Improvement of bio-oil stability in wood pyrolysis process

Pyrolysis is one of several thermochemical technologies that convert solid biomass into more useful and valuable bio-fuels. Pyrolysis is thermal degradation in the complete or partial absence of oxygen. Under carefully controlled conditions, solid biomass can be converted to a liquid known as bie-oil in 75% yield on dry feed. Bio-oil can be used as a fuel but has the drawback of having a high level of oxygen due to the presence of a complex mixture of molecular fragments of cellulose, hemicellulose and lignin polymers. Also, bio-oil has a number of problems in use including high initial viscosity, instability resulting in increased viscosity or phase separation and high solids content. Much effort has been spent on upgrading bio-oil into a more usable liquid fuel, either by modifying the liquid or by major chemical and catalytic conversion to hydrocarbons. The overall primary objective was to improve oil stability by exploring different ways. The first was to detennine the effect of feed moisture content on bio-oil stability. The second method was to try to improve bio-oil stability by partially oxygenated pyrolysis. The third one was to improve stability by co-pyrolysis with methanol. The project was carried out on an existing laboratory pyrolysis reactor system, which works well with this project without redesign or modification too much. During the finishing stages of this project, it was found that the temperature of the condenser in the product collection system had a marked impact on pyrolysis liquid stability. This was discussed in this work and further recommendation given. The quantity of water coming from the feedstock and the pyrolysis reaction is important to liquid stability. In the present work the feedstock moisture content was varied and pyrolysis experiments were carried out over a range of temperatures. The quality of the bio-oil produced was measured as water content, initial viscosity and stability. The result showed that moderate (7.3-12.8 % moisture) feedstock moisture led to more stable bio-oil. One of drawbacks of bio-oil was its instability due to containing unstable oxygenated chemicals. Catalytic hydrotreatment of the oil and zeolite cracking of pyrolysis vapour were discllssed by many researchers, the processes were intended to eliminate oxygen in the bio-oil. In this work an alternative way oxygenated pyrolysis was introduced in order to reduce oil instability, which was intended to oxidise unstable oxygenated chemicals in the bio-oil. The results showed that liquid stability was improved by oxygen addition during the pyrolysis of beech wood at an optimum air factor of about 0.09-0.15. Methanol as a postproduction additive to bio-oil has been studied by many researchers and the most effective result came from adding methanol to oil just after production. Co-pyrolysis of spruce wood with methanol was undertaken in the present work and it was found that methanol improved liquid stability as a co-pyrolysis solvent but was no more effective than when used as a postproduction additive.

The stability of pharmaceutical powders: effect of additives and coating

The decomposition of drugs in the solid state has been studied using aspirin and salsalate as models. The feasibility of using suspension systems for predicting the stability of these drugs in the solid state has been investigated.. It has been found that such systems are inappropriate in defining the effect of excipients on 'the decomposition of the active drug due to chqnges in the degradation pathway. Using a high performance liquid chromatographic method, magnesium stearate was shown to induce the formation of potentlally immunogenic products in aspirin powders. These products which included salicylsalicylic acid .and acetylsalicyclsalicylic acid were not detected in aspirin suspensions which had undergone the same extent of decomposition. By studying the effect of pH and of added excipients on the rate of decomposition of aspirin in suspension systems, it has been shown that excipients such as magnesium stearate containing magnesium oxide, most probably enhance the decomposition of both aspirin and salsalate by alkalinising the aqueous phase. In the solid state, pH effects produced by excipients appear to be relatively unimportant. Evidence is presented to suggest that the critical parameter is a depression in melting point induced by: the added excipient. Microscopical examination in fact showed the formation of clear liquid layers in aspirin samples containing added magnesium stearate but not in control samples. Kinetic equations which take into account both the diffusive barrier presented by the liquid films and the. geometry of the aspirin crystals were developed. Fitting of the .experimental data to these equations showed good agreement. with the postulated theory. Monitorjng of weight issues during the decomposition of aspirin revealed that in the solid systems studied where the bulk of the decomposition product sublimes, it is possible to estimate the extent of degradation from the residual weight, provided the initial weight is known. The corollary is that in such open systems, monitoring of decomposition products is inadequate for assessing the extent of decomposition. In addition to the magnesium stearate-aspirin system, mapyramine maleate-aspirin mixtures were used to model interactive systems. Work carried out in an attempt to stabilise such systems included microencapsulation and film coating. The protection obtained was dependent on the interactive species used. Gelatin for example appeared to stabilise aspirin against the adverse effects of magnesium stearate but increased its decomposition in the presence of mapyramine maleate.

Techniques for determining bias and stability in satellite altimeters

The case for monitoring large-scale sea level variability is established in the context of the estimation of the extent of anthropogenic climate change. Satellite altimeters are identified as having the potential to monitor this change with high resolution and accuracy. Possible sources of systematic errors and instabilities in these instruments which would be hurdles to the most accurate monitoring of such ocean signals are examined. Techniques for employing tide gauges to combat such inaccuracies are proposed and developed. The tide gauge at Newhaven in Sussex is used in conjunction with the nearby satellite laser ranger and high-resolution ocean models to estimate the absolute bias of the TOPEX, Poseidon, ERS 1 and ERS 2 altimeters. The theory which underlies the augmentation of altimeter measurements with tide gauge data is developed. In order to apply this, the tide gauges of the World Ocean Circulation Experiment are assessed and their suitability for altimeter calibration is determined. A reliable subset of these gauges is derived. A method of intra-altimeter calibration is developed using these tide gauges to remove the effect of variability over long time scales. In this way the long-term instability in the TOPEX range measurement is inferred and the drift arising from the on-board ultra stable oscillator is thus detected. An extension to this work develops a method for inter-altimeter calibration, allowing the systematic differences between unconnected altimeters to be measured. This is applied to the TOPEX and ERS 1 altimeters.

Remote sensing applied to slope stability in mountainous roads in Iran

The Alborz Mountain range separates the northern part of Iran from the southern part. It also isolates a narrow coastal strip to the south of the Caspian Sea from the Central Iran plateau. Communication between the south and north until the 1950's was via two roads and one rail link. In 1963 work was completed on a major access road via the Haraz Valley (the most physically hostile area in the region). From the beginning the road was plagued by accidents resulting from unstable slopes on either side of the valley. Heavy casualties persuaded the government to undertake major engineering works to eliminate ''black spots" and make the road safe. However, despite substantial and prolonged expenditure the problems were not solved and casualties increased steadily due to the increase in traffic using the road. Another road was built to bypass the Haraz road and opened to traffic in 1983. But closure of the Haraz road was still impossible because of the growth of settlements along the route and the need for access to other installations such as the Lar Dam. The aim of this research was to explore the possibility of applying Landsat MSS imagery to locating black spots along the road and the instability problems. Landsat data had not previously been applied to highway engineering problems in the study area. Aerial photographs are better in general than satellite images for detailed mapping, but Landsat images are superior for reconnaissance and adequate for mapping at the 1 :250,000 scale. The broad overview and lack of distortion in the Landsat imagery make the images ideal for structural interpretation. The results of Landsat digital image analysis showed that certain rock types and structural features can be delineated and mapped. The most unstable areas comprising steep slopes, free of vegetation cover can be identified using image processing techniques. Structural lineaments revealed from the image analysis led to improved results (delineation of unstable features). Damavand Quaternary volcanics were found to be the dominant rock type along a 40 km stretch of the road. These rock types are inherently unstable and partly responsible for the difficulties along the road. For more detailed geological and morphological interpretation a sample of small subscenes was selected and analysed. A special developed image analysis package was designed at Aston for use on a non specialized computing system. Using this package a new and unique method for image classification was developed, allowing accurate delineation of the critical features of the study area.

An investigation into the wavelength stability of polymer optical fibre Bragg gratings

The inscription of Bragg gratings has been demonstrated in PMMA-based polymer optical fibre. The water affinity of PMMA can introduce significant wavelength change in a polymer optical fibre Bragg grating (POFBG). In polymer optical fibre losses are much higher than with silica fibre. Very strong absorption bands related to higher harmonics of vibrations of the C-H bond dominate throughout the visible and near infrared. Molecular vibration in substances generates heat, which is referred to as the thermal effect of molecular vibration. This means that a large part of the absorption of optical energy in those spectral bands will convert into thermal energy, which eventually drives water content out of the polymer fibre and reduces the wavelength of POFBG. In this work we have investigated the wavelength stability of POFBGs in different circumstances. The experiment has shown that the characteristic wavelength of a POFBG starts decreasing after a light source is applied to it. This decrease continues until equilibrium inside the fibre is established, depending on the initial water content inside the fibre, the surrounding humidity, the optical power applied, and the fibre size. Our investigation has shown that POFBGs operating at around 850 nm show much smaller wavelength reduction than those operating at around 1550 nm in the same fibre; POFBGs with different diameters show different changes; POFBGs powered by a low level light source, or operating in a very dry environment are least affected by this thermal effect.

Personality across working life:the longitudinal and reciprocal influences of personality on work

Summary: This paper focuses on the role of personality at different stages of people's working lives. We begin by reviewing the research in industrial, work, and organizational (IWO) psychology regarding the longitudinal and dynamic influences of personality as an independent variable at different career stages, structuring our review around a framework of people's working lives and careers over time. Next, we review recent studies in the personality and developmental psychology domain regarding the influence of changing life roles on personality. In this domain, personality also serves as a dependent variable. By blending these two domains, it becomes clear that the study of reciprocal effects of work and personality might open a new angle in IWO psychology's long-standing tradition of personality research. To this end, we outline various implications for conceptual development (e.g., trait stability) and empirical research (e.g., personality and work incongruence). Finally, we discuss some methodological and statistical considerations for research in this new research domain. In the end, our review should enrich the way that IWO psychologists understand personality at work, focusing away from its unidirectional predictivist influence on job performance toward a more complex longitudinal reciprocal interplay of personality and working life. © 2013 John Wiley & Sons, Ltd.

Magnetohydrodynamic stability of stochastically driven accretion flows

We investigate the evolution of magnetohydrodynamic (or hydromagnetic as coined by Chandrasekhar) perturbations in the presence of stochastic noise in rotating shear flows. The particular emphasis is the flows whose angular velocity decreases but specific angular momentum increases with increasing radial coordinate. Such flows, however, are Rayleigh stable but must be turbulent in order to explain astrophysical observed data and, hence, reveal a mismatch between the linear theory and observations and experiments. The mismatch seems to have been resolved, at least in certain regimes, in the presence of a weak magnetic field, revealing magnetorotational instability. The present work explores the effects of stochastic noise on such magnetohydrodynamic flows, in order to resolve the above mismatch generically for the hot flows. We essentially concentrate on a small section of such a flow which is nothing but a plane shear flow supplemented by the Coriolis effect, mimicking a small section of an astrophysical accretion disk around a compact object. It is found that such stochastically driven flows exhibit large temporal and spatial autocorrelations and cross-correlations of perturbation and, hence, large energy dissipations of perturbation, which generate instability. Interestingly, autocorrelations and cross-correlations appear independent of background angular velocity profiles, which are Rayleigh stable, indicating their universality. This work initiates our attempt to understand the evolution of three-dimensional hydromagnetic perturbations in rotating shear flows in the presence of stochastic noise. © 2013 American Physical Society.

Stability of multi-agent systems

This work attempts to shed light to the fundamental concepts behind the stability of Multi-Agent Systems. We view the system as a discrete time Markov chain with a potentially unknown transitional probability distribution. The system will be considered to be stable when its state has converged to an equilibrium distribution. Faced with the non-trivial task of establishing the convergence to such a distribution, we propose a hypothesis testing approach according to which we test whether the convergence of a particular system metric has occurred. We describe some artificial multi-agent ecosystems that were developed and we present results based on these systems which confirm that this approach qualitatively agrees with our intuition.

An investigation into the wavelength stability of polymer optical fibre Bragg gratings

The inscription of Bragg gratings has been demonstrated in PMMA-based polymer optical fibre. The water affinity of PMMA can introduce significant wavelength change in a polymer optical fibre Bragg grating (POFBG). In polymer optical fibre losses are much higher than with silica fibre. Very strong absorption bands related to higher harmonics of vibrations of the C-H bond dominate throughout the visible and near infrared. Molecular vibration in substances generates heat, which is referred to as the thermal effect of molecular vibration. This means that a large part of the absorption of optical energy in those spectral bands will convert into thermal energy, which eventually drives water content out of the polymer fibre and reduces the wavelength of POFBG. In this work we have investigated the wavelength stability of POFBGs in different circumstances. The experiment has shown that the characteristic wavelength of a POFBG starts decreasing after a light source is applied to it. This decrease continues until equilibrium inside the fibre is established, depending on the initial water content inside the fibre, the surrounding humidity, the optical power applied, and the fibre size. Our investigation has shown that POFBGs operating at around 850 nm show much smaller wavelength reduction than those operating at around 1550 nm in the same fibre; POFBGs with different diameters show different changes; POFBGs powered by a low level light source, or operating in a very dry environment are least affected by this thermal effect.

Short-term stability in refractive status despite large fluctuations in glucose levels in diabetes mellitus type 1 and 2

Purpose: This work investigates how short-term changes in blood glucose concentration affect the refractive components of the diabetic eye in patients with long-term Type 1 and Type 2 diabetes. Methods: Blood glucose concentration, refractive error components (mean spherical equivalent MSE, J0, J45), central corneal thickness (CCT), anterior chamber depth (ACD), crystalline lens thickness (LT), axial length (AL) and ocular aberrations were monitored at two-hourly intervals over a 12-hour period in: 20 T1DM patients (mean age ± SD) 38±14 years, baseline HbA1c 8.6±1.9%; 21 T2DM patients (mean age ± SD) 56±11 years, HbA1c 7.5±1.8%; and in 20 control subjects (mean age ± SD) 49±23 years, HbA1c 5.5±0.5%. The refractive and biometric results were compared with the corresponding changes in blood glucose concentration. Results: Blood glucose concentration at different times was found to vary significantly within (p<0.0005) and between groups (p<0.0005). However, the refractive error components and ocular aberrations were not found to alter significantly over the day in either the diabetic patients or the control subjects (p>0.05). Minor changes of marginal statistical or optical significance were observed in some biometric parameters. Similarly there were some marginally significant differences between the baseline biometric parameters of well-controlled and poorly-controlled diabetic subjects. Conclusion: This work suggests that normal, short-term fluctuations (of up to about 6 mM/l on a timescale of a few hours) in the blood glucose levels of diabetics are not usually associated with acute changes in refractive error or ocular wavefront aberrations. It is therefore possible that factors other than refractive error fluctuations are sometimes responsible for the transient visual problems often reported by diabetic patients. © 2012 Huntjens et al.

Protocol optimization for the mild detemplation of mesoporous silica nanoparticles resulting in enhanced texture and colloidal stability

Porosity development of mesostructured colloidal silica nanoparticles is related to the removal of the organic templates and co-templates which is often carried out by calcination at high temperatures, 500-600 °C. In this study a mild detemplation method based on the oxidative Fenton chemistry has been investigated. The Fenton reaction involves the generation of OH radicals following a redox Fe3+/Fe2+ cycle that is used as catalyst and H2O2 as oxidant source. Improved material properties are anticipated since the Fenton chemistry comprises milder conditions than calcination. However, the general application of this methodology is not straightforward due to limitations in the hydrothermal stability of the particular system under study. The objective of this work is three-fold: 1) reducing the residual Fe in the resulting solid as this can be detrimental for the application of the material, 2) shortening the reaction time by optimizing the reaction temperature to minimize possible particle agglomeration, and finally 3) investigating the structural and textural properties of the resulting material in comparison to the calcined counterparts. It appears that the Fenton detemplation can be optimized by shortening the reaction time significantly at low Fe concentration. The milder conditions of detemplation give rise to enhanced properties in terms of surface area, pore volume, structural preservation, low Fe residue and high degree of surface hydroxylation; the colloidal particles are stable during storage. A relative particle size increase, expressed as 0.11%·h-1, has been determined.

On the hydrothermal stability of MCM-41. Evidence of capillary tension-induced effects

MCM-41's limited hydrothermal stability has been often related to the hydrolysis of Si-O-Si bonds due to the low degree of condensation, its thin walls or a combination of them. In this work, evidence for an additional factor is provided; a physical effect that occurs during the drying of the hydrothermally treated calcined material due to the intense capillary stress exerted in water. Depending on both physical (i.e. mechanical) and chemical (i.e. hydrolysis) resistances, the structure undergoes differently. Three MCM-41 samples with different degree of condensation were investigated. The most remarkable results are found with un-aged TEOS based material, which gets fully disordered and shrunk for all applied hydrothermal temperatures in water. Comparison between water and a low-surface-tension-solvent drying revealed that capillarity is responsible for the loss of ordering (and shrinkage) at moderate hydrothermal temperatures. The material's structure is hexagonal and shrinkage-free under the low-surface-tension-solvent route. At a high hydrothermal temperature, hydrolysis is extensive and responsible for the loss of ordering. The other remarkable finding regards the aged MCM-41 mesostructure that maintains the hexagonal features at all applied temperatures in water, and it is more stable against capillarity at high temperature. The Na-metasilicate based material is mechanically very stable and gets disordered at high temperature due to hydrolysis.

On the stability of conventional and nano-structured carbon-based catalysts in the oxidative dehydrogenation of ethylbenzene under industrially relevant conditions

Relevant carbon-based materials, home-made carbon-silica hybrids, commercial activated carbon, and nanostructured multi-walled carbon nanotubes (MWCNT) were tested in the oxidative dehydrogenation of ethylbenzene (EB). Special attention was given to the reaction conditions, using a relatively concentrated EB feed (10 vol.% EB), and limited excess of O2 (O 2:EB = 0.6) in order to work at full oxygen conversion and consequently avoid O2 in the downstream processing and recycle streams. The temperature was varied between 425 and 475 °C, that is about 150-200 °C lower than that of the commercial steam dehydrogenation process. The stability was evaluated from runs of 60 h time on stream. Under the applied reactions conditions, all the carbon-based materials are apparently stable in the first 15 h time on stream. The effect of the gasification/burning was significantly visible only after this period where most of them fully decomposes. The carbon of the hybrids decomposes completely rendering the silica matrix and the activated carbon bed is fully consumed. Nano structured MWCNT is the most stable; the structure resists the demanding reaction conditions showing an EB conversion of ∼30% (but deactivating) with a steady selectivity of ∼80%. The catalyst stability under the ODH reaction conditions is predicted from the combustion apparent activation energies. © 2014 Elsevier Ltd. All rights reserved.