Comparison of the effect of pre-treatment and catalysts on liquid quality from fast pyrolysis of biomass

The overall objective of this work was to compare the effect of pre-treatment and catalysts on the quality of liquid products from fast pyrolysis of biomass. This study investigated the upgrading of bio-oil in terms of its quality as a bio-fuel and/or source of chemicals. Bio-oil used directly as a biofuel for heat or power needs to be improved particularly in terms of temperature sensitivity, oxygen content, chemical instability, solid content, and heating values. Chemicals produced from bio-oil need to be able to meet product specifications for market acceptability. There were two main objectives in this research. The first was to examine the influence of pre-treatment of biomass on the fast pyrolysis process and liquid quality. The relationship between the method of pre-treatment of biomass feedstock to fast pyrolysis oil quality was studied. The thermal decomposition behaviour of untreated and pretreated feedstocks was studied by using a TGA (thermogravimetric analysis) and a Py-GC/MS (pyroprobe-gas chromatography/mass spectrometry). Laboratory scale reactors (100g/h, 300g/h, 1kg/h) were used to process untreated and pretreated feedstocks by fast pyrolysis. The second objective was to study the influence of numerous catalysts on fast pyrolysis liquids from wheat straw. The first step applied analytical pyrolysis (Py-GC/MS) to determine which catalysts had an effect on fast pyrolysis liquid, in order to select catalysts for further laboratory fast pyrolysis. The effect of activation, temperature, and biomass pre-treatment on catalysts were also investigated. Laboratory experiments were also conducted using the existing 300g/h fluidised bed reactor system with a secondary catalytic fixed bed reactor. The screening of catalysts showed that CoMo was a highly active catalyst, which particularly reduced the higher molecular weight products of fast pyrolysis. From these screening tests, CoMo catalyst was selected for larger scale laboratory experiments. With reference to the effect of pre-treatment work on fast pyrolysis process, a significant effect occurred on the thermal decomposition of biomass, as well as the pyrolysis products composition, and the proportion of key components in bio-oil. Torrefaction proved to have a mild influence on pyrolysis products, when compared to aquathermolysis and steam pre-treatment.

FDI and the labour market: a review of the evidence and policy implications

This paper presents a series of results concerning the labour-market impact of inward foreign direct investment (FDI) in the UK. The paper demonstrates that one of the crucial impacts of FDI is to increase wage inequality and the use of relatively more skilled labour in the domestic firms. This result is found to be a combination of two effects. First, the entry by a multinational enterprise (MNE) increases the demand for skilled workers in an industry or region, thus increasing wage inequality. Second, technology spillovers occur from foreign to domestic firms. As a result of these spillovers, relative demand for skilled workers increases in the domestic firms, further contributing to aggregate wage inequality and skill upgrading. The paper also considers how FDI impacts upon skill shares by productivity differentials between foreign and domestic firms. Finally, the policy implications of this are discussed, from the perspective of regional development, and the likely effectiveness of attracting FDI to reduce structural unemployment.

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.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Technical and economic simulation of biomass pyrolysis processes for fuels and electricity

There is considerable concern over the increased effect of fossil fuel usage on the environment and this concern has resulted in an effort to find alternative, environmentally friendly energy sources. Biomass is an available alternative resource which may be converted by flash pyrolysis to produce a crude liquid product that can be used directly to substitute for conventional fossil fuels or upgraded to a higher quality fuel. Both the crude and upgraded products may be utilised for power generation. A computer program, BLUNT, has been developed to model the flash pyrolysis of biomass with subsequent upgrading, refining or power production. The program assesses and compares the economic and technical opportunities for biomass thermochemical conversion on the same basis. BLUNT works by building up a selected processing route from a number of process steps through which the material passes sequentially. Each process step has a step model that calculates the mass and energy balances, the utilities usage and the capital cost for that step of the process. The results of the step models are combined to determine the performance of the whole conversion route. Sample results from the modelling are presented in this thesis. Due to the large number of possible combinations of feeds, conversion processes, products and sensitivity analyses a complete set of results is impractical to present in a single publication. Variation of the production costs for the available products have been illustrated based on the cost of a wood feedstock. The effect of selected macroeconomic factors on the production costs of bio-diesel and gasoline are also given.

Investigation of different techniques to upgrade legacy WDM communication systems

This thesis presents experimental investigation of different effects/techniques that can be used to upgrade legacy WDM communication systems. The main issue in upgrading legacy systems is that the fundamental setup, including components settings such as EDFA gains, does not need to be altered thus the improvement must be carried out at the network terminal. A general introduction to optical fibre communications is given at the beginning, including optical communication components and system impairments. Experimental techniques for performing laboratory optical transmission experiments are presented before the experimental work of this thesis. These techniques include optical transmitter and receiver designs as well as the design and operation of the recirculating loop. The main experimental work includes three different studies. The first study involves a development of line monitoring equipment that can be reliably used to monitor the performance of optically amplified long-haul undersea systems. This equipment can provide instant finding of the fault locations along the legacy communication link which in tum enables rapid repair execution to be performed hence upgrading the legacy system. The second study investigates the effect of changing the number of transmitted 1s and Os on the performance of WDM system. This effect can, in reality, be seen in some coding systems, e.g. forward-error correction (FEC) technique, where the proportion of the 1s and Os are changed at the transmitter by adding extra bits to the original bit sequence. The final study presents transmission results after all-optical format conversion from NRZ to CSRZ and from RZ to CSRZ using semiconductor optical amplifier in nonlinear optical loop mirror (SOA-NOLM). This study is mainly based on the fact that the use of all-optical processing, including format conversion, has become attractive for the future data networks that are proposed to be all-optical. The feasibility of the SOA-NOLM device for converting single and WDM signals is described. The optical conversion bandwidth and its limitations for WDM conversion are also investigated. All studies of this thesis employ 10Gbit/s single or WDM signals being transmitted over dispersion managed fibre span in the recirculating loop. The fibre span is composed of single-mode fibres (SMF) whose losses and dispersion are compensated using erbium-doped fibre amplifiers (EDFAs) and dispersion compensating fibres (DCFs), respectively. Different configurations of the fibre span are presented in different parts.

Lumped dispersion mapping and performance margins in existing SMF-DCF terrestrial links

We demonstrate that the transmission of 40 Gbits/s return-to-zero differential phase-shift keying (RZ-DPSK) signals is robust to lumped dispersion mapping on a typical installed terrestrial single-mode fiber/dispersion compensating fiber (SMF-DCF) link and will withstand, in this case, propagation through over 800 km of SMF with zero in-line group-velocity dispersion compensation while maintaining similar performance to configurations with periodic mapping. We establish that upgrading similar point-to-point links, which have lumped dispersion maps, are compatible with 40 Gbits/s RZ-DPSK and that economic benefits can be realized when implementing lumped dispersion mapping in new 40 Gbits/s RZ-DPSK terrestrial links, while incurring a relatively low performance penalty. (c) 2008 Optical Society of America.

Foreign direct investment and employment in Central Europe

This article investigates the effects of foreign direct investment on employment generation in Central Europe. Foreign affiliates operate as a buffer to reductions in overall employment and show significant cross-country differences. A model analyzing the contribution of foreign direct investment to restructuring is developed. This model helps interpret the empirical evidence on the link between foreign direct investment and employment in Central Europe. Increasing differentiation in employment between manufacturing industries dominated by foreign affiliates suggests the importance of diversified sources of foreign direct investment for employment generation and preservation. A disaggregate analysis indeed reveals a much more complex and differentiated role of foreign direct investment in employment preservation, employment generation and structural change than the aggregate picture would suggest. This diversity has important policy implications for attracting and upgrading foreign direct investment.

Pyrolysis and gasification of biomass and acid hydrolysis residues

This research was carried for an EC supported project that aimed to produce ethyl levulinate as a diesel miscible biofuel from biomass by acid hydrolysis. The objective of this research was to explore thermal conversion technologies to recover further diesel miscible biofuels and/or other valuable products from the remaining solid acid hydrolysis residues (AHR). AHR consists of mainly lignin and humins and contains up to 80% of the original energy in the biomass. Fast pyrolysis and pyrolytic gasification of this low volatile content AHR was unsuccessful. However, successful air gasification of AHR gave a low heating value gas for use in engines for power or heat with the aim of producing all the utility requirements in any commercial implementation of the ethyl levulinate production process. In addition, successful fast pyrolysis of the original biomass gave organic liquid yields of up to 63.9 wt.% (dry feed basis) comparable to results achieved using a standard hardwood. The fast pyrolysis liquid can be used as a fuel or upgraded to biofuels. A novel molybdenum carbide catalyst was tested in fast pyrolysis to explore the potential for upgrading. Although there was no deoxygenation, some bio-oil properties were improved including viscosity, pH and homogeneity through decreasing sugars and increasing furanics and phenolics. AHR gasification was explored in a batch gasifier with a comparison with the original biomass. Refractory and low volatile content AHR gave relatively low gas yields (74.21 wt.%), low tar yields (5.27 wt.%) and high solid yields (20.52 wt.%). Air gasification gave gas heating values of around 5MJ/NM3, which is a typical value, but limitations of the equipment available restricted the extent of process and product analysis. In order to improve robustness of AHR powder for screw feeding into gasifiers, a new densification technique was developed based on mixing powder with bio-oil and curing the mixture at 150°C to polymerise the bio-oil.

Place-renewing leadership:trajectories of change for mature manufacturing regions in Europe

The forces of globalisation now impacting on local economies pose threats to the existing paradigm of competences and routines, yet simultaneously offer opportunities to integrate new knowledge and learning. This is particularly pertinent with respect to Europe’s ‘mature regions’, which are undergoing a major economic restructuring by trying to shift from traditional manufacturing activities to hybrid activities that comprise a combination of manufacturing and a higher component of intangible inputs and related knowledge service activities. The objective of the article is to discuss the concept of ‘place leadership’ by looking at how the embedded skills, knowledge and cumulated learning of a place can be used by its institutional infrastructure to identify sustainable growth trajectories. In other words, its aim is to explore how the economic, social, institutional and cultural aspects of places shape the opportunities for upgrading and renovation drawing upon their historical specialisation. The conceptual contribution of the article draws on two case studies, in the West Midlands, UK and in Prato, Tuscany, where we study the processes of decision-making, forms of leadership and ultimately the nature of local leadership.

Engines for combined heat and power

Spark-ignited (SI) gas engines are for the use of fuel gas only and are limited to the flammable range of the gas; this means the range of a concentration of a gas or vapor that will burn after ignition. Fuel gas like syngas from gasification or biogas must meet high quality and chemical purity standards for combustion in SI gas engines. Considerable effort has been devoted to fast pyrolysis over the years and some of the product oils have been tested in diesel or dual-fuel engines since 1993. For biogas conversion, usually dual-fuel engines are used, while for synthesis gas the use of gas engines is more common. The trials using wood derived pyrolysis oil from fast pyrolysis have not yet been a success story and these approaches have usually failed due to the high corrosivity of the pyrolysis oils.

Optimization of dispersion-managed optical fiber lines

We present various approaches to the optimization of optical fiber lines and discuss the ranges of validity of such methods. An effective scheme for upgrading of existing transmission lines using dispersion-management with optimization of the pre- and postcompensating fiber is examined. The theory and numerical methods are illustrated in application to the Upgrade of a specific installed Deutsche Telekom fiber line.

Fast pyrolysis of biomass for the production of liquids

This chapter examines the fast pyrolysis of biomass to produce liquids for use as fuels and chemicals. The technology for fast pyrolysis is described and the characteristics of the main product bio-oil. This primary liquid is characterised by the many properties that affect its use. These properties have caused increasingly extensive research to be undertaken to address properties that need modification and this area is reviewed in terms of physical, catalytic and chemical upgrading. Of particular note is the increasing diversity of upgrading methods. © 2013 Woodhead Publishing Limited All rights reserved.

Cooperative greedy pursuit strategies for sparse signal representation by partitioning

Cooperative Greedy Pursuit Strategies are considered for approximating a signal partition subjected to a global constraint on sparsity. The approach aims at producing a high quality sparse approximation of the whole signal, using highly coherent redundant dictionaries. The cooperation takes place by ranking the partition units for their sequential stepwise approximation, and is realized by means of i)forward steps for the upgrading of an approximation and/or ii) backward steps for the corresponding downgrading. The advantage of the strategy is illustrated by approximation of music signals using redundant trigonometric dictionaries. In addition to rendering stunning improvements in sparsity with respect to the concomitant trigonometric basis, these dictionaries enable a fast implementation of the approach via the Fast Fourier Transform

To what extent and in what manner do Chinese and Indian contract research organisation learn and upgrade with the unbundling the global pharmaceutical R&D value chain?

The paper applies the GVC framework to analyse the organisational and geographical reconfiguration of the global R&D function of leading US and European pharmaceutical MNCs. Though pharmaceutical MNCs have been outsourcing clinical trial activities since the mid-1990s, the outsourcing of discovery research tasks is a phenomenon of the 2000s (Ramirez 2013). Moreover, in the context of a crisis of R&D productivity and increasing pressure from shareholders, a number of US and European pharmaceutical MNCs are breaking up their R&D function in an attempt to increase flexibility and reduce risk as well as costs and are thereby restructuring the global architecture of their R&D function. This break-up, or unbundling (Sako 2006), of the R&D function is particularly interesting given the prevalence of market failure in innovation (Howells et al 2008), the non-modular nature of the R&D process in this industry (Pisano 2006) and the strategic important of this activity to the core competence and long-term competitive advantage of firms in this sector. The focus of this paper is on the outsourcing of R&D activities to Chinese and Indian independently-owned contract research organisations (CROs) and the way these firms are becoming integrated as service providers into the global R&D function (or R&D value chain) of pharmaceutical MNCs. Above all the paper is concerned with the development of capabilities of CROs from these two countries and the dynamics of upgrading in GVCs in knowledge-intensive functions. The paper therefore discusses the role of both knowledge flows within global pharmaceutical R&D value chains as well as national innovation systems on the development of capabilities of Chinese and Indian CROs. Our analysis is based on data from semi-structured interviews collected from senior R&D managers from a sample of ten US and European pharmaceutical MNCs and owners and senior R&D managers from five Chinese and five Indian CROs who are providing research services to MNCs in this industry. We discuss the emergence of R&D outsourcing in this industry and the nature and mechanisms of knowledge flows within R&D value chains. The embeddedness of CROS in the national innovation systems of their home countries is also discussed.