Open Science Research Excellence

Open Science Index

Commenced in January 2007 Frequency: Monthly Edition: International Paper Count: 23

One Dimensional Reactor Modeling for Methanol Steam Reforming to Hydrogen

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.

Catalytic Study of Methanol-to-Propylene Conversion over Nano-Sized HZSM-5

Methanol-to-propylene conversion was carried out in a continuous-flow fixed-bed reactor over nano-sized HZSM-5 zeolites. The HZSM-5 catalysts were synthesized with different Si/Al ratio and silicon sources, and treated with NaOH. The structural property, morphology, and acidity of catalysts were measured by XRD, N2 adsorption, FE-SEM, TEM, and NH3-TPD. The results indicate that the increment of Si/Al ratio decreased the acidity of catalysts and then improved propylene selectivity, while silicon sources had slight impact on the acidity but affected the product distribution. The desilication after alkali treatment could increase intracrystalline mesopores and enhance propylene selectivity.

Preparation and Characterization of Pectin Based Proton Exchange Membranes Derived by Solution Casting Method for Direct Methanol Fuel Cells
Direct methanol fuel cells (DMFCs) are considered to be one of the most promising candidates for portable and stationary applications in the view of their advantages such as high energy density, easy manipulation, high efficiency and they operate with liquid fuel which could be used without requiring any fuel-processing units. Electrolyte membrane of DMFC plays a key role as a proton conductor as well as a separator between electrodes. Increasing concern over environmental protection, biopolymers gain tremendous interest owing to their eco-friendly bio-degradable nature. Pectin is a natural anionic polysaccharide which plays an essential part in regulating mechanical behavior of plant cell wall and it is extracted from outer cells of most of the plants. The aim of this study is to develop and demonstrate pectin based polymer composite membranes as methanol impermeable polymer electrolyte membranes for DMFCs. Pectin based nanocomposites membranes are prepared by solution-casting technique wherein pectin is blended with chitosan followed by the addition of optimal amount of sulphonic acid modified Titanium dioxide nanoparticle (S-TiO2). Nanocomposite membranes are characterized by Fourier Transform-Infra Red spectroscopy, Scanning electron microscopy, and Energy dispersive spectroscopy analyses. Proton conductivity and methanol permeability are determined into order to evaluate their suitability for DMFC application. Pectin-chitosan blends endow with a flexible polymeric network which is appropriate to disperse rigid S-TiO2 nanoparticles. Resulting nanocomposite membranes possess adequate thermo-mechanical stabilities as well as high charge-density per unit volume. Pectin-chitosan natural polymeric nanocomposite comprising optimal S-TiO2 exhibits good electrochemical selectivity and therefore desirable for DMFC application.
Hydrogenation of CO2 to Methanol over Copper-Zinc Oxide-Based Catalyst

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 250oC, 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.

Preparation and Characterization of CuFe2O4/TiO2 Photocatalyst for the Conversion of CO2 into Methanol under Visible Light

A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e−/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e−/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.

Civil Protection in Mass Methanol Poisoning in the Czech Republic

The paper is focused on the methods to solutions of 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.

Efficient Use of Energy through Incorporation of a Gas Turbine in Methanol Plant

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.

Electrical Properties of Roystonea regia Fruit Extract as Dye Sensitized Solar Cells

Utilizing solar energy in producing electricity can minimize environmental pollution generated by fossil fuel in producing electricity. Our research was base on the extraction of dye from Roystonea regia fruit by using methanol as solvent. The dye extracts were used as sensitizers in Dye-sensitized solar cell (DSSCs). Study was done on the electrical properties from the extracts of Roystonea regia fruit as Dye-sensitized solar cell (DSSCs). The absorptions of the extracts and extracts with dye were determined at different wavelengths (350-1000nm). Absorption peak was observed at 1.339 at wavelength 400nm. The obtained values for methanol extract Roystonea regia extract are, Imp = 0.015mA, Vmp = 12.0mV, fill factor = 0.763, Isc= 0.018 mA and Voc = 13.1 mV and efficiency of 0.32%. .The phytochemical screening was taken and it was observed that Roystonea regia extract contained less of anthocyanin compared to flavonoids. The nanostructured dye sensitized solar cell (DSSC) will provide economically credible alternative to present day silicon p–n junction photovoltaic.

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

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 ecotaxes are used and it shows that producing biodiesel form ethanol has less environmental load compare to biodiesel from methanol.

A Brief Review on Recent Trends in Alternative Sources of Energy

Alternative energy is any energy source that is an alternative to fossil fuel. These alternatives are intended to address concerns about such fossil fuels. Today, because of the variety of energy choices and differing goals of their advocates, defining some energy types as "alternative" is highly controversial. Most of the recent and existing alternative sources of energy are discussed below

Dimethyl Ether as an Ignition Improver for Hydrous Methanol Fuelled Homogeneous Charge Compression Ignition (HCCI) Engine

Homogeneous Charge Compression (HCCI) Ignition technology has been around for a long time, but has recently received renewed attention and enthusiasm. This paper deals with experimental investigations of HCCI engine using hydrous methanol as a primary fuel and Dimethyl Ether (DME) as an ignition improver. A regular diesel engine has been modified to work as HCCI engine for this investigation. The hydrous methanol is inducted and DME is injected into a single cylinder engine. Hence, hydrous methanol is used with 15% water content in HCCI engine and its performance and emission behavior is documented. The auto-ignition of Methanol is enabled by DME. The quantity of DME varies with respect to the load. In this study, the experiments are conducted independently and the effect of the hydrous methanol on the engine operating limit, heat release rate and exhaust emissions at different load conditions are investigated. The investigation also proves that the Hydrous Methanol with DME operation reduces the oxides of Nitrogen and smoke to an extreme low level which is not possible by the direct injection CI engine. Therefore, it is beneficial to use hydrous methanol-DME HCCI mode while using hydrous methanol in internal Combustion Engines.

Combustion, Emission and Performance Characteristics of a Light Duty Diesel Engine Fuelled with Methanol Diesel Blends
Combustion, emission and performance characterization of a single cylinder diesel engine using methanol diesel blends was carried out. The blends were 5% (v/v) methanol in diesel (MD05) and 10% (v/v) methanol in diesel (MD10). The problem of solubility of methanol and diesel was addressed by an agitator placed inside the fuel tank to prevent phase separation. The results indicated that total combustion duration was reduced by15.8% for MD05 and 31.27% for MD10compared to the baseline data. Ignition delay was increased with increasing methanol volume fraction in the test fuel. Total cyclic heat release was reduced by 1.5% for MD05 and 6.7% for MD10 as compared to diesel baseline. Emissions of carbon monoxide, hydrocarbons along with smoke were reduced and that of nitrogen oxides were increased with rising methanol contents in the test fuel. Full load brake thermal efficiency was marginally reduced with increased methanol composition in the blend.
Conversion of Methanol to Propylene over a High Silica B-HZSM-5 Catalyst
Hydrothermally synthesized high silica borosilicates with the MFI structure was subjected to several characterization techniques. The effect of boron on the structure and acidity of HZSM-5 catalyst were studied by XRD, SEM, N2 adsorption, solid state NMR, NH3-TPD. It was confirmed that boron had entered the framework in the boron samples. The results also revealed that strong acidity was weakened and weak acidity was strengthened by the boron added zeolite framework compared with parent catalyst. The catalytic performance was carried out in a fixed bed at 460°C for methanol to propylene (MTP) reaction. The results of MTP reaction showed a great increment of the propylene selectivity and excellent stability for the B-HZSM-5. The catalyst exhibited about 81% selectivity to C2 = - C4 = olefins with 40% selectivity of propylene as major component at near 100% methanol conversion, and the stable performance in the studied period was 100h.
Isolation of β-Sitosterol Diarabinoside from Rhizomes of Alpinia Galanga
Alpinia galanga is rhizome, generally known as Greater galangal and is selected for isolation of newer constituents accountable for various therapeutic activities. Present study is intended to isolate glycoside from Alpinia galanga rhizomes. Alpinia galanga methanolic extract was column chromatograph and eluted with ethyl acetate-methanol (99:1) to isolate compound β-Sitosterol Diarabinoside. Herein, the isolation and structural elucidation of new compound is described. Chemical investigation of methanolic extract of rhizomes of Alpinia galanga furnished a new compound β- Sitosterol Diarabinoside. The IR, NMR and MASS investigations of isolated compound confirmed its structure as β-Sitosterol Diarabinoside, which is isolated for the first time from a medicinal plant or any synthetic source.
Adsorption Kinetics of Alcohols over MCM-41 Materials
Adsorption of methanol and ethanol over mesoporous siliceous material are studied in the current paper. The pure mesoporous silica is prepared using tetraethylorthosilicate (TEOS) as silica source and dodecylamine as template at low pH. The prepared material was characterized using nitrogen adsorption,nX-ray diffraction (XRD) and scanning electron microscopy (SEM). The adsorption kinetics of methanol and ethanol from aqueous solution were studied over the prepared mesoporous silica material. The percent removal of alcohol was calculated per unit mass of adsorbent used. The 1st order model is found to be in agreement with both adsorbates while the 2nd order model fit the adsorption of methanol only.
Effect of Gold Loading on CeO2–Fe2O3 for Oxidative Steam Reforming of Methanol

In this study, oxidative steam reforming of methanol (OSRM) over a Au/CeO2–Fe2O3 catalyst prepared by a depositionprecipitation (DP) method was studied to produce hydrogen in order to feed a Proton Exchange Membrane Fuel Cell (PEMFC). The support (CeO2, Fe2O3, and CeO2–Fe2O3) were prepared by precipitation and co-precipitation methods. The impact of the support composition on the catalytic performance was studied by varying the Ce/(Ce+Fe) atomic ratio, it was found that the 1%Au/CF(0.25) calcined at 300 °C exhibited the highest catalytic activity in the whole temperature studied. In addition, the effect of Au content was investigated and 3%Au/CF(0.25) exhibited the highest activity under the optimum condition in the temperature range of 200 °C to 400 °C. The catalysts were characterized by various techniques: XRD, TPR, XRF, and UV-vis.

Intrinsic Kinetics of Methanol Dehydration over Al2O3 Catalyst
Dehydration of methanol to dimethyl ether (DME) over a commercial Al2O3 catalyst was studied in an isothermal integral fixed bed reactor. The experiments were performed on the temperature interval 513-613 K, liquid hourly space velocity (LHSV) of 0.9-2.1h-1, pressures between 0.1 and 1.0 MPa. The effect of different operation conditions on the dehydration of methanol was investigated in a laboratory scale experiment. A new intrinsic kinetics equation based on the mechanism of Langmuir-Hinshelwood dissociation adsorption was developed for the dehydration reaction by fitting the expressions to the experimental data. An activation energy of 67.21 kJ/mol was obtained for the catalyst with the best performance. Statistic test showed that this new intrinsic kinetics equation was acceptable.
Analysis of Catalytic Properties of Ni3Al Thin Foils for the Methanol and Hexane Decomposition
Intermetallic Ni3Al – based alloys belong to a group of advanced materials characterized by good chemical and physical properties (such as structural stability, corrosion resistance) which offer advenced technological applications. The paper presents the study of catalytic properties of Ni3Al foils (thickness approximately 50 &m) in the methanol and hexane decomposition. The egzamined material posses microcrystalline structure without any additional catalysts on the surface. The better catalytic activity of Ni3Al foils with respect to quartz plates in both methanol and hexane decomposition was confirmed. On thin Ni3Al foils the methanol conversion reaches approximately 100% above 480 oC while the hexane conversion reaches approximately 100% (98,5%) at 500 oC. Deposit formed during the methanol decomposition is built up of carbon nanofibers decorated with metal-like nanoparticles.
Biodiesel Fuel Production by Methanolysis of Fish Oil Derived from the Discarded Parts of Fish Catalyzed by Carica papaya Lipase
In this paper, naturally immobilized lipase, Carica papaya lipase, catalyzed biodiesel production from fish oil was studied. The refined fish oil, extracted from the discarded parts of fish, was used as a starting material for biodiesel production. The effects of molar ratio of oil: methanol, lipase dosage, initial water activity of lipase, temperature and solvent were investigated. It was found that Carica papaya lipase was suitable for methanolysis of fish oil to produce methyl ester. The maximum yield of methyl ester could reach up to 83% with the optimal reaction conditions: oil: methanol molar ratio of 1: 4, 20% (based on oil) of lipase, initial water activity of lipase at 0.23 and 20% (based on oil) of tert-butanol at 40oC after 18 h of reaction time. There was negligible loss in lipase activity even after repeated use for 30 cycles.
Methanol Concentration Sensitive SWCNT/Nafion Composites
An aqueous methanol sensor for use in direct methanol fuel cells (DMFCs) applications is demonstrated; the methanol sensor is built using dispersed single-walled carbon nanotubes (SWCNTs) with Nafion117 solution to detect the methanol concentration in water. The study is aimed at the potential use of the carbon nanotubes array as a methanol sensor for direct methanol fuel cells (DMFCs). The concentration of methanol in the fuel circulation loop of a DMFC system is an important operating parameter, because it determines the electrical performance and efficiency of the fuel cell system. The sensor is also operative even at ambient temperatures and responds quickly to changes in the concentration levels of the methanol. Such a sensor can be easily incorporated into the methanol fuel solution flow loop in the DMFC system.
An Experimental Design Approach to Determine Effects of The Operating Parameters on The Rate of Ru promoted Ir Carbonylation of Methanol
carbonylation of methanol in homogenous phase is one of the major routesfor production of acetic acid. Amongst group VIII metal catalysts used in this process iridium has displayed the best capabilities. To investigate effect of operating parameters like: temperature, pressure, methyl iodide, methyl acetate, iridium, ruthenium, and water concentrations on the reaction rate, experimental design for this system based upon central composite design (CCD) was utilized. Statistical rate equation developed by this method contained individual, interactions and curvature effects of parameters on the reaction rate. The model with p-value less than 0.0001 and R2 values greater than 0.9; confirmeda satisfactory fitness of the experimental and theoretical studies. In other words, the developed model and experimental data obtained passed all diagnostic tests establishing this model as a statistically significant.
Processes Simulation Study of Coal to Methanol Based on Gasification Technology

This study presents a simulation model for converting coal to methanol, based on gasification technology with the commercial chemical process simulator, Pro/II® V8.1.1. The methanol plant consists of air separation unit (ASU), gasification unit, gas clean-up unit, and methanol synthetic unit. The clean syngas is produced with the first three operating units, and the model has been verified with the reference data from United States Environment Protection Agency. The liquid phase methanol (LPMEOHTM) process is adopted in the methanol synthetic unit. Clean syngas goes through gas handing section to reach the reaction requirement, reactor loop/catalyst to generate methanol, and methanol distillation to get desired purity over 99.9 wt%. The ratio of the total energy combined with methanol and dimethyl ether to that of feed coal is 78.5% (gross efficiency). The net efficiency is 64.2% with the internal power consumption taken into account, based on the assumption that the efficiency of electricity generation is 40%.

A Review of Methanol Production from Methane Oxidation via Non-Thermal Plasma Reactor

Direct conversion of methane to methanol by partial oxidation in a thermal reactor has a poor yield of about 2% which is less than the expected economical yield of about 10%. Conventional thermal catalytic reactors have been proposed to be superseded by plasma reactors as a promising approach, due to strength of the electrical energy which can break C-H bonds of methane. Among the plasma techniques, non-thermal dielectric barrier discharge (DBD) plasma chemical process is one of the most future promising technologies in synthesizing methanol. The purpose of this paper is presenting a brief review of CH4 oxidation with O2 in DBD plasma reactors based on the recent investigations. For this reason, the effect of various parameters of reactor configuration, feed ratio, applied voltage, residence time (gas flow rate), type of applied catalyst, pressure and reactor wall temperature on methane conversion and methanol selectivity are discussed.

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