Open Science Research Excellence

Open Science Index

Commenced in January 2007 Frequency: Monthly Edition: International Paper Count: 24

Bioleaching of Metals Contained in Spent Catalysts by Acidithiobacillus thiooxidans DSM 26636

Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.

Structure-Activity Relationship of Gold Catalysts on Alumina Supported Cu-Ce Oxides for CO and Volatile Organic Compound Oxidation

The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH3OH and (CH3)2O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH3OH conversion at about 60 and 140 oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al2O3 1:5 exhibited higher activity for CO and CH3OH oxidation in comparison with Au on Cu-Ce/γ-Al2O3 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Microkinetic Modelling of NO Reduction on Pt Catalysts

The major harmful automobile exhausts are nitric oxide (NO) and unburned hydrocarbon (HC). Reduction of NO using unburned fuel HC as a reductant is the technique used in hydrocarbon-selective catalytic reduction (HC-SCR). In this work, we study the microkinetic modelling of NO reduction using propene as a reductant on Pt catalysts. The selectivity of NO reduction to N2O is detected in some ranges of operating conditions, whereas the effect of inlet O2% causes a number of changes in the feasible regimes of operation.

Investigation on Fischer-Tropsch Synthesis over Cobalt-Gadolinium Catalyst
Cobalt-gadolinium catalyst for Fischer-Tropsch synthesis was prepared by impregnation method with commercial silica gel, and its texture properties were characterized by BET, XRD, and TPR. The catalytic performance of the catalyst was tested in a fixed bed reactor. The results showed that the addition of gadolinium to the cobalt catalyst might decrease the size of cobalt particles, and increased the dispersion of catalytic active cobalt phases. The carbon number distributions for the catalysts was calculated by ASF equation.
Alumina Supported Cu-Mn-La Catalysts for CO and VOCs Oxidation
Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al2O3 supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH3OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La2O3, MnO2 and Cu1.5Mn1.5O4. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.
Reaction Kinetics of Biodiesel Production from Refined Cottonseed Oil Using Calcium Oxide
Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.
Volatile Organic Compounds Destruction by Catalytic Oxidation for Environmental Applications
Pt/γ-Al2O3 membrane catalysts were prepared via an evaporative-crystallization deposition method. The obtained Pt/γ- Al2O3 catalyst activity was tested after characterization (SEM-EDAX observation, BET measurement, permeability assessment) in the catalytic oxidation of selected volatile organic compound (VOC) i.e. propane, fed in mixture of oxygen. The VOC conversion (nearly 90%) obtained by varying the operating temperature showed that flow-through membrane reactor might do better in the abatement of VOCs.
Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Catalysts Characterization
In recent research copper and manganese systems were found to be the most active in CO and organic compounds oxidation among the base catalysts. The mixed copper manganese oxide has been widely studied in oxidation reactions because of their higher activity at low temperatures in comparison with single oxide catalysts. The results showed that the formation of spinel CuxMn3−xO4 in the oxidized catalyst is responsible for the activity even at room temperature. That is why the most of the investigations are focused on the hopcalite catalyst (CuMn2O4) as the best coppermanganese catalyst. Now it’s known that this is true only for CO oxidation, but not for mixture of CO and VOCs. The purpose of this study is to investigate the alumina supported copper-manganese catalysts with different Cu/Mn molar ratio in terms of oxidation of CO, methanol and dimethyl ether. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and the catalytic activity measurements were carried out in two stage continuous flow equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions closest possible to the industrial. Gas mixtures on the input and output of the reactor were analyzed with a gas chromatograph, equipped with FID and TCD detectors. The texture characteristics were determined by low-temperature (- 196oС) nitrogen adsorption in a Quantachrome Instruments NOVA 1200e (USA) specific surface area & pore analyzer. Thermal, XRD and TPR analyses were performed. It was established that the active component of the mixed Cu- Mn/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio. Highly active alumina supported Cu-Mn catalysts for CO, methanol and DME oxidation were synthesized. While the hopcalite is the best catalyst for CO oxidation, the best compromise for simultaneous oxidation of all components is the catalyst with Cu/Mn molar ratio 1:5.
Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs Oxidation
This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.
ORR Activity and Stability of Pt-Based Electrocatalysts in PEM Fuel Cell
A comparison of activity and stability of the as-formed Pt/C, Pt-Co and Pt-Pd/C electrocatalysts, prepared by a combined approach of impregnation and seeding, was performed. According to the activity test in a single Proton Exchange Membrane (PEM) fuel cell, the Oxygen Reduction Reaction (ORR) activity of the Pt-M/C electrocatalyst was slightly lower than that of Pt/C. The j0.9 V and E10 mA/cm2 of the as-prepared electrocatalysts increased in the order of Pt/C > Pt-Co/C > Pt-Pd/C. However, in the medium-to-high current density region, Pt-Pd/C exhibited the best performance. With regard to their stability in a 0.5 M H2SO4 electrolyte solution, the electrochemical surface area decreased as the number of rounds of repetitive potential cycling increased due to the dissolution of the metals within the catalyst structure. For long-term measurement, Pt- Pd/C was the most stable than the other three electrocatalysts.
Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Effect of Preparation Method

The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ- Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.

Synthesis of Novel Nanostructured Catalysts for Pyrolysis of Biomass

Nanostructured catalysts were successfully prepared by acidification of diatomite and regeneration of FCC spent catalysts. The obtained samples were characterized by IR, XRD, SEM, EDX, MAS-NMR (27Al and 29Si), NH3-TPD and tested in catalytic pyrolysis of biomass (rice straw). The results showed that the similar bio-oil yield of 41.4% can be obtained by pyrolysis with catalysts at 450oC as compared to that of the pyrolysis without catalyst at 550oC. The bio-oil yield reached a maximum of 42.55% at the pyrolysis temperature of 500oC with catalytic content of 20%. Moreover, by catalytic pyrolysis, bio-oil quality was better as reflected in higher ratio of H/C, lower ratio of O/C. This clearly indicated high application potential of these new nanostructured catalysts in the production of bio-oil with low oxygenated compounds.

Na Promoted Ni/γ-Al2O3 Catalysts Prepared by Solution Combustion Method for Syngas Methanation

Ni-based catalysts with different amounts of Na as promoter from 2 to 6 wt % were prepared by solution combustion method. The catalytic activity was investigated in syngas methanation reaction. Carbon oxides conversion and methane selectivity are greatly influenced by sodium loading. Adding 2 wt% Na remarkably improves catalytic activity and long-term stability, attributed to its smaller mean NiO particle size, better distribution, and milder metal-support interaction. However, excess addition of Na results in deactivation distinctly due to the blockage of active sites.

The Impact of Surface Roughness and PTFE/TiF3/FeF3 Additives in Plain ZDDP Oil on the Friction and Wear Behavior Using Thermal and Tribological Analysis under Extreme Pressure Condition

The use of titanium fluoride and iron fluoride (TiF3/FeF3) catalysts in combination with polutetrafluoroethylene (PTFE) in plain zinc- dialkyldithiophosphate (ZDDP) oil is important for the study of engine tribocomponents and is increasingly a strategy to improve the formation of tribofilm and provide low friction and excellent wear protection in reduced phosphorus plain ZDDP oil. The influence of surface roughness and the concentration of TiF3/FeF3/PTFE were investigated using bearing steel samples dipped in lubricant solution at 100°C for two different heating time durations. This paper addresses the effects of water drop contact angle using different surface; finishes after treating them with different lubricant combination. The calculated water drop contact angles were analyzed using Design of Experiment software (DOE) and it was determined that a 0.05 μm Ra surface roughness would provide an excellent TiF3/FeF3/PTFE coating for antiwear resistance as reflected in the Scanning electron microscopy (SEM) images and the tribological testing under extreme pressure conditions. Both friction and wear performance depend greatly on the PTFE/and catalysts in plain ZDDP oil with 0.05 % phosphorous and on the surface finish of bearing steel. The friction and wear reducing effects, which was observed in the tribological tests, indicated a better micro lubrication effect of the 0.05 μm Ra surface roughness treated at 100°C for 24 hours when compared to the 0.1 μm Ra surface roughness with the same treatment.

Investigation of the Flow Characteristics in a Catalytic Muffler with Perforated Inlet Cone

Emission regulations for diesel engines are being strengthened and it is impossible to meet the standards without exhaust after-treatment systems. Lack of the space in many diesel vehicles, however, make it difficult to design and install stand-alone catalytic converters such as DOC, DPF, and SCR in the vehicle exhaust systems. Accordingly, those have been installed inside the muffler to save the space, and referred to the catalytic muffler. However, that has complex internal structure with perforated plate and pipe for noise and monolithic catalyst for emission reduction. For this reason, flow uniformity and pressure drop, which affect efficiency of catalyst and engine performance, respectively, should be examined when the catalytic muffler is designed. In this work, therefore, the flow uniformity and pressure drop to improve the performance of the catalytic converter and the engine have been numerically investigated by changing various design parameters such as inlet shape, porosity, and outlet shape of the muffler using the three-dimensional turbulent flow of the incompressible, non-reacting, and steady state inside the catalytic muffler. Finally, it can be found that the shape, in which the muffler has perforated pipe inside the inlet part, has higher uniformity index and lower pressure drop than others considered in this work.

An Infrared Investigation on Surface Species over Iron-Based Catalysts: Implications for Oxygenates Formation

The nature of adsorbed species on catalytic surface over an industrial precipitated iron-based high temperature catalyst during FTS was investigated by in-situ DRIFTS and chemical trapping. The formulation of the mechanism of oxygenates formation and key intermediates were also discussed. Numerous oxygenated precursors and crucial intermediates were found by in-situ DRIFTS, such as surface acetate, acetyl and methoxide. The results showed that adsorbed molecules on surface such as methanol or acetaldehyde could react with basic sites such as lattice oxygen or free surface hydroxyls. Adsorbed molecules also had reactivity of oxidizing. Moreover, acetyl as a key intermediate for oxygenates was observed by investigation of CH3OH + CO and CH3I + CO + H2. Based on the nature of surface properties, the mechanism of oxygenates formation on precipitated iron-based high temperature catalyst was discussed.

Environmental Analysis of the Zinc Oxide Nanophotocatalyst Synthesis

Nanophotocatalysts such as titanium (TiO2), zinc (ZnO), and iron (Fe2O3) oxides can be used in organic pollutants oxidation, and in many other applications. But among the challenges for technological application (scale-up) of the nanotechnology scientific developments two aspects are still little explored: research on environmental risk of the nanomaterials preparation methods, and the study of nanomaterials properties and/or performance variability. The environmental analysis was performed for six different methods of ZnO nanoparticles synthesis, and showed that it is possible to identify the more environmentally compatible process even at laboratory scale research. The obtained ZnO nanoparticles were tested as photocatalysts, and increased the degradation rate of the Rhodamine B dye up to 30 times.

Hydrogenation of Acetic Acid on Alumina-Supported Pt-Sn Catalysts
Three alumina-supported Pt-Sn catalysts have been prepared by means of co-impregnation and characterized by XRD and N2 adsorption. The influence of catalyst composition and reaction conditions on the conversion and selectivity were investigated in the hydrogenation of acetic acid in an isothermal integral fixed bed reactor. The experiments were performed on the temperature interval 468-548 K, liquid hourly space velocity (LHSV) of 0.3-0.7h-1, pressures between 1.0 and 5.0Mpa. A good compromise of 0.75%Pt-1.5%Sn can act as an optimized acetic acid hydrogenation catalyst, and the conversion and selectivity can be tuned through the variation of reaction conditions.
Production of Spherical Ag/ZnO Nanocomposite Particles for Photocatalytic Applications
Noble metal participation in nanostructured semiconductor catalysts has drawn much interest because of their improved properties. Recently, it has been discussed by many researchers that Ag participation in TiO2, CuO, ZnO semiconductors showed improved photocatalytic and optical properties. In this research, Ag/ZnO nanocomposite particles were prepared by Ultrasonic Spray Pyrolysis(USP) Method. 0.1M silver and zinc nitrate aqueous solutions were used as precursor solutions. The Ag:Zn atomic ratio of the solution was selected 1:1. Experiments were taken place under constant air flow of 400 mL/min at 800°C furnace temperature. Particles were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Energy Dispersive Spectroscopy (EDS). The crystallite sizes of Ag and ZnO in composite particles are 24.6 nm, 19.7 nm respectively. Although, spherical nanocomposite particles are in a range of 300- 800 nm, these particles are formed by the aggregation of primary particles which are in a range of 20-60 nm.
Adsorption of H2 and CO on Iron-based Catalysts for Fischer-Tropsch Synthesis
The adsorption properties of CO and H2 on iron-based catalyst with addition of Zr and Ni were investigated using temperature programmed desorption process. It was found that on the carburized iron-based catalysts, molecular state and dissociative state CO existed together. The addition of Zr was preferential for the molecular state adsorption of CO on iron-based catalyst and the presence of Ni was beneficial to the dissociative adsorption of CO. On H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron sites and surface oxide sites. On CO reduced catalysts, hydrogen probably existed as the most stable CH and OH species. The addition of Zr was not benefit to the dissociative adsorption of hydrogen on iron-based catalyst and the presence of Ni was preferential for the dissociative adsorption of hydrogen.
La promoted Ni/α-Al2O3 Catalysts for Syngas Methanation
The Ni/α-Al2O3 catalysts with different amounts of La as promoter from 0 to 4 wt % were prepared, characterized and their catalytic activity was investigated in syngas methanation reaction. Effects of reaction temperature and lanthanum loading on carbon oxides conversion and methane selectivity were also studied. Adding certain amount of lanthanum to 10Ni /α-Al2O3 catalysts can decrease the average NiO crystallite diameter which leads to higher activity and stability while excessive addition would cause deactivation quickly. Stability on stream towards deactivation was observed up to 800 min at 500 °C, 0.1MPa and 600000 mL·g-1·h-1.
Structural and Electronic Characterization of Supported Ni and Au Catalysts used in Environment Protection Determined by XRD,XAS and XPS methods
The nickel and gold nanoclusters as supported catalysts were analyzed by XAS, XRD and XPS in order to determine their local, global and electronic structure. The present study has pointed out a strong deformation of the local structure of the metal, due to its interaction with oxide supports. The average particle size, the mean squares of the microstrain, the particle size distribution and microstrain functions of the supported Ni and Au catalysts were determined by XRD method using Generalized Fermi Function for the X-ray line profiles approximation. Based on EXAFS analysis we consider that the local structure of the investigated systems is strongly distorted concerning the atomic number pairs. Metal-support interaction is confirmed by the shape changes of the probability densities of electron transitions: Ni K edge (1s → continuum and 2p), Au LIII-edge (2p3/2 → continuum, 6s, 6d5/2 and 6d3/2). XPS investigations confirm the metal-support interaction at their interface.
Global and Local Structure of Supported Pd Catalysts
The supported Pd catalysts were analyzed by X-ray diffraction and X-ray absorption spectroscopy in order to determine their global and local structure. The average particle size of the supported Pd catalysts was determined by X-ray diffraction method. One of the main purposes of the present contribution is to focus on understanding the specific role of the Pd particle size determined by X-ray diffraction and that of the support oxide. Based on X-ray absorption fine structure spectroscopy analysis we consider that the whole local structure of the investigated samples are distorted concerning the atomic number but the distances between atoms are almost the same as for standard Pd sample. Due to the strong modifications of the Pd cluster local structure, the metal-support interface may influence the electronic properties of metal clusters and thus their reactivity for absorption of the reactant molecules.
Deactivation of Cu - Cr/γ-alumina Catalysts for Combustion of Exhaust Gases
The paper relates to a catalyst, comprising copperchromium spinel, coated on carrier γ-Al2O3. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. It was found that the activity of carbon monoxide, DME, formaldehyde and methanol oxidation reaches a maximum at an active component content of 20 – 30 wt. %. Temperature calcination at 500oC seems to be optimal for the γ– alumina supported CuO-Cr2O3 catalysts for CO, DME, formaldehyde and methanol oxidation. A three months industrial experiment was carried out to elucidate the changes in the catalyst composition during industrial exploitation of the catalyst and the main reasons for catalyst deactivation. It was concluded that the CuO–Cr2O3/γ–alumina supported catalysts have enhanced activity toward CO, DME, formaldehyde and methanol oxidation and that these catalysts are suitable for industrial application. The main reason for catalyst deactivation seems to be the deposition of iron and molybdenum, coming from the main reactor, on the active component surface.
Vol:13 No:02 2019Vol:13 No:01 2019
Vol:12 No:12 2018Vol:12 No:11 2018Vol:12 No:10 2018Vol:12 No:09 2018Vol:12 No:08 2018Vol:12 No:07 2018Vol:12 No:06 2018Vol:12 No:05 2018Vol:12 No:04 2018Vol:12 No:03 2018Vol:12 No:02 2018Vol:12 No:01 2018
Vol:11 No:12 2017Vol:11 No:11 2017Vol:11 No:10 2017Vol:11 No:09 2017Vol:11 No:08 2017Vol:11 No:07 2017Vol:11 No:06 2017Vol:11 No:05 2017Vol:11 No:04 2017Vol:11 No:03 2017Vol:11 No:02 2017Vol:11 No:01 2017
Vol:10 No:12 2016Vol:10 No:11 2016Vol:10 No:10 2016Vol:10 No:09 2016Vol:10 No:08 2016Vol:10 No:07 2016Vol:10 No:06 2016Vol:10 No:05 2016Vol:10 No:04 2016Vol:10 No:03 2016Vol:10 No:02 2016Vol:10 No:01 2016
Vol:9 No:12 2015Vol:9 No:11 2015Vol:9 No:10 2015Vol:9 No:09 2015Vol:9 No:08 2015Vol:9 No:07 2015Vol:9 No:06 2015Vol:9 No:05 2015Vol:9 No:04 2015Vol:9 No:03 2015Vol:9 No:02 2015Vol:9 No:01 2015
Vol:8 No:12 2014Vol:8 No:11 2014Vol:8 No:10 2014Vol:8 No:09 2014Vol:8 No:08 2014Vol:8 No:07 2014Vol:8 No:06 2014Vol:8 No:05 2014Vol:8 No:04 2014Vol:8 No:03 2014Vol:8 No:02 2014Vol:8 No:01 2014
Vol:7 No:12 2013Vol:7 No:11 2013Vol:7 No:10 2013Vol:7 No:09 2013Vol:7 No:08 2013Vol:7 No:07 2013Vol:7 No:06 2013Vol:7 No:05 2013Vol:7 No:04 2013Vol:7 No:03 2013Vol:7 No:02 2013Vol:7 No:01 2013
Vol:6 No:12 2012Vol:6 No:11 2012Vol:6 No:10 2012Vol:6 No:09 2012Vol:6 No:08 2012Vol:6 No:07 2012Vol:6 No:06 2012Vol:6 No:05 2012Vol:6 No:04 2012Vol:6 No:03 2012Vol:6 No:02 2012Vol:6 No:01 2012
Vol:5 No:12 2011Vol:5 No:11 2011Vol:5 No:10 2011Vol:5 No:09 2011Vol:5 No:08 2011Vol:5 No:07 2011Vol:5 No:06 2011Vol:5 No:05 2011Vol:5 No:04 2011Vol:5 No:03 2011Vol:5 No:02 2011Vol:5 No:01 2011
Vol:4 No:12 2010Vol:4 No:11 2010Vol:4 No:10 2010Vol:4 No:09 2010Vol:4 No:08 2010Vol:4 No:07 2010Vol:4 No:06 2010Vol:4 No:05 2010Vol:4 No:04 2010Vol:4 No:03 2010Vol:4 No:02 2010Vol:4 No:01 2010
Vol:3 No:12 2009Vol:3 No:11 2009Vol:3 No:10 2009Vol:3 No:09 2009Vol:3 No:08 2009Vol:3 No:07 2009Vol:3 No:06 2009Vol:3 No:05 2009Vol:3 No:04 2009Vol:3 No:03 2009Vol:3 No:02 2009Vol:3 No:01 2009
Vol:2 No:12 2008Vol:2 No:11 2008Vol:2 No:10 2008Vol:2 No:09 2008Vol:2 No:08 2008Vol:2 No:07 2008Vol:2 No:06 2008Vol:2 No:05 2008Vol:2 No:04 2008Vol:2 No:03 2008Vol:2 No:02 2008Vol:2 No:01 2008
Vol:1 No:12 2007Vol:1 No:11 2007Vol:1 No:10 2007Vol:1 No:09 2007Vol:1 No:08 2007Vol:1 No:07 2007Vol:1 No:06 2007Vol:1 No:05 2007Vol:1 No:04 2007Vol:1 No:03 2007Vol:1 No:02 2007Vol:1 No:01 2007