Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.

Effects of engine cooling water temperature on performance and exhaust emission characteristics of a multi-cylinder CI engine operated with Jatropha-Butanol blend

Renewable alternatives such as biofuels and optimisation of the engine operating parameters can enhance engine performance and reduce emissions. The temperature of the engine coolant is known to have significant influence on engine performance and emissions. Whereas much existing literature describes the effects of coolant temperature in engines using fossil derived fuels, very few studies have investigated these effects when biofuel is used as an alternative fuel. Jatropha oil is a non-edible biofuel which can substitute fossil diesel for compression ignition (CI) engine use. However, due to the high viscosity of Jatropha oil, technique such as transesterification, preheating the oil, mixing with other fuel is recommended for improved combustion and reduced emissions. In this study, Jatropha oil was blended separately with ethanol and butanol, at ratios of 80:20 and 70:30. The fuel properties of all four blends were measured and compared with diesel and jatropha oil. It was found that the 80% jatropha oil + 20% butanol blend was the most suitable alternative, as its properties were closest to that of diesel. A 2 cylinder Yanmar engine was used; the cooling water temperature was varied between 50°C and 95°C. In general, it was found that when the temperature of the cooling water was increased, the combustion process enhanced for both diesel and Jatropha-Butanol blend. The CO2 emissions for both diesel and biofuel blend were observed to increase with temperature. As a result CO, O2 and lambda values were observed to decrease when cooling water temperature increased. When the engine was operated using diesel, NOX emissions correlated in an opposite manner to smoke opacity; however, when the biofuel blend was used, NOX emissions and smoke opacity correlated in an identical manner. The brake thermal efficiencies were found to increase slightly as the temperature was increased. In contrast, for all fuels, the volumetric efficiency was observed to decrease as the coolant temperature was increased. Brake specific fuel consumption was observed to decrease as the temperature was increased and was higher on average when the biofuel was used, in comparison to diesel. The study concludes that the effects of engine coolant temperature on engine performance and emission characteristics differ between biofuel blend and fossil diesel operation. The coolant temperature needs to be optimised depending on the type of biofuel for optimum engine performance and reduced emissions.

Shaken not stirred:mixing semantics into XPDL

Ubiquitous computing requires lightweight approaches to coordinating tasks distributed across smart devices. We are currently developing a semantic workflow modelling approach that blends the proven robustness of XPDL with semantics to support proactive behaviour. We illustrate the potential of the model through an example based on mixing a dry martini.

Characterization and optimization of bilosomes for oral vaccine delivery

Oral vaccines offer significant benefits due to the ease of administration, better patient compliance and non-invasive, needle-free administration. However, this route is marred by the harsh gastro intestinal environment which is detrimental to many vaccine formats. To address this, a range of delivery systems have been considered including bilosomes; these are bilayer vesicles constructed from non-ionic surfactants combined with the inclusion of bile salts which can stabilize the vesicles in the gastro intestinal tract by preventing membrane destabilization. The aim of this study was to investigate the effect of formulation parameters on bilosome carriers using Design of Experiments to select an appropriate formulation to assess in vivo. Bilosomes were constructed from monopalmitoylglycerol, cholesterol, dicetyl phosphate and sodium deoxycholate at different blends ratios. The optimized bilosome formulation was identified and the potential of this formulation as an oral vaccine delivery system were assessed in biodistribution and vaccine efficacy studies. Results showed that the larger bilosomes vesicles (~6 µm versus 2 µm in diameter) increased uptake within the Peyer's patches and were able to reduce median temperature differential change and promote a reduction in viral cell load in an influenza challenge study. © 2013 Informa UK, Ltd.

Potential for broad range multiplexing of fibre Bragg gratings in polymer optical fibres and operation in the 700-nm wavelength range

Refractive index and structural characteristics of optical polymers are strongly influenced by the thermal history of the material. Polymer optical fibres (POF) are drawn under tension, resulting in axial orientation of the polymer molecular chains due to their susceptibility to align in the fibre direction. This change in orientation from the drawing process results in residual strain in the fibre and also affects the transparency and birefringence of the material (1-3). PMMA POF has failure strain as high as over 100%. POF has to be drawn under low tension to achieve this value. The drawing tension affects the magnitude of molecular alignment along the fibre axis, thus affecting the failure strain. The higher the tension the lower the failure stain will be. However, the properties of fibre drawn under high tension can approach that of fibre drawn under low tension by means of an annealing process. Annealing the fibre can generally optimise the performance of POF while keeping most advantages intact. Annealing procedures can reduce index difference throughout the bulk and also reduce residual stress that may cause fracture or distortion. POF can be annealed at temperatures approaching the glass transition temperature (Tg) of the polymer to produce FBG with a permanent blue Bragg wave-length shift at room temperature. At this elevated temperature segmental motion in the structure results in a lower viscosity. The material softens and the molecular chains relax from the axial orientation causing shrinking of the fibre. The large attenuation of typically 1dB/cm in the 1550nm spectral region of PMMA POF has limited FBG lengths to less than 10cm. The more expensive fluorinated polymers with lower absorption have had no success as FBG waveguides. Bragg grating have been inscribed onto various POF in the 800nm spectral region using a 30mW continuous wave 325nm helium cadmium laser, with a much reduced attenuation coefficient of 10dB/m (5). Fabricating multiplexed FBGs in the 800nm spectral region in TOPAS and PMMA POF consistently has lead to fabrication of multiplexed FBG in the 700nm spectral region by a method of prolonged annealing. The Bragg wavelength shift of gratings fabricated in PMMA fibre at 833nm and 867nm was monitored whilst the POF was thermally annealed at 80°C. Permanent shifts exceeding 80nm into the 700nm spectral region was attained by both gratings on the fibre. The large permanent shift creates the possibility of multiplexed Bragg sensors operating over a broad range. -------------------------------------------------------------------------------------------------------------------- 1. Pellerin C, Prud'homme RE, Pézolet M. Effect of thermal history on the molecular orientation in polystyrene/poly (vinyl methyl ether) blends. Polymer. 2003;44(11):3291-7. 2. Dvoránek L, Machová L, Šorm M, Pelzbauer Z, Švantner J, Kubánek V. Effects of drawing conditions on the properties of optical fibers made from polystyrene and poly (methyl methacrylate). Die Angewandte Makromolekulare Chemie. 1990;174(1):25-39. 3. Dugas J, Pierrejean I, Farenc J, Peichot JP. Birefringence and internal stress in polystyrene optical fibers. Applied optics. 1994;33(16):3545-8. 4. Jiang C, Kuzyk MG, Ding JL, Johns WE, Welker DJ. Fabrication and mechanical behavior of dye-doped polymer optical fiber. Journal of applied physics. 2002;92(1):4-12. 5. Johnson IP, Webb DJ, Kalli K, Yuan W, Stefani A, Nielsen K, et al., editors. Polymer PCF Bragg grating sensors based on poly (methyl methacrylate) and TOPAS cyclic olefin copolymer2011: SPIE.

Thermal degradation of a brominated bisphenol a derivative

The thermal degradation of 2,6,2',6'-tetrabromo-4,4-pm-isoproylidene-di phenol (tetrabromobisphenol A) (TBBPA) has been investigated and a mechanism for its thermal degradation is suggested. TBBPA is a comonomer widely used in epoxy and in unsaturated polyester resins to impart fire retardance. These resins find a common use in electric and electronic equipment. The presence of bromine atoms is the key factor in fire retardant activity, while on the other hand it represents an ecological problem when pyrolytic recycling is programmed at the end of the useful life of such items. However, pyrolysis is the more advantageous recycling system for thermosetting resins and thus efforts should be made to control the pyrolysis in order to avoid or minimize the development of toxics. Homolytic scission of the aromatic bromine and condensation of aromatic bromine with phenolic hydroxyl are the main processes occuring in the range 270-340°C. A large amount of charred residue is left as a consequence of condensation reactions. HBr and brominated phenols and bisphenols are the main volatile products formed. Brominated dibenzodioxins structures are included in the charred residue and not evolved in the volatile phases.

Phenols and aromatic amines as thermal stabilizers in polyolefin processing

Scavenging of C- and O-centered free radicals is mandatory in processing stabilization of polypropylene. Phenolic antioxidants act principally as O-radical scavengers only. Aromatic amines, N,N'-disubstituted 1,4-phenylenediamines (PD) and 4,4'disubstituted diphenylamines (DPA), scavenge both C- and O-centered radicals and have consequently a broader activity spectrum. PD cannot be used, however, in polypropylene because of formation of strongly discoloring and staining sacrificial transformation products. Such products formed from DPA have even more discoloring properties. A good processing stability and acceptable extent of discoloration can be achieved by blends of phenols with 4,4'-di-tert.octyl DPA. The effect is considered as a beneficial cooperation between the two chain-breaking antioxidants involving interactions with amine-based transformation products.

Energy production from biomass and waste derived intermediate pyrolysis oils

This study investigates the use of Pyroformer intermediate pyrolysis system to produce alternative diesel engines fuels (pyrolysis oil) from various biomass and waste feedstocks and the application of these pyrolysis oils in a diesel engine generating system for Combined Heat and Power (CHP) production. The pyrolysis oils were produced in a pilot-scale (20 kg/h) intermediate pyrolysis system. Comprehensive characterisations, with a view to use as engine fuels, were carried out on the sewage sludge and de-inking sludge derived pyrolysis oils. They were both found to be able to provide sufficient heat for fuelling a diesel engine. The pyrolysis oils also presented poor combustibility and high carbon deposition, but these problems could be mitigated by means of blending the pyrolysis oils with biodiesel (derived from waste cooking oil). The blends of SSPO (sewage sludge pyrolysis oil) and biodiesel (30/70 and 50/50 in volumetric ratios) were tested in a 15 kWe Lister type stationary generating system for up to 10 hours. There was no apparent deterioration observed in engine operation. With 30% SSPO blended into biodiesel, the engine presents better overall performance (electric efficiency), fuel consumption, and overall exhaust emissions than with 50% SSPO blend. An overall system analysis was carried out on a proposed integrated Pyroformer-CHP system. Combined with real experimental results, this was used for evaluating the costs for producing heat and power and char from wood pellets and sewage sludge. It is concluded that the overall system efficiencies for both types of plant can be over 40%; however the integrated CHP system is not economically viable. This is due to extraordinary project capital investment required.

Understanding the labour–environmental relationship in Britain, 1967–2011:a new narrative using political opportunity structure and coalition theory

Orthodox depictions of a fraught labour–environmental relationship privileging class, ideological and programmatic differences are problematised by newly quantified evidence of British unions' pro-environmental policy-making since 1967. The following narrative blends widely accepted accounts of the fortunes of both movements with an evaluation of Britain's shifting political opportunity structure and coalition theory to identify an alternative range of constraints and opportunities influencing the propensity and capacity of both movements to interact effectively, culminating recently in unions' emergence as environmental actors in their own right.

Fullerene-capped copolymers for bulk heterojunctions: device stability and efficiency improvements

A fullerene end-capped polymer-compatibilizer based on poly(3-hexylthiophene) (P3HT) was synthesized and demonstrated to have a remarkable effect on both the stability and efficiency of devices made from exemplar P3HT and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). P3HT with ethynyl chain-ends and α-azido-ω-bromo-PS were prepared via Grignard metathesis (GRIM) and atom transfer radical polymerisation, respectively. “Click” chemistry resulted in the preparation of poly(3-hexylthiophene)-block-ω-bromo-polystyrene (P3HT-b-PS-Br), and subsequent atom transfer radical addition chemistry with fullerene (C60) yielded the donor–acceptor block copolymer P3HT-b-PS-C60. Both P3HT-b-PS-Br and P3HT-b-PS-C60 were considered as compatibilizers with P3HT/PCBM blends, with the study detailing effects on active-layer morphology, device efficiency and stability. When used at low concentrations, both P3HT-b-PS-Br (1%) and P3HT-b-PS-C60 (0.5%) resulted in considerable 28% and 35% increases in efficiencies with respect to devices made from P3HT/PCBM alone. Furthermore, P3HT-b-PS-C60 (0.5%) resulted in an important improvement in device stability.

Combustion and emission characteristics of a typical biodiesel engine operated on waste cooking oil derived biodiesel

Waste cooking oils can be converted into fuels to provide economical and environmental benefits. One option is to use such fuels in stationary engines for electricity generation, co-generation or tri-generation application. In this study, biodiesel derived from waste cooking oil was tested in an indirect injection type 3-cylinder Lister Petter biodiesel engine. We compared the combustion and emission characteristics with that of fossil diesel operation. The physical and chemical properties of pure biodiesel (B100) and its blends (20% and 60% vol.) were measured and compared with those of diesel. With pure biodiesel fuel, full engine power was achieved and the cylinder gas pressure diagram showed stable operation. At full load, peak cylinder pressure of B100 operation was almost similar to diesel and peak burn rate of combustion was about 13% higher than diesel. For biodiesel operation, occurrences of peak burn rates were delayed compared to diesel. Fuel line injection pressure was increased by 8.5-14.5% at all loads. In comparison to diesel, the start of combustion was delayed and 90% combustion occurred earlier. At full load, the total combustion duration of B100 operation was almost 16% lower than diesel. Biodiesel exhaust gas emissions contained 3% higher CO2 and 4% lower NOx, as compared to diesel. CO emissions were similar at low load condition, but were decreased by 15 times at full load. Oxygen emission decreased by around 1.5%. Exhaust gas temperatures were almost similar for both biodiesel and diesel operation. At full engine load, the brake specific fuel consumption (on a volume basis) and brake thermal efficiency were respectively about 2.5% and 5% higher compared to diesel. Full engine power was achieved with both blends, and little difference in engine performance and emission results were observed between 20% and 60% blends. The study concludes that biodiesel derived from waste cooking oil gave better efficiency and lower NOx emissions than standard diesel. Copyright © 2012 SAE International.

Grewia gum 2:mucoadhesive properties of compacts and gels

Purpose: To compare the mucoadhesive performance of grewia polysaccharide gum with those of guar gum, carboxymethylcellulose, hydroxypropyl methylcellulose and carbopol 971P. Methods: Grewia polysaccharide gum compacts or gels as well as those of guar gum, carboxymethylcellulose, hydroxypropyl methylcellulose or carbopol 971P were prepared. Texturometric and tensile analysis of the polymer gels and compacts were carried out using a software-controlled penetrometre, TA.XTPlus texture analyzer. The polymer gels were evaluated for hardness, stickiness, work of cohesion and work of adhesion. Furthermore, the detachment force of the polymer compacts from a mucin substrate was evaluated. Results: The work of adhesion of guar gels was significantly greater than that of grewia gels (p < 0.001) but the latter showed a significantly greater work of adhesion than carboxymethylcellulose gels (p < 0.05) and hydroxypropyl methylcellulose gels (p < 0.001). However, the work of cohesion for grewia/mucin gel mixture was significantly greater (p < 0.001) than those of carboxymethylcellulose/mucin, hydroxypropyl methylcellulose/mucin and carbopol 971P/mucin gel blends. The difference between the mucoadhesive performance of grewia compacts and those of hydroxypropyl methylcellulose and carbopol 971P compacts was insignificant (p > 0.05). Conclusion: Grewia polysaccharide gum demonstrated good mucoadhesive properties, comparable to those of carbopol 971P, carboxymethylcellulose, guar gum and hydroxypropyl methylcellulose, and therefore, should be suitable for the formulation of retentive drug delivery devices. © Pharmacotherapy Group, Faculty of Pharmacy, University of Benin, Benin City.

The development of a sustainable agricultural industry through the application of biochar and pyroligneous acid

This paper marks the first in a series of studies into the potential use of pyrolysis products in the development of more sustainable practices within the agricultural industry. In this study, the immediate benefits of the application of biochar to crop yields of Raphanus sativus (radishes) are assessed. Furthermore, the study reports on the preliminary findings into the potential application of pyroligneous acid (wood vinegar) as a biocidal agent against crop disease. Although germination tests undertaken on biochar/compost blends of up to 1: 2, by weight, showed no significant adverse effect from the addition of the nutrient rich carbonaceous solid, evidence of substantial increases in crop yield through the addition of biochar were not observed. In sharp contrast, zones of inhibition were observed at 3-10 vol. % upon application of pyroligneous acid to two causal agents responsible for certain diseases in vegetable and fruit crops, i.e. Rhizobium radiobacter (agrobacterium tumefaciens) and Xanthomonas campestris, highlighting the versatility in the application of pyrolysis products and avenues for exploration in the development of this biomass conversion technology.

CO2 absorption into aqueous amine blended solutions containing monoethanolamine (MEA), N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) for post-combustion capture processes

Presently monoethanolamine (MEA) remains the industrial standard solvent for CO2 capture processes. Operating issues relating to corrosion and degradation of MEA at high temperatures and concentrations, and in the presence of oxygen, in a traditional PCC process, have introduced the requisite for higher quality and costly stainless steels in the construction of capture equipment and the use of oxygen scavengers and corrosion inhibitors. While capture processes employing MEA have improved significantly in recent times there is a continued attraction towards alternative solvents systems which offer even more improvements. This movement includes aqueous amine blends which are gaining momentum as new generation solvents for CO2 capture processes. Given the exhaustive array of amines available to date endless opportunities exist to tune and tailor a solvent to deliver specific performance and physical properties in line with a desired capture process. The current work is focussed on the rationalisation of CO2 absorption behaviour in a series of aqueous amine blends incorporating monoethanolamine, N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) as solvent components. Mass transfer/kinetic measurements have been performed using a wetted wall column (WWC) contactor at 40°C for a series of blends in which the blend properties including amine concentration, blend ratio, and CO2 loadings from 0.0-0.4 (moles CO2/total moles amine) were systematically varied and assessed. Equilibrium CO2 solubility in each of the blends has been estimated using a software tool developed in Matlab for the prediction of vapour liquid equilibrium using a combination of the known chemical equilibrium reactions and constants for the individual amine components which have been combined into a blend.From the CO2 mass transfer data the largest absorption rates were observed in blends containing 3M MEA/3M Am2 while the selection of the Am2 component had only a marginal impact on mass transfer rates. Overall, CO2 mass transfer in the fastest blends containing 3M MEA/3M Am2 was found to be only slightly lower than a 5M MEA solution at similar temperatures and CO2 loadings. In terms of equilibrium behaviour a slight decrease in the absorption capacity (moles CO2/mole amine) with increasing Am2 concentration in the blends with MEA was observed while cyclic capacity followed the opposite trend. Significant increases in cyclic capacity (26-111%) were observed in all blends when compared to MEA solutions at similar temperatures and total amine concentrations. In view of the reasonable compromise between CO2 absorption rate and capacity a blend containing 3M MEA and 3M AMP as blend components would represent a reasonable alternative in replacement of 5M MEA as a standalone solvent.

Identification of the degradation mechanisms of organic solar cells:active layer and interfacial layers

Organic Solar Cells (OSCs) represent a photovoltaic technology with multiple interesting application properties. However, the establishment of this technology into the market is subject to the achievement of operational lifetimes appropriate to their application purposes. Thus, comprehensive understanding of the degradation mechanisms occurring in OSCs is mandatory in both selecting more intrinsically stable components and/or device architectures and implementing strategies that mitigate the encountered stability issues. Inverted devices can suffer from mechanical stress and delamination at the interface between the active layer, e.g. poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM), and the hole transport layer, e.g. poly(3,4-ethylenedioxythiophene):poly(p-styrene sulfonate) (PEDOT:PSS). This work proposes the incorporation of a thin adhesive interlayer, consisting of a diblock copolymer composed of a P3HT block and a thermally-triggerable, alkyl-protected PSS block. In this context, the synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) with controlled molar mass and low dispersity (Ð ≤ 1.50) via Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisation has been extensively studied. Subsequently, Atomic Force Microscopy (AFM) was explored to characterise the thermal deprotection of P3HT-b-PNSS thin layers to yield amphiphilic P3HT-b-PSS, indicating that surface deprotection prior to thermal treatment could occur. Finally, structural variation of the alkyl protecting group in PSS allowed reducing the thermal treatment duration from 3 hours (P3HT-b-PNSS) to 45 minutes for the poly(isobutyl p-styrene sulfonate) (PiBSS) analogous copolymer. Another critical issue regarding the stability of OSCs is the sunlight-driven chemical degradation of the active layer. In the study herein, the combination of experimental techniques and theoretical calculations has allowed identification of the structural weaknesses of poly[(4,4’- bis(2-ethylhexyl) dithieno [3,2-b:2’,3’-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5’-diyl], Si-PCPDTBT, upon photochemical treatment in air. Additionally, the study of the relative photodegradation rates in air of a series of polymers with systematically modified backbones and/or alkyl side chains has shown no direct correlation between chemical structure and stability. It is proposed instead that photostability is highly dependent on the crystalline character of the deposited films. Furthermore, it was verified that photostability of blends based on these polymers is dictated by the (de)stabilising effect that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has over each polymer. Finally, a multiscale analysis on the degradation of solar cells based on poly[4,4' bis(2- ethylhexyl) dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-[2,5 bis(3 tetradecylthiophen 2-yl)thiazole[5,4-d]thiazole)-1,8-diyl] and PCBM, indicated that by judicious selection of device layers, architectures, and encapsulation materials, operational lifetimes up to 3.3 years with no efficiency losses can be successfully achieved.