Variation in Miscanthus chemical composition and implications for conversion by pyrolysis and thermo-chemical bio-refining for fuels and chemicals

Different species and genotypes of Miscanthus were analysed to determine the influence of genotypic variation and harvest time on cell wall composition and the products which may be refined via pyrolysis. Wet chemical, thermo-gravimetric (TGA) and pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS) methods were used to identify the main pyrolysis products and determine the extent to which genotypic differences in cell wall composition influence the range and yield of pyrolysis products. Significant genotypic variation in composition was identified between species and genotypes, and a clear relationship was observed between the biomass composition, yields of pyrolysis products, and the composition of the volatile fraction. Results indicated that genotypes other than the commercially cultivated Miscanthus x giganteus may have greater potential for use in bio-refining of fuels and chemicals and several genotypes were identified as excellent candidates for the generation of genetic mapping families and the breeding of new genotypes with improved conversion quality characteristics.

Genetic and environmentally derived variation in the cell wall composition of miscanthus and implications for thermo-chemical conversion

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 and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin, acid detergent fibre, and neutral detergent fibre from sample spectra. The developed equations were shown to predict cell wall components with a good degree of accuracy and significant genetic and environmental variation was identified. The influence of nitrogen and potassium fertiliser on the dry matter yield and cell wall composition of M. x giganteus was investigated. A detrimental affect on feedstock quality was observed to result from application of these inputs which resulted in an overall reduction in concentrations of cell wall components and increased accumulation of ash within the biomass. Pyrolysis-gas chromatography-mass spectrometry and thermo-gravimetric analysis indicates that genotypes other than the commercially cultivated M. x giganteus have potential for use in energy conversion processes and in the bio-refining. The yields and quality parameters of the pyrolysis liquids produced from Miscanthus compared favourably with that produced from SRC willow and produced a more stable pyrolysis liquid with a higher lower heating value. Overall, genotype had a more significant effect on cell wall composition than environment. This indicates good potential for dissection of this trait by QTL analysis and also for plant breeding to produce new genotypes with improved feedstock characteristics for energy conversion.

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.

Impact of Miscanthus x giganteus senescence times on fast pyrolysis bio-oil quality

In this study the impact of senescence and harvest time in Miscanthus on the quality of fast pyrolysis liquid (bio-oil) was investigated. Bio-oil was produced using a 1kgh fast pyrolysis reactor to obtain a quantity of bio-oil comparable with existing industrial reactors. Bio-oil stability was measured using viscosity, water content, pH and heating value changes under specific conditions. Plant developmental characteristics were significantly different (P=0.05) between all harvest points. The stage of crop senescence was correlated with nutrient remobilisation (N, P, K; r=0.9043, r=0.9920, r=0.9977 respectively) and affected bio-oil quality. Harvest time and senescence impacted bio-oil quality and stability. For fast pyrolysis processing of Miscanthus, the harvest time of Miscanthus can be extended to cover a wider harvest window whilst still maintaining bio-oil quality but this may impact mineral depletion in, and long term sustainability of, the crop unless these minerals can be recycled. © 2012 Elsevier Ltd.

The influence of harvest and storage on the properties of and fast pyrolysis products from Miscanthus x giganteus

The research investigates the fuel property variations associated with the time of harvest and the duration of storage of Miscanthus x giganteus over a one year period. The crop has been harvested at three different times: early (September 2009), conventional (April 2010) and late (June 2010). Once harvested the crop was baled and stored. Biomass properties of samples taken from different storage zones were compared. The thermochemical properties have been investigated using a range of analytical equipment including thermogravimetric analysis (TGA) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). In addition, bio-oil has been produced from the early, conventional and late harvest using a laboratory scale (300gh) fast pyrolysis unit. The potential organic liquid yield (ondry basis, also excluding the reaction water generated) based on the laboratory fast pyrolysis processing undertaken in this study, was found to vary between 2.82 and 3.18 dry tha for the early and the late harvest respectively. The bio-oil organic yield was reduced by approximately 11% (0.36tha) between the early and the late harvest. Char yield was also reduced by approximately 18% (0.61tha). The highest gas yield (18.03%-1.60tha) was observed for the conventional harvest. Gas chromatography-mass spectrometry (GC-MS) analysis of the bio-oil shows that levoglucosan, methylbenzaldehyde and 1,2-benzenediol all increase as a consequence of delayed harvest. It was also observed that by delaying the harvest time the O:C atomic ratio is reduced and a more carbonaceous feedstock is produced. © 2013 Elsevier Ltd.

Fast pyrolysis processing of surfactant washed Miscanthus

Miscanthus × giganteus was subjected to pre-treatment with deionised water, hydrochloric acid or Triton X-100 surfactant, and subsequently fast pyrolysed in a fluidised bed reactor at 535 °C to obtain bio-oil. Triton X-100 surfactant was identified as a promising pre-treatment medium for removal of inorganic matter because its physicochemical nature was expected to mobilise inorganic matter in the biomass matrix. The influence of different concentrations of Triton X-100 pre-treatment solutions on the quality of bio-oil produced from fast pyrolysis was studied, as defined by a single phase bio-oil, viscosity index and water content index. The highest concentration of Triton X-100 surfactant produced the best quality bio-oil with high organic yield and low reaction water content. The calculated viscosity index from the accelerated ageing test showed that bio-oil stability improved as the concentration of Triton X-100 increased. © 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.

Kinetic study of the pyrolysis of miscanthus and its acid hydrolysis residue by thermogravimetric analysis

The kinetic parameters of the pyrolysis of miscanthus and its acid hydrolysis residue (AHR) were determined using thermogravimetric analysis (TGA). The AHR was produced at the University of Limerick by treating miscanthus with 5 wt.% sulphuric acid at 175 °C as representative of a lignocellulosic acid hydrolysis product. For the TGA experiments, 3 to 6 g of sample, milled and sieved to a particle size below 250 μm, were placed in the TGA ceramic crucible. The experiments were carried out under non-isothermal conditions heating the samples from 50 to 900 °C at heating rates of 2.5, 5, 10, 17 and 25 °C/min. The activation energy (EA) of the decomposition process was determined from the TGA data by differential analysis (Friedman) and three isoconversional methods of integral analysis (Kissinger–Akahira–Sunose, Ozawa–Flynn–Wall, Vyazovkin). The activation energy ranged from 129 to 156 kJ/mol for miscanthus and from 200 to 376 kJ/mol for AHR increasing with increasing conversion. The reaction model was selected using the non-linear least squares method and the pre-exponential factor was calculated from the Arrhenius approximation. The results showed that the best fitting reaction model was the third order reaction for both feedstocks. The pre-exponential factor was in the range of 5.6 × 1010 to 3.9 × 10+ 13 min− 1 for miscanthus and 2.1 × 1016 to 7.7 × 1025 min− 1 for AHR.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Viscosity of aged bio-oils from fast pyrolysis of beech wood and miscanthus:shear rate and temperature dependence

The viscosity of four aged bio-oil samples was measured experimentally at various shear rates and temperatures using a rotational viscometer. The experimental bio-oils were derived from fast pyrolysis of beech wood at 450, 500, and 550 °C and Miscanthus at 500 °C (in this work, they were named as BW1, BW2, BW3, and MXG) in a bubbling fluidized bed reactor. The viscosity of all bio-oils was kept constant at various shear rates at the same temperature, which indicated that they were Newtonian fluids. The viscosity of bio-oils was strongly dependent upon the temperature, and with the increase of the temperature from 30 to 80 °C, the viscosity of BW1, BW2, BW3, and MXG decreased by 90.7, 93.3, 92.6, and 90.2%, respectively. The Arrhenius viscosity model, which has been commonly used to represent the temperature dependence of the viscosity of many fluids, did not fit the viscosity-temperature experimental data of all bio-oils very well, especially in the low- and high-temperature regions. For comparison, the Williams-Landel-Ferry (WLF) model was also used. The results showed that the WLF model gave a very good description of the viscosity-temperature relationship of each bio-oil with very small residuals and the BW3 bio-oil had the strongest viscosity-temperature dependence.

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.

The development and optimisation of a fast pyrolysis process for bio-oil production

A two-tier study is presented in this thesis. The first involves the commissioning of an extant but at the time, unproven bubbling fluidised bed fast pyrolysis unit. The unit was designed for an intended nominal throughput of 300 g/h of biomass. The unit came complete with solids separation, pyrolysis vapour quenching and oil collection systems. Modifications were carried out on various sections of the system including the reactor heating, quenching and liquid collection systems. The modifications allowed for fast pyrolysis experiments to be carried out at the appropriate temperatures. Bio-oil was generated using conventional biomass feedstocks including Willow, beechwood, Pine and Miscanthus. Results from this phase of the research showed however, that although the rig was capable of processing biomass to bio-oil, it was characterised by low mass balance closures and recurrent operational problems. The problems included blockages, poor reactor hydrodynamics and reduced organic liquid yields. The less than optimal performance of individual sections, particularly the feed and reactor systems of the rig, culminated in a poor overall performance of the system. The second phase of this research involved the redesign of two key components of the unit. An alternative feeding system was commissioned for the unit. The feed system included an off the shelf gravimetric system for accurate metering and efficient delivery of biomass. Similarly, a new bubbling fluidised bed reactor with an intended nominal throughput of 500g/h of biomass was designed and constructed. The design leveraged on experience from the initial commissioning phase with proven kinetic and hydrodynamic studies. These units were commissioned as part of the optimisation phase of the study. Also as part of this study, two varieties each, of previously unreported feedstocks namely Jatropha curcas and Moringa olifiera oil seed press cakes were characterised to determine their suitability as feedstocks for liquid fuel production via fast pyrolysis. Consequently, the feedstocks were used for the production of pyrolysis liquids. The quality of the pyrolysis liquids from the feedstocks were then investigated via a number of analytical techniques. The oils from the press cakes showed high levels of stability and reduced pH values. The improvements to the design of the fast pyrolysis unit led to higher mass balance closures and increased organic liquid yields. The maximum liquid yield obtained from the press cakes was from African Jatropha press cake at 66 wt% on a dry basis.

Estimation of the production cost of fast pyrolysis bio-oil

A number of papers and reports covering the techno-economic analysis of bio-oil production has been published. These have had different scopes, use different feedstocks and reflected national cost structures. This paper reviews and compares their cost estimates and the experimental results that underpin them. A comprehensive cost and performance model was produced based on consensus data from the previous studies or stated scenarios where data is not available that reflected UK costs. The model takes account sales of bio-char that is a co-product of pyrolysis and the electricity consumption of the pyrolysis plant and biomass pre-processing plants. It was concluded that it should be able to produce bio-oil in the UK from energy crops for a similar cost as distillate fuel oil. It was also found that there was little difference in the processing cost for woodchips and baled miscanthus. © 2011 Elsevier Ltd.

The characterisation and optimisation of modified herbaceous grasses for identifying pyrolisis-oil quality traits

The primary objective of this work is to relate the biomass fuel quality to fast pyrolysis-oil quality in order to identify key biomass traits which affect pyrolysis-oil stability. During storage the pyrolysis-oil becomes more viscous due to chemical and physical changes, as reactions and volatile losses occur due to aging. The reason for oil instability begins within the pyrolysis reactor during pyrolysis in which the biomass is rapidly heated in the absence of oxygen, producing free radical volatiles which are then quickly condensed to form the oil. The products formed do not reach thermodynamic equilibrium and in tum the products react with each other to try to achieve product stability. The first aim of this research was to develop and validate a rapid screening method for determining biomass lignin content in comparison to traditional, time consuming and hence costly wet chemical methods such as Klason. Lolium and Festuca grasses were selected to validate the screening method, as these grass genotypes exhibit a low range of Klason /Acid Digestible Fibre lignin contents. The screening methodology was based on the relationship between the lignin derived products from pyrolysis and the lignin content as determined by wet chemistry. The second aim of the research was to determine whether metals have an affect on fast pyrolysis products, and if any clear relationships can be deduced to aid research in feedstock selection for fast pyrolysis processing. It was found that alkali metals, particularly Na and K influence the rate and yield of degradation as well the char content. Pre-washing biomass with water can remove 70% of the total metals, and improve the pyrolysis product characteristics by increasing the organic yield, the temperature in which maximum liquid yield occurs and the proportion of higher molecular weight compounds within the pyrolysis-oil. The third aim identified these feedstock traits and relates them to the pyrolysis-oil quality and stability. It was found that the mineral matter was a key determinant on pyrolysis-oil yield compared to the proportion of lignin. However the higher molecular weight compounds present in the pyrolysis-oil are due to the lignin, and can cause instability within the pyrolysis-oil. The final aim was to investigate if energy crops can be enhanced by agronomical practices to produce a biomass quality which is attractive to the biomass conversion community, as well as giving a good yield to the farmers. It was found that the nitrogen/potassium chloride fertiliser treatments enhances Miscanthus qualities, by producing low ash, high volatiles yields with acceptable yields for farmers. The progress of senescence was measured in terms of biomass characteristics and fast pyrolysis product characteristics. The results obtained from this research are in strong agreement with published literature, and provides new information on quality traits for biomass which affects pyrolysis and pyrolysis-oils.

A techno-economic assessment of the use of fast pyrolysis bio-oil from UK energy crops in the production of electricity and combined heat and power

This thesis investigates the cost of electricity generation using bio-oil produced by the fast pyrolysis of UK energy crops. The study covers cost from the farm to the generator’s terminals. The use of short rotation coppice willow and miscanthus as feedstocks was investigated. All costs and performance data have been taken from published papers, reports or web sites. Generation technologies are compared at scales where they have proved economic burning other fuels, rather than at a given size. A pyrolysis yield model was developed for a bubbling fluidised bed fast pyrolysis reactor from published data to predict bio-oil yields and pyrolysis plant energy demands. Generation using diesel engines, gas turbines in open and combined cycle (CCGT) operation and steam cycle plants was considered. The use of bio-oil storage to allow the pyrolysis and generation plants to operate independently of each other was investigated. The option of using diesel generators and open cycle gas turbines for combined heat and power was examined. The possible cost reductions that could be expected through learning if the technology is widely implemented were considered. It was found that none of the systems analysed would be viable without subsidy, but with the current Renewable Obligation Scheme CCGT plants in the 200 to 350 MWe range, super-critical coal fired boilers co-fired with bio-oil, and groups of diesel engine based CHP schemes supplied by a central pyrolysis plant would be viable. It was found that the cost would reduce with implementation and the planting of more energy crops but some subsidy would still be needed to make the plants viable.

Analysis of transport costs for energy crops for use in biomass pyrolysis plant networks

Fast pyrolysis of biomass produces a liquid bio-oil that can be used for electricity generation. Bio-oil can be stored and transported so it is possible to decouple the pyrolysis process from the generation process. This allows each process to be separately optimised. It is necessary to have an understanding of the transport costs involved in order to carry out techno-economic assessments of combinations of remote pyrolysis plants and generation plants. Published fixed and variable costs for freight haulage have been used to calculate the transport cost for trucks running between field stores and a pyrolysis plant. It was found that the key parameter for estimating these costs was the number of round trips a day a truck could make rather than the distance covered. This zone costing approach was used to estimate the transport costs for a range of pyrolysis plants size for willow woodchips and baled miscanthus. The possibility of saving transport costs by producing bio-oil near to the field stores and transporting the bio-oil to a central plant was investigated and it was found that this would only be cost effective for large generation plants.