first-order upwind scheme and central difference approximation has been used to discretize the diffusive parts. k-ε turbulence model with standard wall function has been employed. SIMPLE solution procedure has been implemented for the curvilinear coordinate system. Based on this solution method, 3-D Computational Fluid Dynamics (CFD) code has been developed. In order to demonstrate the capability of this CFD code in supercritical fluid flows, heat transfer to supercritical water in circular tubes has been considered as a test problem. Results obtained by code have been compared with experimental results reported in literature.

Keywords: curvilinear coordinate, body-fitted mesh, momentum interpolation, non-staggered grid, supercritical fluids

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Authors: Monika Šípová, Daniela Marušáková, Claudia Aparicio

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New sources and ways of producing energy are still seeking, and one of the sustainable ways is Generation IV nuclear reactors. The supercritical water-cooled reactor is one of the six nuclear reactors of Generation IV, and as a consequence of the development of light water, reactors seem to be the most perspective. Thus, materials usually used in light water reactors are also tested under the expected operating conditions of the supercritical water-cooled reactor. Austenitic stainless steel 08Cr18Ni10Ti is widely used in the eastern types of light water nuclear power plants. Therefore, specimens of 08Cr18Ni10Ti were exposed to conditions close to the pseudo-critical point of water and high-temperature supercritical water. The description and evaluation of the corrosion behaviour of austenitic stainless steel have been done based on the results of X-ray diffraction in combination with energy dispersive spectroscopy and electron backscatter diffraction. Thus, significant differences have been found in the structure and composition of oxides formed depending on the temperature of exposure. The high temperature of supercritical water resulted in localised form of corrosion in contrast to the thin oxide layer of 1 µm present on the surface of specimens exposed close to the pseudo-critical point of water. The obtained results are important for further research as the supercritical water can be successfully used as a coolant for small modular reactors, which are currently of interest.

Keywords: localised corrosion, supercritical water, stainless steel, electron backscatter diffraction

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Authors: Hamza Javar Magnier, Leslie V. Woodcock

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We report extensive molecular dynamics (MD) computational investigations into the thermodynamic description of supercritical properties for a model fluid that is the simplest realistic representation of atoms or molecules. The pair potential is a hard-sphere repulsion of diameter σ with a very short attraction of length λσ. When λ = 1.005 the range is so short that the model atoms are referred to as “adhesive spheres”. Molecular dimers, trimers …etc. up to large clusters, or droplets, of many adhesive-sphere atoms are unambiguously defined. This then defines percolation transitions at the molecular level that bound the existence of gas and liquid phases at supercritical temperatures, and which define the existence of a supercritical mesophase. Both liquid and gas phases are seen to terminate at the loci of percolation transitions, and below a second characteristic temperature (Tc2) are separated by the supercritical mesophase. An analysis of the distribution of clusters in gas, meso- and liquid phases confirms the colloidal nature of this mesophase. The general phase behaviour is compared with both experimental properties of the water-steam supercritical region and also with formally exact cluster theory of Mayer and Mayer. Both are found to be consistent with the present findings that in this system the supercritical mesophase narrows in density with increasing T > Tc and terminates at a higher Tc2 at a confluence of the primary percolation loci. The expended plot of the MD data points in the mesophase of 7 critical and supercritical isotherms in highlight this narrowing in density of the linear-slope region of the mesophase as temperature is increased above the critical. This linearity in the mesophase implies the existence of a linear combination rule between gas and liquid which is an extension of the Lever rule in the subcritical region, and can be used to obtain critical parameters without resorting to experimental data in the two-phase region. Using this combination rule, the calculated critical parameters Tc = 0.2007 and Pc = 0.0278 are found be agree with the values found by of Largo and coworkers. The properties of this supercritical mesophase are shown to be consistent with an alternative description of the phenomenon of critical opalescence seen in the supercritical region of both molecular and colloidal-protein supercritical fluids.

Keywords: critical opalescence, supercritical, square-well, percolation transition, critical parameters.

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Authors: N. R. Putra, A. H. Abdul Aziz, A. S. Zaini, Z. Idham, F. Idrus, M. Z. Bin Zullyadini, M. A. Che Yunus

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The content of omega-3 in soybean oil is important in the development of infants and is an alternative for the omega-3 in fish oils. The investigation of extraction of soybean oil is needed to obtain the bioactive compound in the extract. Supercritical carbon dioxide extraction is modern and green technology to extract herbs and plants to obtain high quality extract due to high diffusivity and solubility of the solvent. The aim of this study was to obtain the optimum condition of soybean oil extraction by modified supercritical carbon dioxide. The soybean oil was extracted by using modified supercritical carbon dioxide (SC-CO₂) under the temperatures of 40, 60, 80 °C, pressures of 150, 250, 350 Bar, and constant flow-rate of 10 g/min as the parameters of extraction processes. An experimental design was performed in order to optimize three important parameters of SC-CO₂ extraction which are pressure (X₁), temperature (X₂) to achieve optimum yields of soybean oil. Box Behnken Design was applied for experimental design. From the optimization process, the optimum condition of extraction of soybean oil was obtained at pressure 338 Bar and temperature 80 °C with oil yield of 2.713 g. Effect of pressure is significant on the extraction of soybean oil by modified supercritical carbon dioxide. Increasing of pressure will increase the oil yield of soybean oil.

Keywords: soybean oil, SC-CO₂ extraction, yield, optimization

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Authors: Igor Svishchev, Kashif Choudhry

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Progress in advanced energy technologies is not feasible without understanding how engineering materials perform under extreme environmental conditions. The corrosion behaviour of Fe-Ni-Cr and Zr alloys has been systematically examined under high-temperature and supercritical water flow conditions. The changes in elemental release rate and dissolved gas concentration provide valuable insights into the mechanism of passivation by forming oxide films. A non-intrusive method for monitoring the extent of surface oxidation based on hydrogen release rate has been developed. This approach can be used for the on-line monitoring corrosion behavior of reactor materials without the need to interrupt the flow and remove corrosion coupons. Surface catalysed thermochemical reactions may generate sufficient hydrogen to have an effect on the accumulation of oxidizing species generated by radiolytic processes in the heat transport systems of the supercritical water cooled nuclear reactor.

Keywords: high-temperature corrosion, non-intrusive monitoring, reactor materials, supercritical water

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Authors: Junaid Bin Aamir, Ma Fanhua

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Methanol is one of the most suitable alternative fuels for replacing gasoline in present and future spark-ignited engines. However, for pure methanol engines, cold start problems and misfires are observed under certain operating conditions. Hydrogen provides a solution for such problems. This paper experimentally investigated the effect of hydrogen on the performance of a pure methanol SI-engine at city driving conditions (1500 rpm speed and 1.18 excess air ratio). Hydrogen was used as a part of methanol reformed syngas (67% hydrogen by volume). 4% by mass of the total methanol converted to hydrogen and other constituent gases, was used in each cycle. Port fuel injection was used to inject methanol and hydrogen-rich syngas into the 4-cylinder engine. The results indicated an increase in brake thermal efficiency up to 5% with the addition of hydrogen, a decrease in brake specific fuel consumption up to 200 g/kWh, and a decrease in exhaust gas temperature by 100°C for all mean effective pressures. Hydrogen addition also decreased harmful exhaust emissions significantly. There was a reduction in THC emissions up to 95% and CO emissions up to 50%. NOx emissions were slightly increased (up to 15%), but they can be reduced to zero by lean burn strategy.

Keywords: alternative fuels, hydrogen, methanol, performance, spark ignition engines

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Authors: Hongfang Ma, Mingchuan Zhou, Haitao Zhang, Weiyong Ying

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One dimensional pseudo-homogenous modeling has been performed for methanol steam reforming reactor. The results show that the models can well predict the industrial data. The reactor had minimum temperature along axial because of endothermic reaction. Hydrogen productions and temperature profiles along axial were investigated regarding operation conditions such as inlet mass flow rate and mass fraction of methanol, inlet temperature of external thermal oil. Low inlet mass flow rate of methanol, low inlet temperature, and high mass fraction of methanol decreased minimum temperature along axial. Low inlet mass flow rate of methanol, high mass fraction of methanol, and high inlet temperature of thermal oil made cold point forward. Low mass fraction, high mass flow rate, and high inlet temperature of thermal oil increased hydrogen production. One dimensional models can be a guide for industrial operation.

Keywords: reactor, modeling, methanol, steam reforming

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Authors: Junaid Bin Aamir, Ma Fanhua

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Methanol and hydrogen are the most suitable alternative fuel resources for the existing and future internal combustion engines. This paper experimentally examined the effects of hydrogen addition on the performance and emission characteristics of a spark-ignition engine fueled with methanol at part load conditions. The experiments were carried out for various engine speeds and loads. Hydrogen-rich syngas was used to enhance the performance of the test engine. It was formed by catalytic dissociation of methanol itself, and volumetric hydrogen fraction in syngas was about 67%. A certain amount of syngas dissociated from methanol was injected into the intake manifold in each engine cycle, and the low heating value (LHV) of hydrogen-rich syngas used was 4% of methanol in each cycle. Both the fuels were injected separately using port fuel injectors. The results showed that brake thermal efficiency of the engine was enhanced by 3-5% with hydrogen addition, while brake specific fuel consumption and exhaust gas temperature were reduced. There was a significant reduction (90-95%) in THC and (35-50%) in CO emissions at the exhaust. NOx emissions from hydrogen blended methanol increased slightly (10-15%), but they can be reduced by using lean fuel-air mixture to keep the cylinder temperature low.

Keywords: hydrogen, methanol, alternative fuel, emissions, spark ignition engines

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M. S. Shaharun

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Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO₂ to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO₂ to methanol in microactivity fixed-bed reactor at 250^oC, 2.25 MPa, and H₂/CO₂ ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H₂ and CO₂ and accelerate the CO₂ conversion, resulting in higher methanol production under mild reaction conditions.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, Cu/ZnO-based catalyst, mesoporous silica (SBA-15), metal ratio

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Authors: Hamza Javar Magnier, Leslie V. Woodcock

Abstract:

It has been reported that at temperatures above the critical there is no “continuity of liquid and gas”, as originally hypothesized by van der Waals. Rather, both gas and liquid phases, with characteristic properties as such, extend to supercritical temperatures. Each phase is bounded by the locus of a percolation transition, i.e. a higher-order thermodynamic phase change associated with percolation of gas clusters in a large void, or liquid interstitial vacancies in a large cluster. Between these two-phase bounds, it is reported there exists a mesophase that resembles an otherwise homogeneous dispersion of gas micro-bubbles in liquid (foam) and a dispersion of liquid micro-droplets in gas (mist). Such a colloidal-like state of a pure one-component fluid represents a hitherto unchartered equilibrium state of matter besides pure solid, liquid or gas. Here we provide compelling evidence, from molecular dynamics (MD) simulations, for the existence of this supercritical mesophase and its colloidal nature. We report preliminary results of computer simulations for a model fluid using a simplistic representation of atoms or molecules, i.e. a hard-core repulsion with an attraction so short that the atoms are referred to as “adhesive spheres”. Molecular clusters, and hence percolation transitions, are unambiguously defined. Graphics of color-coded clusters show colloidal characteristics of the supercritical mesophase.

Keywords: critical phenomena, mesophase, supercritical, square-well, critical parameters

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Authors: Chun-Ying Lee, Mei-Wen Wu, Li-Yi Cheng, Chiang-Ho Cheng

Abstract:

This research studies the electroplating of zinc coating in the zinc chloride bath mixed with supercritical CO2. The sodium fluoride (NaF) was used as the bath additive to change the structure and property of the coating, and therefore the roughness and corrosion resistance of the zinc coating was investigated. The surface characterization was performed using optical microscope (OM), X-ray diffractometer (XRD), and α-step profilometer. Moreover, the potentiodynamic polarization measurement in 3% NaCl solution was employed in the corrosion resistance evaluation. Because of the emulsification of the electrolyte mixed in Sc-CO2, the electroplated zinc produced the coating with smoother surface, smaller grain, better throwing power and higher corrosion resistance. The main role played by the NaF was to reduce the coating’s roughness and grain size. In other words, the CO2 mixed with the electrolyte under the supercritical condition performed the similar function as brighter and leveler in zinc electroplating to enhance the throwing power and corrosion resistance of the coating.

Keywords: supercritical CO2, zinc-electroplating, sodium fluoride, electroplating

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Authors: Lazic Marina, Sugden Scott, Sharma Kanta Hem, Sauvageau Dominic, Stein Lisa

Abstract:

Methane is a highly potent greenhouse gas mostly released through anthropogenic activities. Methane represents a low-cost and sustainable feedstock used for the biological production of value-added compounds by bacteria known as methanotrophs. In addition to methane, these organisms can utilize methanol, another cheap carbon source that is a common industrial by-product. Alphaproteobacteria methanotrophs can utilize both methane and methanol to produce the biopolymer polyhydroxybutyrate. The goal of this study was to examine the effect of methanol on polyhydroxybutyrate production in Methylocystis sp. Rockwell and to identify the optimal methane: methanol ratio that will improve PHB without reducing biomass production. Three methane: methanol ratios (4, 2.5., and 0.5) and three nitrogen source (ammonium or nitrate) concentrations (10 mM, 1 mM, and 0.1 mM) were combined to generate 18 growing conditions (9 per carbon source). The production of polyhydroxybutyrate and biomass was analyzed at the end of growth. Overall, the methane: methanol ratios that promoted polyhydroxybutyrate synthesis without reducing biomass were 4 and 2.5 and the optimal nitrogen concentration was 1 mM for both ammonium and nitrate. The physiological mechanism behind the beneficial effect of combining methane and methanol as carbon sources remain to be discovered. One possibility is that methanol has a dual role as a carbon source at lower concentrations and as a stringent response trigger at higher concentrations. Nevertheless, the beneficial effect of methanol and optimal nitrogen concentration for PHB production was confirmed, providing a basis for future physiological analysis and conditions for process scale-up.

Keywords: methane, methanol, methanotrophs, polyhydroxybutyrate, methylocystis sp. rockwell, single carbon bioconversions

Procedia PDF Downloads 131