Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.

The effects of solid contamination in hydraulic fluids on axial piston pumps

The fluids used in hydraulic systems inevitably contain large numbers of small, solid particles, a phenomenon known as 'fluid contamination'. Particles enter a hydraulic system from the environment, and are generated within it by processes of wear. At the same time, particles are removed from the system fluid by sedimentation and in hydraulic filters. This thesis considers the problems caused by fluid contamination, as they affect a manufacturer of axial piston pumps. The specific project aim was to investigate methods of predicting or determining the effects of fluid contamination on this type of pump. The thesis starts with a theoretical analysis of the contaminated lubrication of a slipper-pad bearing. Statistical methods are used to develop a model of the blocking, by particles, of the control capillaries used in such bearings. The results obtained are compared to published, experimental data. Poor correlation between theory and practice suggests that more research is required in this area before such theoretical analysis can be used in industry. Accelerated wear tests have been developed in the U.S.A. in an attempt to predict pump life when operating on contaminated fluids. An analysis of such tests shows that reliability data can only be obtained from extensive test programmes. The value of contamination testing is suggested to be in determining failure modes, and in identifying those pump components which are susceptible to the effects of contamination. A suitable test is described, and the results of a series of tests on axial piston pumps are presented and discussed. The thesis concludes that pump reliability data can only be obtained from field experience. The level of confidence which can be placed in results from normal laboratory testing is shown to be too low for the data to be of real value. Recommendations are therefore given for the ways in which service data should be collected and analysed.

Investigating the molecular structures of solid dispersions by the simulated annealing method

Knowledge of the molecular structures of solid dispersions is vital, yet, despite thousands of reports in this area, it remains unclear. The aim of this research is to investigate the molecular structure of solid dispersions with hot melt preparation method by the simulated annealing method. Simulation results showed linear polymer chains form the random coils under heat and the drug molecules stick on the surface of polymer coils, while drug molecules are dispersed molecularly but irregularly within the amorphous low molecular weight carriers. This research presents more reasonable molecular images of solid dispersions than the existed theory.

Optimising the nanoporous architecture of solid acid and base catalysts for biodiesel synthesis

Dwindling oil reserves and growing concerns over CO2 emissions and associated climate change are driving the utilisation of renewable feedstocks as alternative, sustainable fuel sources. While rising oil prices are improving the commercial feasibility of biodiesel production, many current processes still employ homogeneous acid and/or base catalysts to transform plant or algae oil into the fatty acid methyl ester (FAME) components of biodiesel. Fuel purification requires energy intensive aqueous quench and neutralization steps, thus the rational design of new high activity catalysts is required to deliver biodiesel as a major player in the 21st century sustainable energy portfolio. Advances in the development of heterogeneous catalysts for biodiesel synthesis require catalysts with pore architectures designed to improve the accessibility of bulky viscous reactants typical of plant oils. Here we discuss how improvements to active site accessibility and catalyst activity in transesterification or esterification reactions can be achieved either by designing hierarchical pore networks or by pore expansion and use of interconnected pore architectures.

Quantitative analysis of solid-state processes studied with isothermal microcalorimetry

Quantitative analysis of solid-state processes from isothermal microcalorimetric data is straightforward if data for the total process have been recorded and problematic (in the more likely case) when they have not. Data are usually plotted as a function of fraction reacted (α); for calorimetric data, this requires knowledge of the total heat change (Q) upon completion of the process. Determination of Q is difficult in cases where the process is fast (initial data missing) or slow (final data missing). Here we introduce several mathematical methods that allow the direct calculation of Q by selection of data points when only partial data are present, based on analysis with the Pérez-Maqueda model. All methods in addition allow direct determination of the reaction mechanism descriptors m and n and from this the rate constant, k. The validity of the methods is tested with the use of simulated calorimetric data, and we introduce a graphical method for generating solid-state power-time data. The methods are then applied to the crystallization of indomethacin from a glass. All methods correctly recovered the total reaction enthalpy (16.6 J) and suggested that the crystallization followed an Avrami model. The rate constants for crystallization were determined to be 3.98 × 10-6, 4.13 × 10-6, and 3.98 × 10 -6 s-1 with methods 1, 2, and 3, respectively. © 2010 American Chemical Society.

The potential of solid phase microextraction (SPME) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Results for use of GC/ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives. ^

The potential of solid phase microextraction (spme) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Re suits for use of GC[ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives.