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.

Characterisation of the plasma membrane subproteome of bloodstream form Trypanosoma brucei

Proteome analysis by conventional approaches is biased against hydrophobic membrane proteins, many of which are also of low abundance. We have isolated plasma membrane sheets from bloodstream forms of Trypanosoma brucei by subcellular fractionation, and then applied a battery of complementary protein separation and identification techniques to identify a large number of proteins in this fraction. The results of these analyses have been combined to generate a subproteome for the pellicular plasma membrane of bloodstream forms of T. brucei as well as a separate subproteome for the pellicular cytoskeleton. In parallel, we have used in silico approaches to predict the relative abundance of proteins potentially expressed by bloodstream form trypanosomes, and to identify likely polytopic membrane proteins, providing quality control for the experimentally defined plasma membrane subproteome. We show that the application of multiple high-resolution proteomic techniques to an enriched organelle fraction is a valuable approach for the characterisation of relatively intractable membrane proteomes. We present here the most complete analysis of a protozoan plasma membrane proteome to date and show the presence of a large number of integral membrane proteins, including 11 nucleoside/nucleobase transporters, 15 ion pumps and channels and a large number of adenylate cyclases hitherto listed as putative proteins.

Fast pyrolysis of biomass in a circulating fluidised bed reactor

The objective of this work was to design, construct, test and operate a novel circulating fluid bed fast pyrolysis reactor system for production of liquids from biomass. The novelty lies in incorporating an integral char combustor to provide autothermal operation. A reactor design methodology was devised which correlated input parameters to process variables, namely temperature, heat transfer and gas/vapour residence time, for both the char combustor and biomass pyrolyser. From this methodology a CFB reactor was designed with integral char combustion for 10 kg/h biomass throughput. A full-scale cold model of the CFB unit was constructed and tested to derive suitable hydrodynamic relationships and performance constraints. Early difficulties encountered with poor solids circulation and inefficient product recovery were overcome by a series of modifications. A total of 11 runs in a pyrolysis mode were carried out with a maximum total liquids yield of 61.50% wt on a maf biomass basis, obtained at 500°C and with 0.46 s gas/vapour residence time. This could be improved by improved vapour recovery by direct quenching up to an anticipated 75 % wt on a moisture-and-ash-free biomass basis. The reactor provides a very high specific throughput of 1.12 - 1.48 kg/hm2 and the lowest gas-to-feed ratio of 1.3 - 1.9 kg gas/kg feed compared to other fast pyrolysis processes based on pneumatic reactors and has a good scale-up potential. These features should provide significant capital cost reduction. Results to date suggest that the process is limited by the extent of char combustion. Future work will address resizing of the char combustor to increase overall system capacity, improvement in solid separation and substantially better liquid recovery. Extended testing will provide better evaluation of steady state operation and provide data for process simulation and reactor modeling.

Intumescent formulations incorporating melamine phosphate

Once familiar with the fire test rig constructed by M Kay, and modified to allow incorporation of both video and computer facilities, Melamine Phosphate production was scaled up from small to large laboratory scale, and then commercial scale production was considered. Samples produced at each stage were compared analytically, visually and in fire testing. The separation and drying stages on a commercial scale lay unresolved practically, due to lack of test facilities. Different cure regimes for the Araldite MY753 and Versamid system were investigated along with weathering tests and cured samples. Surface priming is suggested for large scale application, though on a small scale a clean unprimed surface was thought sufficient. Some samples heat, aired, cracked at the edges but remained bonded on fire testing. An intumescent sample containing Melamine Phosphate, Araldite and Versamid could not be applied to a vertical surface successfully, the viscosity had to be increased to allow application and curing, various additives were tested, two successful ones being fumed silica and a solvent, isopropanol. The low percentages fumed silica used was incorporated into the sample and the viscosity and fire test results compared with a `standard sample'. An expanding graphite incorporated into a standard sample made mixing and application increasingly difficult, due to the lubricating affect of graphite, but the char produced was a good quality, stable char. A suitable formulation could now be mixed, applied and cured, and assuming no adverse interaction between the additives would protect the sample in the event of a fire.

Ablative pyrolysis of biomass

The primary objectives of this work were to design, construct, test and operate a novel ablative pyrolysis reactor and product recovery system. Other key objectives included the development of an ablative pyrolysis reactor design methodology, mathematical modelling of the ablation process and measurement of empirical ablation rate data at 500°C. The constructed reactor utilised a rotating blade approach to achieve particle ablation in a 258mm internal diameter reactor. By fulfilling the key requirements of high relative motion and high contact pressure, pine wood particles of maximum size 6.35 mm were successfully ablated.Sixteen experiments were carried out: five initial commissioning experiments were used to test the rotating blade concept and to solve char separation problems. Mass balances were obtained for the other eleven experiments with good closures. Based on ablatively pyrolysed dry wood, a maximum organic liquid yield of 65.9 wt% was achieved with corresponding yields of 12.4 wt% char, 11.5 wt% water and 9.2 wt% non-condensable gas. Reactor throughputs of 2 kg/h dry ablated wood were achieved at 600°C. The theoretical ablative pyrolysis reactor design methodology was simplified and improved based upon empirical data derived from wood rod ablation experiments. Yields of chemicals were qualitatively similar to those of other fast pyrolysis processes.The product recovery system, comprising hot char removal, liquids collection in two ice-cooled condensers followed by gas filtration and drying, gave good mass balance closures. The most significant problem was char separation and removal from the reactor. This was solved by using a nitrogen blow line. In general, the reactor and product collection systems performed well.Future development of the reactor would involve modification of the reactor feed tube to allow the reactor residence time to be reduced and testing of the rotating blade approach with different blade angles, configurations and numbers of blades.

Oxidation studies of a novel barrier polymer system

The thermal oxidation of two model compounds representing the aromatic polyamide, MXD6 (poly m-xylylene adipamide) have been investigated. The model compounds (having different chemical structures, viz, one corresponding to the aromatic part of the chain and the other to the aliphatic part), based on the structure of MXD6 were prepared and reactions with different concentrations of cobalt ions examined with the aim of identifying the role of the different structural components of MXD6 on the mechanism of oxidation. The study showed that cobalt, in the presence of sodium phosphite (which acts as an antioxidant for MXD6 and the model compounds), increases the oxidation of the model compounds. It is believed that the cobalt acts predominantly as a catalyst for the decomposition of hydroperoxides, formed during oxidation of the models in the melt phase, to free radical products and to a lesser extent as a catalyst for the initiation of the oxidation reaction by complex formation with the amide, which is more likely to take place in the solid phase. An oxidation cycle has been proposed consisting of two parts both of which will occur, to some extent under all conditions of oxidation (in the melt and in the solid phase), but their individual predominance must be determined by the prevailing oxygen pressure at the reaction site. The different aspects of this proposed mechanism were examined from extensive model compound studies, and the evidence based on the nature of product formation and the kinetics of these reactions. Main techniques used to compare the rates of oxidation and the study of kinetics included, oxygen absorption, FT-IR, UV and TGA. HPLC was used for product separation and identification.

Smart microsystems for cell manipulations

This thesis documents the design, manufacture and testing of a passive and non-invasive micro-scale planar particle-from-fluid filter for segregating cell types from a homogeneous suspension. The microfluidics system can be used to separate spermatogenic cells from testis biopsy samples, providing a mechanism for filtrate retrieval for assisted reproduction therapy. The system can also be used for point-of-service diagnostics applications for hospitals, lab-on-a-chip pre-processing and field applications such as clinical testing in the third world. Various design concepts are developed and manufactured, and are assessed based on etched structure morphology, robustness to variations in the manufacturing process, and design impacts on fluid flow and particle separation characteristics. Segregation was measured using image processing algorithms that demonstrate efficiency is more than 55% for 1 µl volumes at populations exceeding 1 x 107. the technique supports a significant reduction in time over conventional processing, in the separation and identification of particle groups, offering a potential reduction in the associated cost of the targeted procedure. The thesis has developed a model of quasi-steady wetting flow within the micro channel and identifies the forces across the system during post-wetting equalisation. The model and its underlying assumptions are validated empirically in microfabricated test structures through a novel Micro-Particle Image Velocimetry technique. The prototype devices do not require ancillary equipment nor additional filtration media, and therefore offer fewer opportunities for sample contamination over conventional processing methods. The devices are disposable with minimal reagent volumes and process waste. Optimal processing parameters and production methods are identified with any improvements that could be made to enhance their performance in a number of identified potential applications.

Psychophysical investigations of human peripheral vision

This thesis investigates various aspects of peripheral vision, which is known not to be as acute as vision at the point of fixation. Differences between foveal and peripheral vision are generally thought to be of a quantitative rather than a qualitative nature. However, the rate of decline in sensitivity between foveal and peripheral vision is known to be task dependent and the mechanisms underlying the differences are not yet well understood. Several experiments described here have employed a psychophysical technique referred to as 'spatial scaling'. Thresholds are determined at several eccentricities for ranges of stimuli which are magnified versions of one another. Using this methodology a parameter called the E2 value is determined, which defines the eccentricity at which stimulus size must double in order to maintain performance equivalent to that at the fovea. Experiments of this type have evaluated the eccentricity dependencies of detection tasks (kinetic and static presentation of a differential light stimulus), resolution tasks (bar orientation discrimination in the presence of flanking stimuli, word recognition and reading performance), and relative localisation tasks (curvature detection and discrimination). Most tasks could be made equal across the visual field by appropriate magnification. E2 values are found to vary widely dependent on the task, and possible reasons for such variations are discussed. The dependence of positional acuity thresholds on stimulus eccentricity, separation and spatial scale parameters is also examined. The relevance of each factor in producing 'Weber's law' for position can be determined from the results.

Spatial tuning studies of the pattern evoked electroretinogram

The locus of origin of the pattern evoked electroretinogram, (PERG), has been the subject of considerable discussion. A novel approach was adopted in this study to further elaborate the nature of the PERG evoked by pattern onset/offset presentation. The PERG was found to be linearly related to stimulus contrast and in particular was linearly related to the temporal contrast of the retinal image, when elicited by patterns of low spatial frequency. At high spatial frequencies the retinal image contrast is significantly reduced because of optical degradation. This is described by the eye's modulation transfer function (MTF). The retinal contrast of square wave grating and chequerboard patterns of increasing spatial frequency were found by filtering their Fourier transforms by the MTF. The filtered pattern harmonics were then resynthesised to constitute a profile of retinal image illuminance from which the temporal and spatial contrast of the image could be calculated. If the PERG is a pure illuminance response it should be spatially insensitive and dependent upon the temporal contrast of stimulation. The calculated loss of temporal contrast for finer patterns was expressed as a space-averaged temporal contrast attentuation factor. This factor, applied to PERGs evoked by low spatial frequency patterns, was used to predict the retinal illuminance response elicited by a finer pattern. The predicted response was subtracted from the recorded signal and residual waveform was proposed to represent specific activity. An additional correction for the attenuation of spatial contrast was applied to the extracted pattern specific response. Pattern specific responses computed for different spatial frequency patterns in this way are the predicted result of iso-contrast pattern stimulation. The pattern specific responses demonstrate a striking bandpass spatial selectivity which peaks at higher spatial frequencies in the more central retina. The variation of spatial sensitivity with eccentricity corresponds closely with estimated ganglion receptive field centre separation and psychophysical data. The variation of retinal structure with eccentricity, in the form of the volumes of the nuclear layers, was compared with the amplitudes of the computed retinal illuminance and pattern specific responses. The retinal illuminance response corresponds more closely to the outer and inner nuclear layers whilst the pattern specific response appears more closely related to the ganglion cell layer. In general the negative response transients correspond to the more proximal retinal layers. This thesis therefore supports the proposed contribution of proximal retinal cell activity to the PERG and describes techniques which may be further elaborated for more detailed studies of retinal receptive field dimensions.

Investigations into visual hyperacuity

Visual hyperacuities.are a group of thresholds whose values surpass that expected by the anatomical and optical constraints of the eye. There are many variables which affect hyperacuities of which this thesis considers the following .. 1. The effect of contrast on displacement detection and bisection acuity. It is proposed that spatial summation may account for the different response of these two hyperacuities compared with the contrast response of vernier acuity. 2. The effect of references on displacement detection. These were shown to greatly enhance performance when present. Their effect was, however, dependent upon the temporal characteristics of the displacement. 3. The effect of spatial frequency on vernier acuity. Evidence from this experiment suggests that vernier performance can be explained on the basis of the output of orientationally selective spatial frequency filters. 4. Evidence for a weighting function for visual location using random dot clusters. The weighting attached to different parts of the retinal light distribution was found to alter non-linearly with increasing offset from the geometric center of the cluster. A relationship between dot density and peak amplitude of the weighting function was found. 5. Spatial scaling of vernier acuity in the peripheral field. With careful choice of a technique which did not allow separation and eccentricity to co-vary it was found possible to scale vernier acuity both for two lines and two separated dots. 6. The effect of increasing age on hyperacuity. No change in vernier acuity with age was found which contrasted with displacement detection and bisection acuity both of which showed a significant decline with increasing age.

Product innovation in a medium size mature manufacturing company

This thesis is concerned with the management of product innovation inside the medium size, mature, manufacturing company. An academic perspective of innovation is integrated with an account of direct participation acquired over a two year period. The emergent synthesis provides fresh insight into some of the problems associated with producing and sustaining innovation. Product innovation is a very complex activity, and it presents particular difficulties for mature industry. However, the ability to innovate is fundamental to a company's continued survival. Three aspects of product innovation are examined in detail. Firstly, is the requirement to separate innovation activity from the on-going business interests; dependency between the degree of separation and novelty is supported. Secondly, a simple sequential model of the innovation process is tested and shown to be of considerable practical value. Thirdly a relationship is established between the age of the recipient market and the type of innovation to be found in that market All three aspects are found to have important implications for management in their pursuit of innovation. Management deficiencies which inhibited the successful resolution of innovation-linked problems are described and solutions which stress the need for commitment and coherency are proposed. The long existing management structure in the mature company which mitigates against successful and continuing innovation are examined in detail and a strategy is evolved which uses the intrinsic strengths of the mature company to promote innovation of a kind compatible with success in the market. A set of guidelines of practical value is presented for those managers wishing to pursue, and sustain, product innovation in the medium size mature company.

A solar-powered reverse osmosis system for high recovery of freshwater from saline groundwater

Desalination of groundwater is essential in arid regions that are remote from both seawater and freshwater resources. Desirable features of a groundwater desalination system include a high recovery ratio, operation from a sustainable energy source such as solar, and high water output per unit of energy and land. Here we propose a new system that uses a solar-Rankine cycle to drive reverse osmosis (RO). The working fluid such as steam is expanded against a power piston that actuates a pump piston which in turn pressurises the saline water thus passing it through RO membranes. A reciprocating crank mechanism is used to equalise the forces between the two pistons. The choice of batch mode in preference to continuous flow permits maximum energy recovery and minimal concentration polarisation in the vicinity of the RO membrane. This study analyses the sizing and efficiency of the crank mechanism, quantifies energy losses in the RO separation and predicts the overall performance. For example, a system using a field of linear Fresnel collectors occupying 1000 m2 of land and raising steam at 200 °C and 15.5 bar could desalinate 350 m3/day from saline water containing 5000 ppm of sodium chloride with a recovery ratio of 0.7.

HTHP syngas cleaning concept of two stage biomass gasification for FT synthesis

The EU intends to increase the fraction of fuels from biogenic energy sources from 2% in 2005 to 8% in 2020. This means a minimum of 30 million TOE/a of fuels from biomass. This makes technical-scale generation of syngas from high-grade biomass, e.g. straw, hay, bark, or paper/cardboard waste, and the production of synthetic fuels by Fischer-Tropsch (FT) synthesis highly attractive. The BTL concept (Biomass to Liquids) of the Karlsruhe Research Center, labeled bioliq, focuses on this challenge by locally concentrating the biomass energy content by fast pyrolysis in a coke/oil slurry followed by slurry conversion to syngas in a central entrained flow gasifier at 1200C and pressures above 4MPa. FT synthesis generates intermediate products for synthetic fuels. To prevent the sensitive catalysts from being poisoned the syngas must be free of tar and particulates. Trace concentrations of H2S, COS, CS2, HCl, NH3, and HCN must be on the order of a few ppb. Moreover, maximum conversion efficiency will be achieved by cleaning the gas above the synthesis conditions. (T>350C, P>4MPa). The concept of an innovative dry HTHP syngas cleaning process is presented. Based on HT particle filtration and suitable sorption and catalysis processes for the relevant contaminants, an overall concept will be derived, which leads to a syngas quality required for FT synthesis in only two combined stages. Results of filtration experiments on a pilot scale are presented. The influence of temperature on the separation and conversion, respectively, of particulates and gaseous contaminants is discussed on the basis of experimental results obtained on a laboratory and pilot scale. Extensive studies of this concept are performed in a scientific network comprising the Karlsruhe Research Center and five universities; funding is provided by the Helmholtz Association of National Research Centers in Germany.

Surfactant-free purification of membrane proteins with intact native membrane environment

In order to study the structure and function of a protein, it is generally required that the protein in question is purified away from all others. For soluble proteins, this process is greatly aided by the lack of any restriction on the free and independent diffusion of individual protein particles in three dimensions. This is not the case for membrane proteins, as the membrane itself forms a continuum that joins the proteins within the membrane with one another. It is therefore essential that the membrane is disrupted in order to allow separation and hence purification of membrane proteins. In the present review, we examine recent advances in the methods employed to separate membrane proteins before purification. These approaches move away from solubilization methods based on the use of small surfactants, which have been shown to suffer from significant practical problems. Instead, the present review focuses on methods that stem from the field of nanotechnology and use a range of reagents that fragment the membrane into nanometre-scale particles containing the protein complete with the local membrane environment. In particular, we examine a method employing the amphipathic polymer poly(styrene-co-maleic acid), which is able to reversibly encapsulate the membrane protein in a 10 nm disc-like structure ideally suited to purification and further biochemical study.

Hierarchical nanoporous solid base catalysts for biofuels

Novel macroporous solid bases have been developed as alternative clean technologies to existing commercial homogeneous catalysts for the production of biodiesel from triglycerides; the latter suffer process disadvantages including complex separation and associated saponification and engine corrosion, and are unsuitable for continuous operation. To this end, tuneable macroporous MgAl hydrotalcites have been prepared by an alkali-free route and characterised by TGA, XRD, SEM and XPS. The macropore architecture improves diffusion of bulky triglyceride molecules to the active base sites, increasing activity. Lamellar and macroporous hydrotalcites will be compared for the transesterification of both model and plant oil feedstocks, and structure-reactivity relations identified.