Organosulfonic acid-functionalized mesoporous composites based on natural rubber and hexagonal mesoporous silica

This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO₃H), a series of NR/HMS-SO₃H composites were prepared via an in situ sol–gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO₃H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO₃H composites. The textural properties of NR/HMS-SO₃H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO₃H. NR/HMS-SO₃H exhibited higher hydrophobicity than HMS-SO₃H, as revealed by H₂O adsorption–desorption measurements. Moreover, the NR/HMS-SO₃H catalysts possessed a superior specific activity to HMS-SO₃H in the esterification of lauric acid with ethanol, resulting in a higher conversion level.     

Chi river basin irrigation demand model

The calculation of irrigation demands and return flows is an essential component of the Chi Basin (Northeast Thailand) simulation model. The irrigation demand model is based on a simple field water balance so does not use the concept of effective rainfall. The paper describes the structure of the model. A sensitivity analysis on the model output is described.     

Biodiesel production through transesterification over natural calciums

Transesterification of palm kernel oil (PKO) with methanol over various natural calciums, including limestone calcite, cuttlebone, dolomite, hydroxyapatite, and dicalcium phosphate, has been investigated at 60 °C and 1 atm. The study showed that dolomite, mainly consisting of CaCO₃ and MgCO₃, is the most active catalyst. The calcination temperature largely affected the physicochemical properties, as evidenced by N₂ adsorption-desorption measurement, TGA, SEM and XRD, and the transesterification performance of the resultant catalysts. It was found that the calcination of dolomite at 800 °C resulted in a highly active mixed oxide. CaO was suggested to be the catalytically active site responsible for the methyl ester formation. Under the suitable reaction conditions, the amount of dolomite calcined at 800 °C = 6 wt.% based on the weight of oil, the methanol/oil molar ratio = 30, and the reaction time = 3 h, the methyl ester content of 98.0% can be achieved. The calcined dolomite can be reused many times. The analyses of some important fuel properties indicated that the biodiesel produced had the properties that meet the standard of biodiesel and diesel fuel issued by the Department of Energy Business, Ministry of Energy, Thailand.     

The design of linear and circular polarization for dual band microstrip slot antenna

This paper presents a lightweight antenna for wireless communication systems. The proposed antenna has been designed to be a dual‐band and dual‐polarized antenna by using a right‐angled slot structure fed a by microstrip line. The designed antenna is composed of three right‐angled slot radiators on the ground plane. The first two radiators are right‐angled slots of similar scale which are added to generate circular polarization at 4.95 GHz, while the last one has been designed for linear polarization at 2.45 GHz. Furthermore, in order to achieve dual‐band operation and dual polarization with good matching, a special arrangement is proposed. The results of simulation and measurements such as return loss, axial ratio, and radiation patterns are shown at the resonant frequencies of 2.45 and 4.95 GHz. Details of the experimental results are presented and discussed. In addition, the presented antenna can operate and cover the applications of a wireless local area network (WLAN IEEE 802.11 a/b/g/j/n). © 2014 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Controllable Band‐Notched Slot Antenna for UWB Communication Systems

We propose a slot antenna consisting of a rectangular slot on the ground plane, fed by a microstrip line with a rectangular‐ring‐shaped tuning stub that can be deployed in ultra‐wideband (UWB) communication systems to avoid interference with wireless local area network (WLAN) communication. Our antenna can achieve a single band‐notched property from the 5 GHz frequency to the 6 GHz frequency owing to a controllable band notch that uses L‐ and J‐shaped parasitic elements. The antenna characteristics can be modified to tune the band‐notched property (4 GHz to 5 GHz or 6 GHz to 7 GHz) and the bandwidth of the band notch (1 GHz to 2 GHz). Furthermore, the shifted notch with enhanced width of the band notch from 1 GHz to 1.5 GHz is described in this paper. The UWB slot antenna and L‐ and J‐shaped parasitic elements also provide the band‐rejection function for reference in the WiMAX (3.5 GHz) and WLAN (5 GHz to 6 GHz) regions of the spectrum. Experiment results evidence the return loss performance, radiation patterns, and antenna gains at different operational frequencies.     

Green, Blue and Grey Water Footprints of Primary Crops Production in Nepal

This study aims to estimate the green, blue and grey water footprints (WFs) of nine primary crops production in 75 districts, 5 developmental regions and 3 physiographic divisions of Nepal using local meteorological, agronomical and irrigation data at high spatial resolution. The estimates are based on the framework prescribed by the guideline of the Water Footprint Network. The green and blue WFs are calculated using a water balance model whereas the grey WF is estimated as the volume of freshwater needed to dilute nitrate pollution to an acceptable level. WF varies across different crops considered, different districts, development regions and physiographic divisions. WF of potato and wheat in Nepal is comparable to the world average; but paddy, barley and pulses have higher while sugarcane and maize have lower values compared to the world average. WFs of paddy, maize, potato and wheat are lower in Terai than the Hills and Mountains due to the accessibility of irrigation system and higher crop yield. Millet, pulses, oilseeds and barley have lower WFs and are suitable for Mountains. Similarly, sugarcane is suitable for both Terai and Mountain divisions because of its lower WF. Crops in Far Western Development Region generally have higher WFs due to the low crop productivity, and higher fertilizer use.     

Novel mesoporous composites based on natural rubber and hexagonal mesoporous silica: Synthesis and characterization

The present study is the first report on the synthesis and characterization of mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). A series of NR/HMS composites were prepared in tetrahydrofuran via an in situ sol–gel process using tetraethylorthosilicate as the silica precursor. The physicochemical properties of the composites were characterized by various techniques. The effects of the gel composition on the structural and textural properties of the NR/HMS composites were investigated. The Fourier-transform infrared spectroscopy (FTIR) and ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR) results revealed that the surface silanol groups of NR/HMS composites were covered with NR molecules. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated an expansion of the hexagonal unit cell and channel wall thickness due to the incorporation of NR molecules into the mesoporous structure. NR/HMS composites also possessed nanosized particles (∼79.4 nm) as confirmed by scanning electron microscopy (SEM) and particle size distribution analysis. From N₂ adsorption–desorption measurement, the NR/HMS composites possessed a high BET surface area, large pore volume and narrow pore size distribution. Further, they were enhanced hydrophobicity confirmed by H₂O adsorption–desorption measurement. In addition, the mechanistic pathway of the NR/HMS composite formation was proposed.     

Al2O3-supported alkali and alkali earth metal oxides for transesterification of palm kernel oil and coconut oil

Transesterification of palm kernel oil (PKO) and coconut oil (CCO) with methanol was investigated under a heterogeneous catalysis system. Various Al₂O₃-supported alkali and alkali earth metal oxides prepared via an impregnation method were applied as solid catalysts. The supported alkali metal catalysts, LiNO₃/Al₂O₃, NaNO₃/Al₂O₃ and KNO₃/Al₂O₃, with active metal oxides formed at calcination temperatures of 450–550 °C, showed very high methyl ester (ME) content (>93%). XRF analysis suggests this is likely to be due to a homogeneous catalysis of dissoluted alkali oxides. On the other hand, Ca(NO₃)₂/Al₂O₃ calcined at 450 °C yielded the ME content as high as 94% with only a small loss of active oxides from the catalyst, whereas calcined Mg(NO₃)₂/Al₂O₃ catalyst possessed an inactive magnesium-aluminate phase, resulting in very low ME formation. At calcination temperatures of >650 °C, alkali metal- and alkali earth metal-aluminate compounds were formed. Whilst the water-soluble alkali metal aluminates formed over NaNO₃/Al₂O₃ and KNO₃/Al₂O₃ were catalytically active, the aluminate compounds on LiNO₃/Al₂O₃ and Ca(NO₃)₂/Al₂O₃ are less soluble, giving very low ME content. The suitable conditions for heterogeneously catalyzed transesterification of PKO and CCO over Ca(NO₃)₂/Al₂O₃ are the methanol/oil molar ratio of 65, temperature of 60 °C and reaction time of 3 h, with 10 and 15–20% (w/w) catalyst to oil ratio for PKO and CCO, respectively. Some important physical and fuel properties of the resultant biodiesel products meet the standards of diesel fuel and biodiesel issued by Department of Energy Business, Ministry of Energy, Thailand.     

Adsorptive removal of thiophene and benzothiophene over zeolites from Mae Moh coal fly ash

Zeolites have been hydrothermally synthesized using Thai coal fly ash from Mae Moh Power Plant as silica and alumina sources. The synthesis conditions, i.e., SiO₂/Al₂O₃ ratio, amount of water, amount of base, and aging temperature, were varied to prepare different topologies of zeolitic products. The zeolites attained were sodalite (SOD), gismondine (GIS), and cancrinite (CAN). The zeolites have been applied to adsorption of thiophene and benzothiophene in n-hexane solution. It was found that GIS with higher specific surface area and average pore volume had superior performance to other synthesized materials. Adsorption capacity of our developed zeolites was compared to those of commercial zeolites, i.e. NaY, HUSY, beta, and ZSM-5 obtained via the conventional synthesis methods. The results suggested a potential of zeolites derived from Mae Moh coal fly ash for removal of refractory sulfur compounds, such as benzothiophene.     

Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution

The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS.