Search results for: supercritical methanol
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 578

Search results for: supercritical methanol

548 Performance of CO₂/N₂ Foam in Enhanced Oil Recovery

Authors: Mohamed Hassan, Rahul Gajbhiye

Abstract:

The high mobility and gravity override of CO₂ gas can be minimized by generating the CO₂ foam with the aid of surfactant. However, CO₂ is unable to generate the foam/stable foam above its supercritical point (1100 psi, 31°C). These difficulties with CO₂ foam is overcome by adding N₂ in small fraction to enhance the foam generation of CO₂ at supercritical conditions. This study shows how the addition of small quantity of N₂ helps in generating the CO₂ foam and performance of the CO₂/N₂ mixture foam in enhanced oil recovery. To investigate the performance of CO₂/N₂ foam, core-flooding experiments were conducted at elevated pressure and temperature condition (higher than supercritical CO₂ - 50°C and 1500 psi) in sandstone cores. Fluorosurfactant (FS-51) was used as a foaming agent, and n-decane was used as model oil in all the experiments. The selection of foam quality and N₂ fraction was optimized based on foam generation and stability tests. Every gas or foam flooding was preceded by seawater injection to simulate the behavior in the reservoir. The results from the core-flood experiments showed that the CO₂ and CO₂/N₂ foam flooding recovered an additional 34-40% of Original Initial Oil in Place (OIIP) indicating that foam flooding succeeded in producing more oil than pure CO₂ gas injection processes. Additionally, the performance CO₂/N₂ foam injection was better than CO₂ foam injection.

Keywords: CO₂/N₂ foam, enhanced oil recovery (EOR), supercritical CO₂, sweep efficiency

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547 A Comparative Study on Supercritical C02 and Water as Working Fluids in a Heterogeneous Geothermal Reservoir

Authors: Musa D. Aliyu, Ouahid Harireche, Colin D. Hills

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The incapability of supercritical C02 to transport and dissolve mineral species from the geothermal reservoir to the fracture apertures and other important parameters in heat mining makes it an attractive substance for Heat extraction from hot dry rock. In other words, the thermodynamic efficiency of hot dry rock (HDR) reservoirs also increases if supercritical C02 is circulated at excess temperatures of 3740C without the drawbacks connected with silica dissolution. Studies have shown that circulation of supercritical C02 in homogenous geothermal reservoirs is quite encouraging; in comparison to that of the water. This paper aims at investigating the aforementioned processes in the case of the heterogeneous geothermal reservoir located at the Soultz site (France). The MultiPhysics finite element package COMSOL with an interface of coupling different processes encountered in the geothermal reservoir stimulation is used. A fully coupled numerical model is developed to study the thermal and hydraulic processes in order to predict the long-term operation of the basic reservoir parameters that give optimum energy production. The results reveal that the temperature of the SCC02 at the production outlet is higher than that of water in long-term stimulation; as the temperature is an essential ingredient in rating the energy production. It is also observed that the mass flow rate of the SCC02 is far more favourable compared to that of water.

Keywords: FEM, HDR, heterogeneous reservoir, stimulation, supercritical C02

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546 Simulation and Optimization of an Annular Methanol Reformer

Authors: Shu-Bo Yang, Wei Wu, Yuan-Heng Liu

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This research aims to design a heat-exchanger type of methanol reformer coupled with a preheating design in gPROMS® environment. The endothermic methanol steam reforming reaction (MSR) and the exothermic preferential oxidation reaction (PROX) occur in the inner tube and the outer tube of the reformer, respectively. The effective heat transfer manner between the inner and outer tubes is investigated. It is verified that the countercurrent-flow type reformer provides the higher hydrogen yield than the cocurrent-flow type. Since the hot spot temperature appears in the outer tube, an improved scheme is proposed to suppress the hot spot temperature by splitting the excess air flowing into two sites. Finally, an optimization algorithm for maximizing the hydrogen yield is employed to determine optimal operating conditions.

Keywords: methanol reformer, methanol steam reforming, optimization, simulation

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545 Preventive Effects of Silymarin in Retinal Intoxication with Methanol in Rat: Transmission Electron Microscope Study

Authors: A. Zarenezhad, A. Esfandiari, E. Zarenezhad, M. Mardkhoshnood

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The aim of this study was to investigate the ultra-structure of the photoreceptor layer of male rats under the effect of methanol intoxication and protective effect of silymarin against the methanol toxicity. Fifteen adult male rats were divided into three groups: Control group, Experimental group I (received 4g/kg methanol by intraperitoneal injection for five days), Experimental group II (received 4 g/kg methanol by intraperitoneal injection for five days and received 250 mg/kg silymarin orally for three months). At the end of the experiment, the eyes were removed; retina was separated near the optic disc and studied by transmission electron microscope. Results showed that the retina in the experimental group I exhibited loss of outer segments and disorganization in inner segment. Increased extra cellular space, disappearance of outer limiting membrane and pyknotic nuclei were seen in this group. But normal outer segment, organized inner segment and normal outer limiting membrane were obvious after treatment with silymarin in experimental group II. These findings show that methanol causes damage in the photoreceptor layer of the rat retina and silymarin can protect the damage to retina against the methanol intoxication.

Keywords: ultra-structure, photoreceptor layer, methanol intoxication, silymarin, rat

Procedia PDF Downloads 261
544 Extraction of M. paradisiaca L. Inflorescences Using Compressed Propane

Authors: Michele C. Mesomo, Madeline de Souza Correa, Roberta L. Kruger, Luis R. S. Kanda, Marcos L. Corazza

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Natural extracts of plants have been used for many years for different purposes and recently they have been screened for their potential use as alternative remedies and food preservatives. Inflorescences of M. paradisiaca L., also known as the heart of the banana, have great economic interest due to its fruit. All parts of the banana are used for many different purposes, including use in folk medicine. The use of extraction via supercritical technology has grown in recent years, though it is still necessary to obtain experimental information for the construction of industrial plants. This work reports the extraction of Musa paradisiaca L. using compressed propane as solvent. The effects of the supercritical extraction conditions, pressure and temperature on the yield were evaluated. The raw material, inflorescences banana, was dried at 313.15 K and milled. The particle size used for the packaging of the extraction cell was 12 mesh (23.5%), 16 mesh (23.5%), 32 mesh (34.5%), 48 mesh (18.5%). The extractions were performed in a laboratory scale unit at pressures of 3.0 MPa, 6.5 MPa and 10.0 MPa and at 308.15 K, 323.15 K and 338.15 K. The operating conditions tested achieved a maximum yield of 2.94 wt% for the CO2 extraction at 10.0 MPa and 338.15 K, higher pressure and temperature. The lower yield, 2.29 wt%, was obtained in the condition of lower pressure and higher temperature. Temperature presented significant and positive effect on the extraction yield with supercritical CO2, while pressure had no effect on the yield. The overall extraction curves showed typical behavior obtained for the supercritical extraction procedure and and reached a constant extraction rate of about 80 to 100 min. The largest amount of extract was obtained at the beginning of the process, within 10 to 60 min.

Keywords: banana, natural products, supercritical extraction, temperature

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543 Experimental and Characterization Studies on Micro Direct Methanol Fuel Cell

Authors: S. Muthuraja Soundrapandian, C.K. Subramaniam

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A micro Direct Methanol Fuel Cell (DMFC) of 1 cm2 active area with selective sensor materials to sense methanol for redox, has been developed. Among different Pt alloys, Pt-Sn/C was able to produce high current density and repeatability. Membrane Elecctrode Assembly (MEA) of anode catalyst Pt-Sn/C was prepared with nafion as active membrane and Pt black as cathode catalyst. The sensor’s maximum ability to detect the trace levels of methanol in ppm has been analyzed. A compact sensor set up has also been made and the characterization studies were carried out. The acceptable value of current density was derived by the cell and the results are able to fulfill the needs of DMFC technology for the practical applications.

Keywords: DMFC, sensor, MEA, Pt-Sn

Procedia PDF Downloads 104
542 Supercritical CO2 Extraction of Cymbopogon martini Essential Oil and Comparison of Its Composition with Traditionally Extracted Oils

Authors: Aarti Singh, Anees Ahmad

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Essential oil was extracted from lemon grass (Cymbopogon martini) with supercritical carbondioxide (SC-CO2) at pressure of 140 bar and temperature of 55 °C and CO2 flow rate of 8 gmin-1, and its composition and yield were compared with other conventional extraction methods of oil, HD (Hydrodistillation), SE (Solvent Extraction), UAE (Ultrasound Assisted Extraction). SC-CO2 extraction is a green and sustainable extraction technique. Each oil was analysed by GC-MS, the major constituents were neral (44%), Z-citral (43%), geranial (27%), caryophyllene (4.6%) and linalool (1%). The essential oil of lemon grass is valued for its neral and citral concentration. The oil obtained by supercritical carbon-dioxide extraction contained maximum concentration of neral (55.05%) whereas ultrasonication extracted oil contained minimum content (5.24%) and it was absent in solvent extracted oil. The antioxidant properties have been assessed by DPPH and superoxide scavenging methods.

Keywords: cymbopogon martini, essential oil, FT-IR, GC-MS, HPTLC, SC-CO2

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541 Towards a Rigorous Analysis for a Supercritical Particulate Process

Authors: Yousef Bakhbakhi

Abstract:

Crystallization with supercritical fluids (SCFs), as a developed technology to produce particles of micron and sub-micron size with narrow size distribution, has found appreciable importance as an environmentally friendly technology. Particle synthesis using SCFs can be achieved employing a number of special processes involving solvent and antisolvent mechanisms. In this study, the compressed antisolvent (PCA) process is utilized as a model to analyze the theoretical complexity of crystallization with supercritical fluids. The population balance approach has proven to be an effectual technique to simulate and predict the particle size and size distribution. The nucleation and growth mechanisms of the particles formation in the PCA process is investigated using the population balance equation, which describes the evolution of the particle through coalescence and breakup levels with time. The employed mathematical population balance model contains a set of the partial differential equation with algebraic constraints, which demands a rigorous numerical approach. The combined Collocation and Galerkin finite element method are proposed as a high-resolution technique to solve the dynamics of the PCA process.

Keywords: particle formation, particle size and size distribution, PCA, supercritical carbon dioxide

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540 Copper Selenide Nanobelts: An Electrocatalyst for Methanol Electro-Oxidation Reaction

Authors: Nabi Ullah

Abstract:

The energy crisis of the current society has attracted research attention for alternative energy sources. Methanol oxidation is the source of energy but needs efficient electrocatalysts like Pt. However, their practical ability is hindered due to cost and poisoning effects. In this regard, an efficient catalyst is required for methanol oxidation. Herein, high temperature, pressure, and diethylenetryamine (DETA) as reaction medium/structure directing agent during the solvothermal method are used for nanobelt Cu₃Se₂/Cu₁.₈Se (mostly hexagonal appearance) formation. The electrocatalyst shows optimized methanol electrooxidation reaction (MOR) response in 1 M KOH and 0.5 M methanol at a scan rate of 50 mV/s and delivers a current density of 7.12 mA/mg at a potential of 0.65 V (vs Ag/AgCl). The catalyst exhibits high electrochemical active surface area (ECSA) (0.088 mF/cm²) and low Rct with good stability for 3600 s, which favors its high MOR performance. This high response is due to its 2D hexagonal nanobelt morphology, which provides a large surface area for reaction. The space among nanobelts reduces diffusion kinetics, and the rough/irregular edge increases the reaction site to improve the methanol oxidation reaction overall.

Keywords: energy application, electrocatalysis, MOR, nanobelt

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539 Scale-Up Process for Phyllanthus niruri Enriched Extract by Supercritical Fluid Extraction

Authors: Norsyamimi Hassim, Masturah Markom

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Supercritical fluid extraction (SFE) has been known as a sustainable and safe extraction technique for plant extraction due to the minimal usage of organic solvent. In this study, a scale-up process for the selected herbal plant (Phyllanthus niruri) was investigated by using supercritical carbon dioxide (SC-CO2) with food-grade (ethanol-water) cosolvent. The quantification of excess ethanol content in the final dry extracts was conducted to determine the safety of enriched extracts. The extraction yields obtained by scale-up SFE unit were not much different compared to the predicted extraction yields with an error of 2.92%. For component contents, the scale-up extracts showed comparable quality with laboratory-scale experiments. The final dry extract showed that the excess ethanol content was 1.56% g/g extract. The fish embryo toxicity test (FETT) on the zebrafish embryos showed no toxicity effects by the extract, where the LD50 value was found to be 505.71 µg/mL. Thus, it has been proven that SFE with food-grade cosolvent is a safe extraction technique for the production of bioactive compounds from P. niruri.

Keywords: scale-up, supercritical fluid extraction, enriched extract, toxicity, ethanol content

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538 Nickel Electroplating in Post Supercritical CO2 Mixed Watts Bath under Different Agitations

Authors: Chun-Ying Lee, Kun-Hsien Lee, Bor-Wei Wang

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The process of post-supercritical CO2 electroplating uses the electrolyte solution after being mixed with supercritical CO2 and released to atmospheric pressure. It utilizes the microbubbles that form when oversaturated CO2 in the electrolyte returns to gaseous state, which gives the similar effect of pulsed electroplating. Under atmospheric pressure, the CO2 bubbles gradually diffuse. Therefore, the introduction of ultrasound and/or other agitation can potentially excite the CO2 microbubbles to achieve an electroplated surface of even higher quality. In this study, during the electroplating process, three different modes of agitation: magnetic stirrer agitation, ultrasonic agitation and a combined mode (magnetic + ultrasonic) were applied, respectively, in order to obtain an optimal surface morphology and mechanical properties for the electroplated Ni coating. It is found that the combined agitation mode at a current density of 40 A/dm2 achieved the smallest grain size, lower surface roughness, and produced an electroplated Ni layer that achieved hardness of 320 HV, much higher when compared with conventional method, which were usually in the range of 160 to 300 HV. However, at the same time, the electroplating with combined agitation developed a higher internal stress of 320 MPa due to the lower current efficiency of the process and finer grain in the coating. Moreover, a new control methodology for tailoring the coating’s mechanical property through its thickness was demonstrated by the timely introduction of ultrasonic agitation during the electroplating process with post supercritical CO2 mixed electrolyte.

Keywords: nickel electroplating, micro-bubbles, supercritical carbon dioxide, ultrasonic agitation

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537 Tuning Cubic Equations of State for Supercritical Water Applications

Authors: Shyh Ming Chern

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Cubic equations of state (EoS), popular due to their simple mathematical form, ease of use, semi-theoretical nature and, reasonable accuracy are normally fitted to vapor-liquid equilibrium P-v-T data. As a result, They often show poor accuracy in the region near and above the critical point. In this study, the performance of the renowned Peng-Robinson (PR) and Patel-Teja (PT) EoS’s around the critical area has been examined against the P-v-T data of water. Both of them display large deviations at critical point. For instance, PR-EoS exhibits discrepancies as high as 47% for the specific volume, 28% for the enthalpy departure and 43% for the entropy departure at critical point. It is shown that incorporating P-v-T data of the supercritical region into the retuning of a cubic EoS can improve its performance above the critical point dramatically. Adopting a retuned acentric factor of 0.5491 instead of its genuine value of 0.344 for water in PR-EoS and a new F of 0.8854 instead of its original value of 0.6898 for water in PT-EoS reduces the discrepancies to about one third or less.

Keywords: equation of state, EoS, supercritical water, SCW

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536 Modelling of Organic Rankine Cycle for Waste Heat Recovery Process in Supercritical Condition

Authors: Jahedul Islam Chowdhury, Bao Kha Nguyen, David Thornhill, Roy Douglas, Stephen Glover

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Organic Rankine Cycle (ORC) is the most commonly used method for recovering energy from small sources of heat. The investigation of the ORC in supercritical condition is a new research area as it has a potential to generate high power and thermal efficiency in a waste heat recovery system. This paper presents a steady state ORC model in supercritical condition and its simulations with a real engine’s exhaust data. The key component of ORC, evaporator, is modelled using finite volume method, modelling of all other components of the waste heat recovery system such as pump, expander and condenser are also presented. The aim of this paper is to investigate the effects of mass flow rate and evaporator outlet temperature on the efficiency of the waste heat recovery process. Additionally, the necessity of maintaining an optimum evaporator outlet temperature is also investigated. Simulation results show that modification of mass flow rate is the key to changing the operating temperature at the evaporator outlet.

Keywords: Organic Rankine cycle, supercritical condition, steady state model, waste heat recovery

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535 The Photocatalytic Approach for the Conversion of Polluted Seawater CO₂ into Renewable Source of Energy

Authors: Yasar N. Kavil, Yasser A. Shaban, Radwan K. Al Farawati, Mohamed I. Orif, Shahed U. M. Khanc

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Photocatalytic way of reduction of CO₂ in polluted seawater into chemical fuel, methanol, was successfully gained over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. A homemade stirred batch annular reactor was used to carry out the photocatalytic reduction experiments. Photocatalysts with various Cu loadings (0, 0.5, 1, 3, 5 and 7 wt.%) were synthesized by the sol-gel procedure and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. The photocatalytic production of methanol was promoted by the co-doping with C and Cu into TiO₂. This improvement was attributed to the modification of bandgap energy and the hindrance of the charges recombination. The polluted seawater showing the yield depended on its background hydrographic parameters. We assessed two types of polluted seawater system, the observed yield was 2910 and 990 µmol g⁻¹ after 5 h of illumination under UV and natural sunlight respectively in system 1 and the corresponding yield in system 2 was 2250 and 910 µmol g⁻¹ after 5 h of illumination. The production of methanol in the case of oxygen-depleted water was low, this is mainly attributed to the competition of methanogenic bacteria over methanol production. The results indicated that the methanol yield produced by Cu-C/TiO₂ was much higher than those of carbon-modified titanium oxide (C/TiO₂) and Degussa (P25-TiO₂). Under the current experimental condition, the optimum loading was achieved by the doping of 3 wt % of Cu. The highest methanol yield was obtained over 1 g L-1 of 3wt% Cu/C-TiO₂.

Keywords: CO₂ photoreduction, copper, Cu/C-co-doped TiO₂, methanol, seawater

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534 Analysis of Caffeic Acid from Myrica nagi Leaves by High Performance Liquid Chromatography

Authors: Preeti Panthari, Harsha Kharkwal

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Myrica nagi belongs to Myricaceae family. It is known for its therapeutic use since ancient times. The leaves were extracted with methanol and further fractioned with different solvents with increasing polarity. The n-butanol fraction of methanol extract was passed through celite, on separation through silica gel column chromatography yielded ten fractions. For the first time we report isolation of Caffeic acid from n-butanol fraction of Myrica nagi leaves in Chloroform: methanol (70:30) fraction. The mobile phase used for analysis in HPLC was Methanol: water (60:40) at the flow rate of 1 ml/min at wavelength of 280 nm. The retention time was 2.66 mins.

Keywords: Myrica nagi, column chromatography, retention time, caffeic acid

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533 Aerogel Fabrication Via Modified Rapid Supercritical Extraction (RSCE) Process - Needle Valve Pressure Release

Authors: Haibo Zhao, Thomas Andre, Katherine Avery, Alper Kiziltas, Deborah Mielewski

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Silica aerogels were fabricated through a modified rapid supercritical extraction (RSCE) process. The silica aerogels were made using a tetramethyl orthosilicate precursor and then placed in a hot press and brought to the supercritical point of the solvent, ethanol. In order to control the pressure release without a pressure controller, a needle valve was used. The resulting aerogels were then characterized for their physical and chemical properties and compared to silica aerogels created using similar methods. The aerogels fabricated using this modified RSCE method were found to have similar properties to those in other papers using the unmodified RSCE method. Silica aerogel infused glass blanket composite, graphene reinforced silica aerogel composite were also successfully fabricated by this new method. The modified RSCE process and system is a prototype for better gas outflow control with a lower cost of equipment setup. Potentially, this process could be evolved to a continuous low-cost high-volume production process to meet automotive requirements.

Keywords: aerogel, automotive, rapid supercritical extraction process, low cost production

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532 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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531 Development and Validation of a HPLC Method for Standardization of Methanolic Extract of Hypericum sinaicum Hochst

Authors: Taghreed A. Ibrahim, Atef A. El-Hela, Hala M. El-Hefnawy

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The chromatographic profile of methanol extract of Hypericum sinaicum was determined using HPLC-DAD. Apigenin was used as an external standard in the development and validation of the HPLC method. The proposed method is simple, rapid and reliable and can be successfully applied for standardization of Hypericum sinaicum methanol extract.

Keywords: quality control, standardization, falvonoids, methanol extract

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530 Life Cycle Assessment Comparison between Methanol and Ethanol Feedstock for the Biodiesel from Soybean Oil

Authors: Pawit Tangviroon, Apichit Svang-Ariyaskul

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As the limited availability of petroleum-based fuel has been a major concern, biodiesel is one of the most attractive alternative fuels because it is renewable and it also has advantages over the conventional petroleum-base diesel. At Present, productions of biodiesel generally perform by transesterification of vegetable oils with low molecular weight alcohol, mainly methanol, using chemical catalysts. Methanol is petrochemical product that makes biodiesel producing from methanol to be not pure renewable energy source. Therefore, ethanol as a product produced by fermentation processes. It appears as a potential feed stock that makes biodiesel to be pure renewable alternative fuel. The research is conducted based on two biodiesel production processes by reacting soybean oils with methanol and ethanol. Life cycle assessment was carried out in order to evaluate the environmental impacts and to identify the process alternative. Nine mid-point impact categories are investigated. The results indicate that better performance on Abiotic Depletion Potential (ADP) and Acidification Potential (AP) are observed in biodiesel production from methanol when compared with biodiesel production from ethanol due to less energy consumption during the production processes. Except for ADP and AP, using methanol as feed stock does not show any advantages over biodiesel from ethanol. The single score method is also included in this study in order to identify the best option between two processes of biodiesel production. The global normalization and weighting factor based on eco-taxes are used and it shows that producing biodiesel form ethanol has less environmental load compare to biodiesel from methanol.

Keywords: biodiesel, ethanol, life cycle assessment, methanol, soybean oil

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529 Microstructure of AlCrFeNiMn High Entropy Alloy and Its Corrosion Behavior in Supercritical CO₂ Environment

Authors: Yang Wanhuan, Zou Jichun, LI Shen, Zhong Weihua, Yang Wen

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High entropy alloys (HEAs) have aroused significant concern in high-temperature supercritical carbon dioxide (S-CO2) environments due to their unique microstructures and outstanding properties. However, the anti-corrosion ability and mechanism of these HEAs in the S-CO₂ remain unclear. Herein, we developed a new AlCrFeNiMn (AM)-HEA with double phases by vacuum arc melting furnace. The corrosion behavior of AM-HEA in the S-CO₂ at 500 ℃ under 25 MPa for 400 hours was deciphered by multiple characterization techniques. The results show that the discrepancy of corrosion between the matrix and boundary was accounted for by their microstructure and components. The role and mechanism of Mn contents for their oxide scales in boundary zones were emphasized. More importantly, the nano-precipitated second phase and numerous boundaries for the outstanding anti-corrosion ability of the matrix were proposed.

Keywords: high entropy alloy, microstructure, corrosion, supercritical carbon oxide, AlCrFeNiMn

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528 Determinaton of Processing Parameters of Decaffeinated Black Tea by Using Pilot-Scale Supercritical CO₂ Extraction

Authors: Saziye Ilgaz, Atilla Polat

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There is a need for development of new processing techniques to ensure safety and quality of final product while minimizing the adverse impact of extraction solvents on environment and residue levels of these solvents in final product, decaffeinated black tea. In this study pilot scale supercritical carbon dioxide (SCCO₂) extraction was used to produce decaffeinated black tea in place of solvent extraction. Pressure (250, 375, 500 bar), extraction time (60, 180, 300 min), temperature (55, 62.5, 70 °C), CO₂ flow rate (1, 2 ,3 LPM) and co-solvent quantity (0, 2.5, 5 %mol) were selected as extraction parameters. The five factors BoxBehnken experimental design with three center points was performed to generate 46 different processing conditions for caffeine removal from black tea samples. As a result of these 46 experiments caffeine content of black tea samples were reduced from 2.16 % to 0 – 1.81 %. The experiments showed that extraction time, pressure, CO₂ flow rate and co-solvent quantity had great impact on decaffeination yield. Response surface methodology (RSM) was used to optimize the parameters of the supercritical carbon dioxide extraction. Optimum extraction parameters obtained of decaffeinated black tea were as follows: extraction temperature of 62,5 °C, extraction pressure of 375 bar, CO₂ flow rate of 3 LPM, extraction time of 176.5 min and co-solvent quantity of 5 %mol.

Keywords: supercritical carbon dioxide, decaffeination, black tea, extraction

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527 Civil Protection in Mass Methanol Poisoning in the Czech Republic

Authors: Michaela Vašková, Jiří Barta, Otakar J. Mika, Jan Hrdlička, Josef Kellner

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The paper is focused on the method to solutions the crisis situation in the Czech Republic associated with the mass methanol poisoning. The emphasis is put on tasks of individual state bodies and of Integrated Rescue System during the handling of the crisis. The theoretical part describes poisonings, ways of intoxication, types of intoxicants and cases of mass poisoning by dangerous substances in the world. The practical part describes the development, causes and solutions of extraordinary event, mass methanol poisoning in the Czech Republic. The main emphasis was put on the crisis management of the Czech Republic in solving this situation.

Keywords: crisis management, poisoning, methanol, hazardous substances, extraordinary event

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526 The Thermochemical Conversion of Lactic Acid in Subcritical and Supercritical Water

Authors: Shyh-Ming Chern, Hung-Chi Tu

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One way to utilize biomass is to thermochemically convert it into gases and chemicals. For conversion of biomass, glucose is a particularly popular model compound for cellulose, or more generally for biomass. The present study takes a different approach by employing lactic acid as the model compound for cellulose. Since lactic acid and glucose have identical elemental composition, they are expected to produce similar results as they go through the conversion process. In the current study, lactic acid was thermochemically converted to assess its reactivity and reaction mechanism in subcritical and supercritical water, by using a 16-ml autoclave reactor. The major operating parameters investigated include: The reaction temperature, from 673 to 873 K, the reaction pressure, 10 and 25 MPa, the dosage of oxidizing agent, 0 and 0.5 chemical oxygen demand, and the concentration of lactic acid in the feed, 0.5 and 1.0 M. Gaseous products from the conversion were generally found to be comparable to those derived from the conversion of glucose.

Keywords: lactic acid, subcritical water, supercritical water, thermochemical conversion

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525 Effect of Pressure and Dissolved Oxygen on Stress Corrosion Cracking Susceptibility of Inconel 617 in Steam and Supercritical Water

Authors: Hasan Izhar Khan, Naiqiang Zhang, Hong Xu, Zhongliang Zhu, Dongfang Jiang

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Inconel 617, a nickel-based alloy designed for high-temperature applications, got an excellent amalgamation of strength and oxidation resistance at high temperatures. For a better understanding of its suitability to be used in superheater and reheater tubes in ultra-supercritical power plants, stress corrosion cracking (SCC) susceptibility must be evaluated. In the present study, the effect of medium environment on SCC behavior of Inconel 617, in the form of a round bar tensile specimen, was tested via slow strain rate tensile tests in steam and supercritical water (SCW) at 650 °C. The results showed that SCC susceptibility has a linear relationship with exposed pressure and increases monotonically with an increase in pressure. A severe SCC susceptibility was observed in SCW followed by that in a steam environment. Fracture and gage surface showed apparent characteristics of brittle fracture. Intergranular cracks initiated from the edge region and propagated into the matrix through cross section until ductile rupture. When dissolved oxygen contents were decreased in SCW environment, it showed no noticeable effect on mechanical properties but SCC susceptibility slightly decreased. The research revealed the influence of environment on SCC susceptibility of Inconel 617 in steam and SCW.

Keywords: Inconel 617, steam, supercritical water, stress corrosion cracking

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524 Assisted Supercritical Carbon Dioxide Extraction of Tocotrienols from Palm Fatty Acid Distillate

Authors: Najwa Othman, Norhidayah Suleiman, Gun Hean Chong

Abstract:

Palm fatty acid distillate (PFAD) is a by-product of palm oil refineries which contains valuable compounds such as phytosterols, squalene, polycosanol, co-enzyme Q10 and vitamin E (tocopherols and tocotrienols). Approximately 0.7-1.0% of vitamin E accumulates in PFAD, and it functions as antioxidants and anti-inflammatory. The objective of this research is to evaluate the effect of manipulated variables in supercritical carbon dioxide towards the recovery of tocotrienols in PFAD. The vitamin E concentrate isolated varies depending on the pre-treatment of sample and extraction techniques. In this research, tocotrienols in PFAD was concentrated by removing the extraneous matters, especially free fatty acid (FFA) and acylglycerols. Pre-treatment method such as enzymatic hydrolysis by using lipase from Candida rugosa as an enzyme was used to remove FFA and improve recovery of vitamin E. After that, treated PFAD was extracted by using supercritical fluid extraction in co-current glass beads packed column (22 cm x 75 cm i.d) at different temperatures (40-60°C) and pressures (100-300 bar) for 5 hours. After the extraction, the sample was analyzed by using high-pressure liquid chromatography (HPLC) system to quantify the tocotrienols. The results indicated that a combined pressure (200 bar) and temperature (60°C) was predicted to provide highest tocotrienols yield and the extraction yield obtained was 106.45%.

Keywords: enzymatic hydrolysis, palm fatty acid distillate, supercritical fluid extraction, tocotrienols

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523 In-vitro Antioxidant Activity of Two Selected Herbal Medicines

Authors: S. Vinotha, I. Thabrew, S. Sri Ranjani

Abstract:

Hot aqueous and methanol extracts of the two selected herbal medicines such are Vellarugu Chooranam (V.C) and Amukkirai Chooranam (A.C) were examined for total phenolic and flavonoid contents and in-vitro antioxidant activity using four different methods. The total phenolic and flavonoid contents in methanol extract of V.C were found to be higher (44.41±1.26 mg GAE⁄g; 174.44±9.32 mg QE⁄g) than in the methanol extract of A.C (20.56±0.67 mg GAE⁄g;7.21±0.85 mg QE⁄g). Hot methanol and aqueous extracts of both medicines showed low antioxidant activity in DPPH, ABTS, and FRAP methods and Iron chelating activity not found at highest possible concentration. V.C contains higher concentrations of total phenolic and flavonoid contents than A.C and can also exert greater antioxidant activity than A.C, although the activities demonstrated were lower than the positive control Trolox. The in-vitro antioxidant activity was not related with the total phenolic and flavonoid contents of the methanol and aqueous extracts of both herbal medicines (A.C and V.C).

Keywords: activity, different extracts, herbal medicines, in-vitro antioxidant

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522 Pervaporation of Dimethyl Carbonate / Methanol / Water Mixtures Using Zeolite Membranes

Authors: Jong-Ho Moon, Dong-Ho Lee, Hyunuk Kim, Young Cheol Park, Jong-Seop Lee, Jae-deok Jeon, Hyung-Keun Lee

Abstract:

A novel membrane reactor process for DMC synthesis from carbon dioxide has been developing in Korea Institute of Energy Research. The scheme of direct synthesis of DMC from CO₂ and Methanol is 'CO₂ + 2MeOH ↔ DMC + H₂O'. Among them, reactants are CO₂ and MeOH, product is DMC, and byproduct is H₂O (water). According to Le Chatelier’s principle, removing byproduct (water) can shift the reaction equilibrium to the right (DMC production). The main purpose of this process is removing water during the reaction. For efficient in situ water removal (dehydration) and DMC separation, zeolite 4A membranes with very small pore diameter and hydrophilicity were introduced. In this study, pervaporation performances of binary and ternary DMC / methanol / water mixtures were evaluated.

Keywords: dimehtyl carbonate, methanol, water, zeolite membrane, pervaporation

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521 Insect Inducible Methanol Production in Plants for Insect Resistance

Authors: Gourav Jain, Sameer Dixit, Surjeet Kumar Arya, Praveen C. Verma

Abstract:

Plant cell wall plays a major role in defence mechanism against biotic and abiotic stress as it constitutes the physical barrier between the microenvironment and internal component of the cell. It is a complex structure composed of mostly carbohydrates among which cellulose and hemicelluloses are most abundant that is embedded in a matrix of pectins and proteins. Multiple enzymes have been reported which plays a vital role in cell wall modification, Pectin Methylesterase (PME) is one of them which catalyses the demethylesterification of homogalacturonans component of pectin which releases acidic pectin and methanol. As emitted methanol is toxic to the insect pest, we use PME gene for the better methanol production. In the current study we showed overexpression of PME gene isolated from Withania somnifera under the insect inducible promoter causes enhancement of methanol production at the time of insect feeds to plants, and that provides better insect resistance property. We found that the 85-90% mortality causes by transgenic tobacco in both chewing (Spodoptera litura larvae and Helicoverpa armigera) and sap-sucking (Aphid, mealybug, and whitefly) pest. The methanol content and emission level were also enhanced by 10-15 folds at different inducible time point interval (15min, 30min, 45min, 60min) which would be analysed by Purpald/Alcohol Oxidase method.

Keywords: methanol, Pectin methylesterase, inducible promoters, Purpald/Alcohol oxidase

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520 Methanol Steam Reforming with Heat Recovery for Hydrogen-Rich Gas Production

Authors: Horng-Wen Wu, Yi Chao, Rong-Fang Horng

Abstract:

This study is to develop a methanol steam reformer with a heat recovery zone, which recovers heat from exhaust gas of a diesel engine, and to investigate waste heat recovery ratio at the required reaction temperature. The operation conditions of the reformer are reaction temperature (200 °C, 250 °C, and 300 °C), steam to carbonate (S/C) ratio (0.9, 1.1, and 1.3), and N2 volume flow rate (40 cm3/min, 70 cm3/min, and 100 cm3/min). Finally, the hydrogen concentration, the CO, CO2, and N2 concentrations are measured and recorded to calculate methanol conversion efficiency, hydrogen flow rate, and assisting combustion gas and impeding combustion gas ratio. The heat source of this reformer comes from electric heater and waste heat of exhaust gas from diesel engines. The objective is to recover waste heat from the engine and to make more uniform temperature distribution within the reformer. It is beneficial for the reformer to enhance the methanol conversion efficiency and hydrogen-rich gas production. Experimental results show that the highest hydrogen flow rate exists at N2 of the volume rate 40 cm3/min and reforming reaction temperature of 300 °C and the value is 19.6 l/min. With the electric heater and heat recovery from exhaust gas, the maximum heat recovery ratio is 13.18 % occurring at water-methanol (S/C) ratio of 1.3 and the reforming reaction temperature of 300 °C.

Keywords: heat recovery, hydrogen-rich production, methanol steam reformer, methanol conversion efficiency

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519 The Effect of Supercritical Carbon Dioxide Process Variables on The Recovery of Extracts from Bentong Ginger: Study on Process Variables

Authors: Muhamad Syafiq Hakimi Kamaruddin, Norhidayah Suleiman

Abstract:

Ginger extracts (Zingiber officinale Rosc.) have been attributed therapeutic properties primarily as antioxidant, anticancer, and anti-inflammatory properties. Conventional extractions including Soxhlet and maceration are commonly used to extract the bioactive compounds from plant material. Nevertheless, high energy consumption and being non-environmentally friendly are the predominant limitations of the conventional extractions method. Herein, green technology, namely supercritical carbon dioxide (scCO2) extraction, is used to study process variables' effects on extract yields. Herein, green technology, namely supercritical carbon dioxide (scCO2) extraction, is used to study process variables' effects on extract yields. A pressure (10-30 MPa), temperature (40-60 °C), and median particle size (300-600 µm) were conducted at a CO2 flow rate of 0.9 ± 0.2 g/min for 120 mins. The highest overall yield was 4.58% obtained by the scCO2 extraction conditions of 300 bar and 60 °C with 300µm of ginger powder for 120 mins. In comparison, the yield of the extract was increased considerably within a short extraction time. The results show that scCO2 has a remarkable ability over ginger extract and is a promising technology for extracting bioactive compounds from plant material.

Keywords: conventional, ginger, non-environmentally, supercritical carbon dioxide, technology

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