Genotypic and environmentally derived variation in the cell wall composition of Miscanthus in relation to its use as a biomass feedstock

Fifteen Miscanthus genotypes grown in five locations across Europe were analysed to investigate the influence of genetic and environmental factors on cell wall composition. Chemometric techniques combining near infrared reflectance spectroscopy (NIRS) and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin (ADL), acid detergent fibre (ADF), and neutral detergent fibre (NDF) from sample spectra. Results generated were subsequently converted to lignin, cellulose and hemicellulose content and used to assess the genetic and environmental variation in cell wall composition of Miscanthus and to identify genotypes which display quality traits suitable for exploitation in a range of energy conversion systems. The NIRS calibration models developed were found to predict concentrations with a good degree of accuracy based on the coefficient of determination (R2), standard error of calibration (SEC), and standard error of cross-validation (SECV) values. Across all sites mean lignin, cellulose and hemicellulose values in the winter harvest ranged from 76–115 g kg-1, 412–529 g kg-1, and 235–338 g kg-1 respectively. Overall, of the 15 genotypes Miscanthus x giganteus and Miscanthus sacchariflorus contained higher lignin and cellulose concentrations in the winter harvest. The degree of observed genotypic variation in cell wall composition indicates good potential for plant breeding and matching feedstocks to be optimised to different energy conversion processes.

Thermochemical characterisation of various biomass feedstock and bio-oil generated by fast pyrolysis

The projected decline in fossil fuel availability, environmental concerns, and security of supply attract increased interest in renewable energy derived from biomass. Fast pyrolysis is a possible thermochemical conversion route for the production of bio-oil, with promising advantages. The purpose of the experiments reported in this thesis was to extend our understanding of the fast pyrolysis process for straw, perennial grasses and hardwoods, and the implications of selective pyrolysis, crop harvest and storage on the thermal decomposition products. To this end, characterisation and laboratory-scale fast pyrolysis were conducted on the available feedstocks, and their products were compared. The variation in light and medium volatile decomposition products was investigated at different pyrolysis temperatures and heating rates, and a comparison of fast and slow pyrolysis products was conducted. Feedstocks from different harvests, storage durations and locations were characterised and compared in terms of their fuel and chemical properties. A range of analytical (e.g. Py-GC-MS and TGA) and processing equipment (0.3 kg/h and 1.0 kg/h fast pyrolysis reactors and 0.15 kg slow pyrolysis reactor) was used. Findings show that the high bio-oil and char heating value, and low water content of willow short rotation coppice (SRC) make this crop attractive for fast pyrolysis processing compared to the other investigated feedstocks in this project. From the analytical sequential investigation of willow SRC, it was found that the volatile product distribution can be tailored to achieve a better final product, by a variation of the heating rate and temperature. Time of harvest was most influential on the fuel properties of miscanthus; overall the late harvest produced the best fuel properties (high HHV, low moisture content, high volatile content, low ash content), and storage of the feedstock reduced the moisture and acid content.

New insights in the deactivation of sulfonic modified SBA-15 catalysts for biodiesel production from low-grade oleaginous feedstock

Arenesulfonic-acid functionalized SBA-15 materials have been used in the production of biodiesel from low grade oleaginous feedstock. These materials display an outstanding catalytic activity, being able to promote the transformation of crude palm oil with methanol into fatty acid methyl esters with high yield (85%) under mild reaction conditions. However, high sensitivity of the catalyst against poisoning by different substances has also been detected. Thus, alkaline metal cations, such as sodium or potassium exert a negative influence on the catalytic activity of these materials, being necessary amounts around 500 ppm of sodium in the reaction media to decrease the catalytic activity of these materials to a half of its initial value in just two reaction runs. The deactivation of arenesulfonic acid functionalized SBA-15 materials seems to occur in this case by ion exchange of the acid protons at the sulfonic groups. Organic unsaponifiable compounds like lecithin or retinol also induce a negative influence in the catalytic activity of these sulfonic acid-based materials, though not so intense as in the case of alkaline metals. The deactivating mechanism associated to the influence of the organic compounds seems to be linked to the adsorption of such substances onto the catalytic acid sites as well as on the silica surface. The accumulation of lecithin in the surface of catalyst, observed by means of thermogravimetric analysis, suggest the creation of a strong interaction, probably by ion pair, between this compound and the sulfonic acid group.

Comprehensive characterization of Napier grass as a feedstock for thermochemical conversion

Study on Napier grass leaf (NGL), stem (NGS) and leaf and stem (NGT) was carried out. Proximate, ultimate and structural analyses were evaluated. Functional groups and crystalline components in the biomass were examined. Pyrolysis study was conducted in a thermogravimetric analyzer under nitrogen atmosphere of 20 mL/min at constant heating rate of 10 K/min. The results reveal that Napier grass biomass has high volatile matter, higher heating value, high carbon content and lower ash, nitrogen and sulfur contents. Structural analysis shows that the biomass has considerable cellulose and lignin contents which are good candidates for good quality bio-oil production. From the pyrolysis study, degradation of extractives, hemicellulose, cellulose and lignin occurred at temperature around 478, 543, 600 and above 600 K, respectively. Kinetics of the process was evaluated using reaction order model. New equations that described the process were developed using the kinetic parameters and data compared with experimental data. The results of the models fit well to the experimental data. The proposed models may be a reliable means for describing thermal decomposition of lignocellulosic biomass under nitrogen atmosphere at constant heating rate.

Miscanthus as a feedstock for fast-pyrolysis:does agronomic treatment affect quality?

The objectives of the experiment were to assess the impact of nitrogen (N) and potassium (K) fertiliser application on the cell wall composition and fast-pyrolysis conversion quality of the commercially cultivated hybrid Miscanthus x giganteus. Five different fertiliser treatments were applied to mature Miscanthus plants which were sampled at five intervals over a growing season. The different fertiliser treatments produced significant variation in concentrations of cell wall components and ash within the biomass and affected the composition and quality of the resulting fast-pyrolysis liquids. The results indicated that application of high rates of N fertiliser had a negative effect on feedstock quality for this conversion pathway: reducing the proportion of cell wall components and increasing accumulation of ash in the harvested biomass. No exclusive effect of potassium fertiliser was observed. The low-N fertiliser treatment produced high quality, low ash-high lignin biomass most suitable as a feedstock for thermo-chemical conversion. © 2010.

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.

Spray-dried powders for pulmonary drug delivery

Powders for inhalation are traditionally prepared using a destructive micronization process such as jet milling to reduce the particle size of the drug to 2-5 μm. The resultant particles are typically highly cohesive and display poor aerosolization properties, necessitating the addition of a coarse carrier particle to the micronized drug to improve powder flowability. Spray-drying technology offers an alternative, constructive particle production technique to the traditional destructive approach, which may be particularly useful when processing biotechnology products that could be adversely affected by high-energy micronization processes. Advantages of spray drying include the ability to incorporate a wide range of excipients into the spray-drying feedstock, which could modify the aerosolization and stability characterizations of the resultant powders, as well as modify the drug release and absorption profiles following inhalation. This review discusses some of the reasons why pulmonary drug delivery is becoming an increasingly popular route of administration and describes the various investigations that have been undertaken in the preparation of spray-dried powders for pulmonary drug delivery. © 2007 by Begell House, Inc.

The pre-treatment and pyrolysis of biomass for the production of liquids for fuels and speciality chemicals

Fast pyrolysis of biomass is a significant technology for producing pyrolysis liquids [also known as bio-oil], which contain a number of chemicals. The pyrolysis liquid can be used as a fuel, can be produced solely as a source of chemicals or can have some of the chemicals extracted and the residue used as a fuel. There were two primary objectives of this work. The first was to determine the fast pyrolysis conditions required to maximise the pyrolysis liquid yield from a number of biomass feedstocks. The second objective was to selectively increase the yield of certain chemicals in the pyrolysis liquid by pre-treatment of the feedstock prior to pyrolysis. For a particular biomass feedstock the pyrolysis liquid yield is affected by the reactor process parameters. It has been found that, providing the other process parameters are restricted to the values shown below, reactor temperature is the controlling parameter. The maximum pyrolysis liquid yield and the temperature at which it occurs has been found by a series of pyrolysis experiments over the temperature range 400-600°C. high heating rates > 1000°C/s; pyrolysis vapour residence times <2 seconds; pyrolysis vapour temperatures >400 but <500°C; rapid quenching of the product vapours. Pre-treatment techniques have been devised to modify the chemical composition and/or structure of the biomass in such a way as to influence the chemical composition of the pyrolysis liquid product. The pre-treatments were divided into two groups, those that remove material from the biomass and those which add material to the biomass. Component removal techniques have selectively increased the yield of levoglucosan from 2.45 to 18.58 mf wt.% [dry feedstock basis]. Additive techniques have selectively increased the yield of hydroxyacetaldehyde from 7.26 to 11.63 mf w.% [dry feedstock basis]. Techno-economic assessment has been carried out on an integrated levoglucosan production process [incorporating pre-treatment, pyrolysis and chemical extraction stages] to assess which method of chemical production is the more cost effective. It has been found that it is better to pre-treat the biomass in order to increase the yield of specific chemicals in the pyrolysis liquid and hence improve subsequent chemicals extraction.

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 effect of lignin and inorganic species in biomass on pyrolysis oil yields, quality and stability

This paper investigates four reference fuels and three low lignin Lolium Festuca grasses which were subjected to pyrolysis to produce pyrolysis oils. The oils were analysed to determine their quality and stability, enabling the identification of feedstock traits which affect oil stability. Two washed feedstocks were also subjected to pyrolysis to investigate whether washing can enhance pyrolysis oil quality. It was found that the mineral matter had the dominate effect on pyrolysis in compared to lignin content, in terms of pyrolysis yields for organics, char and gases. However the higher molecular weight compounds present in the pyrolysis oil are due to the lignin derived compounds as determined by results of GPC and liquid-GC/MS. The light organic fraction also increased in yield, but reduced in water content as metals increased at the expense of the lignin content. It was found that the fresh oil and aged oil had different compound intensities/concentrations, which is due to a large number of reactions occurring when the oil is aged day by day. These findings agree with previous reports which suggest that a large amount of re-polymerisation occurs as levoglucosan yields increase during the aging progress, while hydroxyacetaldehyde decrease. In summary the paper reports a window for producing a more stable pyrolysis oil by the use of energy crops, and also show that washing of biomass can improve oil quality and stability for high ash feedstocks, but less so for the energy crops.

Intermediate pyrolysis:a sustainable biomass-to-energy concept-biothermal valorisation of biomass (BtVB) process

Wastewater treatment coupled with energy crop cultivation provides an attractive source of cheap feedstock. This study reviews an advanced, closed-loop bioenergy conversion process [biothermal valorisation of biomass (BtVB)], in which pyroformer is coupled to a gasifier. BtVB process was developed at European Bioenergy Research Institute (EBRI), Aston University, UK and demonstrates an improved method for thermal conversion of ash-rich biomass.

A comparison of integrated biomass to electricity systems

This thesis presents a comparison of integrated biomass to electricity systems on the basis of their efficiency, capital cost and electricity production cost. Four systems are evaluated: combustion to raise steam for a steam cycle; atmospheric gasification to produce fuel gas for a dual fuel diesel engine; pressurised gasification to produce fuel gas for a gas turbine combined cycle; and fast pyrolysis to produce pyrolysis liquid for a dual fuel diesel engine. The feedstock in all cases is wood in chipped form. This is the first time that all three thermochemical conversion technologies have been compared in a single, consistent evaluation.The systems have been modelled from the transportation of the wood chips through pretreatment, thermochemical conversion and electricity generation. Equipment requirements during pretreatment are comprehensively modelled and include reception, storage, drying and communication. The de-coupling of the fast pyrolysis system is examined, where the fast pyrolysis and engine stages are carried out at separate locations. Relationships are also included to allow learning effects to be studied. The modelling is achieved through the use of multiple spreadsheets where each spreadsheet models part of the system in isolation and the spreadsheets are combined to give the cost and performance of a whole system.The use of the models has shown that on current costs the combustion system remains the most cost-effective generating route, despite its low efficiency. The novel systems only produce lower cost electricity if learning effects are included, implying that some sort of subsidy will be required during the early development of the gasification and fast pyrolysis systems to make them competitive with the established combustion approach. The use of decoupling in fast pyrolysis systems is a useful way of reducing system costs if electricity is required at several sites because• a single pyrolysis site can be used to supply all the generators, offering economies of scale at the conversion step. Overall, costs are much higher than conventional electricity generating costs for fossil fuels, due mainly to the small scales used. Biomass to electricity opportunities remain restricted to niche markets where electricity prices are high or feed costs are very low. It is highly recommended that further work examines possibilities for combined beat and power which is suitable for small scale systems and could increase revenues that could reduce electricity prices.

Studies on the deactivation and reactivation of spent hydroprocessing catalyst

A study is reported on the deactivation of hydroprocessing catalysts and their reactivation by the removal of coke and metal foulants. The literature on hydrotreating catalyst deactivation by coke and metals deposition, the environmental problems associated with spent catalyst disposal, and its reactivation/rejuvenation process were reviewed. Experimental studies on catalyst deactivation involved problem analysis in industrial hydroprocessing operations, through characterization of the spent catalyst, and laboratory coking studies. A comparison was made between the characteristics of spent catalysts from fixed bed and ebullating bed residue hydroprocessing reactor units and the catalyst deactivation pattern in both types of reactor systems was examined. In the laboratory the nature of initial coke deposited on the catalyst surface and its role on catalyst deactivation were studied. The influence of initial coke on catalyst surface area and porosity was significant. Both catalyst acidity and feedstock quality had a remarkable influence on the amount and the nature of the initial coke. The hydroenitrogenation function (HDN) of the catalyst was found to be deactivated more rapidly by the initial coke than the hydrodesulphurization function (HDS). In decoking experiments, special attention was paid to the initial conditions of coke combustion, since the early stages of contact between the coke on the spent catalyst surface and the oxygen are crucial in the decoking process. An increase in initial combustion temperature above 440oC and the oxygen content of the regeneration gas above 5% vanadium led to considerable sintering of the catalyst. At temperatures above 700oC there was a substantial loss of molybdenum from the catalyst, and phase transformations in the alumina support. The preferred leaching route (coked vs decoked form of spent catalyst) and a comparison of different reagents (i.e., oxalic acid and tartaric acid) and promoters (i.e., Hydrogen Peroxide and Ferric Nitrate) for better selectivity in removing the major foulant (vanadium), characterization and performance evaluation of the treated catalysts and modelling of the leaching process were addressed in spent catalyst rejuvenation studies. The surface area and pore volume increased substantially with increasing vanadium extraction from the spent catalyst; the HDS activity showed a parallel increase. The selectivity for leaching of vanadium deposits was better, and activity recovery was higher, for catalyst rejuvenated by metal leaching prior to decoking.

The design, evaluation and costing of biomass gasifiers

The objective of this study has been to enable a greater understanding of the biomass gasification process through the development and use of process and economic models. A new theoretical equilibrium model of gasification is described using the operating condition called the adiabatic carbon boundary. This represents an ideal gasifier working at the point where the carbon in the feedstock is completely gasified. The model can be used as a `target' against which the results of real gasifiers can be compared, but it does not simulate the results of real gasifiers. A second model has been developed which uses a stagewise approach in order to model fluid bed gasification, and its results have indicated that pyrolysis and the reactions of pyrolysis products play an important part in fluid bed gasifiers. Both models have been used in sensitivity analyses: the biomass moisture content and gasifying agent composition were found to have the largest effects on performance, whilst pressure and heat loss had lesser effects. Correlations have been produced to estimate the total installed capital cost of gasification systems and have been used in an economic model of gasification. This has been used in a sensitivity analysis to determine the factors which most affect the profitability of gasification. The most important influences on gasifier profitability have been found to be feedstock cost, product selling price and throughput. Given the economic conditions of late 1985, refuse gasification for the production of producer gas was found to be viable at throughputs of about 2.5 tonnes/h dry basis and above, in the metropolitan counties of the United Kingdom. At this throughput and above, the largest element of product gas cost is the feedstock cost, the cost element which is most variable.

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.