Surface segregation of siloxane containing component in polysiloxane‐block‐polyimide and s‐BPDA/ODA polyimide blends

Surface segregation in polymer blend systems between 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐diaminodiphenyl ether (s‐BPDA/ODA) polyimide and block copolymer based on polysiloxane‐block‐polyimide (SPI) has been investigated. These polyimide blends, having various compositions of the SPI, were processed by a solution casting method. The glass substrate used in the film‐casting process shows significant effect on the migration of surface segregated species to enrich the air‐exposed surface, whereas the more polar s‐BPDA/ODA tends to remain close to the polar glass substrate. X‐ray photoelectron spectroscopy reveals that even at low SPI concentration, the siloxane moieties in the block copolymer tend to segregate into the air side surface. Contact angle measurement evidently indicates an enrichment of the hydrophobic siloxane fraction on the blend film surface. The average water contact angle of glass side surface is 77°C whereas that of the air side is about 102°C in every blend ratio. This behavior confirms the surface segregation phase separation in these polymer blends. Finally, the surface morphology observed by atomic force microscopy also suggests segregation type of phase separation in these blend systems. POLYM. ENG. SCI., 47:489–498, 2007. © 2007 Society of Plastics Engineers.     

Simulation and thermodynamic analysis of chemical looping reforming and CO2 enhanced chemical looping reforming

The production of hydrogen from methane via two chemical looping reforming (CLR) processes was simulated and thermodynamically analysed, one process being the conventional CLR process, the other being a CO₂ sorption enhanced process. The aim of the work was to identify suitable operating conditions for obtaining an optimum hydrogen gas purity and yield, whilst operating auto-thermally, at atmospheric pressure and with no carbon formation. In both simulations, the reactors were simulated using the Gibbs minimisation technique. NiO was used as the oxygen storing species, whilst CaO was used as the CO₂ adsorbent.     

Thermodynamic study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications

This study presents a thermodynamic analysis of hydrogen production from an autothermal reforming of crude glycerol derived from a biodiesel production process. As a composition of crude glycerol depends on feedstock and processes used in biodiesel production, a mixture of glycerol and methanol, major components in crude glycerol, at different ratios was used to investigate its effect on the autothermal reforming process. Equilibrium compositions of reforming gas obtained were determined as a function of temperature, steam to crude glycerol ratio, and oxygen to crude glycerol ratio. The results showed that at isothermal condition, raising operating temperature increases hydrogen yield, whereas increasing steam to crude glycerol and oxygen to crude glycerol ratios causes a reduction of hydrogen concentration. However, high temperature operation also promotes CO formation which would hinder the performance of low-temperature fuel cells. The steam to crude glycerol ratio is a key factor to reduce the extent of CO but a dilution effect of steam should be considered if reforming gas is fed to fuel cells. An increase in the ratio of glycerol to methanol in crude glycerol can increase the amount of hydrogen produced. In addition, an optimal operating condition of glycerol autothermal reforming at a thermoneutral condition that no external heat to sustain the reformer operation is required, was investigated.     

Active power filter for three-phase four-wire electric systems using neural networks

This paper presents the design of neural networks compared with the conventional technique, a hysteresis controller for active power filter for three-phase four-wire electric system. A particular three-layer neural network structure is studied in some detail. Simulation and experimental results of the active power filter with both controllers are also presented to verify the feasibility of such controller. The simulation and experimental result show that both controller techniques can reduce harmonics in three-phase four-wire electric systems drawn by nonlinear loads and can reduce neutral current. The advantage of the neural network controller technique over hysteresis controller technique are less voltage ripple of d.c. bus, and less switching loss. Furthermore, the neural networks controller has better fault tolerance than the hysteresis controller.     

Isosynthesis via CO hydrogenation over SO4–ZrO2 catalysts

Catalytic performances of sulfated zirconia catalysts with various contents of sulfur (from 0.1 to 0.75%) on isosynthesis were studied. It was firstly found that undoped-zirconia synthesized from zirconyl nitrate provided higher activity towards isosynthesis reaction (106 μmol kg-cat^?1 s^?1) compared to that synthesized from zirconyl chloride (84.9 μmol kg-cat^?1 s^?1). Nevertheless, the selectivity of isobutene in hydrocarbons was relatively lower. It was then observed that the catalytic reactivity and selectivity significantly improved by sulfur loading. The most suitable sulfur loading content seems to be at 0.1%, which gave the highest reaction rate and selectivity of isobutene. By applying several characterization techniques, i.e. BET, XRD, NH₃- and CO₂-TPD and SEM, it was revealed that the high reaction rate and selectivity towards isosynthesis reaction of sulfated zirconia catalysts are related to the acid–base properties, Zr³⁺ quantity and phase composition.     

Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

Production of ethyltert-butyl ether fromtert-butyl alcohol and ethanol catalyzed byβ-zeolite in reactive distillation

The synthesis of ethyl tert-butyl ether (ETBE) from a liquid phase reaction between tert-butyl alcohol (TBA) and ethanol (EtOH) in reactive distillation has been studied.β-Zeolite catalysts with three compositions (Si/Al ratio=13, 36 and 55) were compared by testing the reaction in a semi-batch reactor. Although they showed almost the same performance, the one with Si/Al ratio of 55 was selected for the kinetic and reactive distillation studies because it is commercially available and present in a ready-to-use form. The kinetic parameters of the reaction determined by fitting parameters with the experimental results at temperature in the range of 343–363 K were used in an ASPEN PLUS simulator. Experimental results of the reactive distillation at a standard condition were used to validate a rigorous reactive distillation model of the ASPEN PLUS used in a simulation study. The effects of various operating parameters such as condenser temperature, feed molar flow rate, reflux ratio, heat duty and mole ratio of H₂O : EtOH on the reactive distillation performance were then investigated via simulation using the ASPEN PLUS program. The results were compared between two reactive distillation columns: one packed withβ-zeolite and the other with conventional Amberlyst-15. It was found that the effect of various operating parameters for both types of catalysts follows the same trend; however, the column packed withΒ-zeolite outperforms that with Amberlyst-15 catalyst due to the higher selectivity of the catalyst.     

Performance evaluation of combined solid oxide fuel cells with different electrolytes

The performance of a hybrid system of solid oxide fuel cells with different electrolytes, i.e., an oxygen-ion conducting electrolyte (SOFC-O²⁻) and a proton-conducting electrolyte (SOFC-H⁺) is evaluated in this study. Due to an internal reforming operation, SOFC-O²⁻ can produce electrical power as well as high-temperature exhaust gas containing remaining fuel, i.e., H₂ and CO that can be used for SOFC-H⁺ operation. The remaining CO can further react with H₂O via water gas-shift reaction to produce more H₂ within SOFC-H⁺ and thus, the possibility of carbon formation in SOFC-H⁺ can be eliminated and overall system efficiency can be improved. The simulation results show that the performance of the SOFC-O²⁻–SOFC-H⁺ system provides a higher efficiency (54.11%) compared with the use of a single SOFC. Further, the SOFC hybrid system performance is investigated with respect to important operating conditions, such as temperature, pressure, degree of pre-reforming, inlet fuel velocity, and cell voltage.     

Analysis of a pressurized solid oxide fuel cell–gas turbine hybrid power system with cathode gas recirculation

A pressurized solid oxide fuel cell–gas turbine hybrid system (SOFC–GT system) has been received much attention for a distributed power generation due to its high efficiency. When considering an energy management of the system, it is found that a heat input is highly required to preheat air before being fed to the SOFC stack. The recirculation of a high-temperature cathode exhaust gas is probably an interesting option to reduce the requirement of an external heat for the SOFC–GT system. This study aims to analyze the pressurized SOFC–GT hybrid system fed by ethanol with the recycle of a cathode exhaust gas via a simulation study. Effect of important operating parameters on the electrical efficiency and heat management of the system is investigated. The results indicate that an increase in the operating pressure dramatically improves the system electrical efficiency. The suitable pressure is in a range of 4–6 bar, achieving the highest system electrical efficiency and the lowest recuperation energy from the waste heat of the GT exhaust gas. In addition, it is found that the waste heat obtained from the GT is higher than the heat required for the system, leading to a possibility of the SOFC–GT system to be operated at a self-sustainable condition. Under a high pressure operation, the SOFC–GT system requires a high recirculation of the cathode exhaust gas to maintain the system without supplying the external heat; however, the increased recirculation ratio of the cathode exhaust gas reduces the system electrical efficiency.     

Experimental study of dual fixed bed biochar-catalytic gasification with simultaneous feed of O2-steam-CO2 for synthesis gas or hydrogen production

The catalytic gasification of biochar was investigated in the presence of a Ni/SiO₂ catalyst in a fixed bed reactor with an O₂-steam-CO₂ gas feed. The effects of operating temperature, catalyst nickel loading and composition of O₂-steam-CO₂ feed gas on biochar carbon conversion and gas products were investigated. The results indicate that the highest biochar carbon conversion could be obtained at approximately 800 °C, whilst the 10% Ni/SiO₂ catalyst was shown to produce the greatest syngas yields. The presence of O₂ in the feed gas can result in slightly more CO in the gas product, whilst a higher steam content leads to more H₂ in the gas product. The CO₂ offered a benefit as an adjusting agent for achieving a desired H₂/CO ratio. No evidence of coke deposition on the catalyst was found under any of the tested conditions.