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Journal Articles

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Lynch, D., Low, F., Henihan, A.M.,, Garcia, A.,, Kwapinski, W.,, Zhang, L.,, Leahy, J.J. (2014) Behavior of heavy metals during fluidized bed combustion of poultry litter, Energy and Fuels

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In this study, we have examined the behavior of heavy metals during fluidized bed combustion of poultry litter. Heavy metals examined include As, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, V and Zn. Solid and gaseous streams were analyzed and compared with relevant guidelines to determine the potential environmental impact of combustion, and subsequent land spreading or landfill of the resulting ash. The majority of heavy metals were associated with the solid ash fraction, with low gaseous emissions. Pb and As were concentrated in the fine baghouse ash (160oC) due to their volatility. The remaining heavy metals, excluding Cd, were enriched in the heat exchangers and cyclone, where flue gas temperatures ranged from 580oC to 220oC. Under the waste acceptance criteria, all samples of process ash, excluding bed ash, exceeded the limits for non-hazardous landfill waste, as a result of high levels of water soluble Cr. Water soluble Cr indicated the presence of Cr(VI), and its presence was confirmed using X-ray absorption near-edge structure spectroscopy (18.4 % to 38.3%). The source of Cr was identified as the bedding material (wood shavings), its conversion to Cr(VI) was temperature-dependent, and could be facilitated by the high alkali content found in poultry litter.


Hayes, D. J. M. (2013) Second-generation biofuels: why they are taking so long, Wiley Interdisciplinary Reviews: Energy and Environment 2(3):304–334

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There has been a significant degree of hype regarding the commercial potential of second?generation biofuels (2GBs; biofuels sourced from lignocellulosic materials). In 2007, ambitious targets for the mass substitution of fossil?fuel?derived transport fuels by 2GBs were put forward in the United States and similar targets exist for other countries. However, as of May 2012, no commercial?scale 2GB facilities are currently operating. The technical and financial obstacles that have delayed the deployment of these facilities are discussed, as are recent advancements in research that may help to overcome some of these. There are six commercial?scale facilities currently (May, 2012) in construction and many more are planned in the near term. The prospects for 2GBs are more promising now than in the past but the delays in getting to this point mean that the ambitious targets of several years ago are unlikely to be reached in the near term.


Girisuta, B.K. DussanD. HavertyJ.J. LeahyM.H.B. Hayes (2013) A kinetic study of acid catalysed hydrolysis of sugarcane bagasse to levulinic acid, Chemical Engineering Journal 217:61-70

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There is a significant research effort worldwide to identify attractive chemical conversion routes for lignocellulosic biomass to organic (bulk-)chemicals. This study has focussed on the acid-catalysed hydrolysis of sugar cane bagasse for the production of levulinic acid (LA), a platform chemical used for the synthesis of a variety of materials for applications such as fuel additives and polymer and resin precursors. The objectives of this study were to develop a broadly applicable kinetic model for the acid-catalysed hydrolysis of sugar cane bagasse to LA and to determine the optimum reaction conditions for its production. Systematic kinetic experiments were carried out by varying the reaction temperature between 150 and 200 °C, and the sulphuric acid concentration between 0.11 and 0.55 M. The highest LA yield was obtained at 150 °C and 0.55 M H2SO4 at 63 mol%, which equates to the production of 194 kg of LA from 1 dry tonne of sugar cane bagasse. The kinetic model developed was in good agreement with the experimental data and also with the previous kinetic models developed for cellulose and sugar cane bagasse. Our kinetic model, though developed for the sugar cane bagasse, can be applied over a wide range of hydrolysis reaction conditions for lignocellulosic biomass. Based on the optimisation study carried out using our kinetic model, an empirical equation is proposed to predict the LA yield at a particular temperature and acid concentration.


Troy S.M., Nolan T., Leahy J.J., Lawlor P.G., Healy M.G., Kwapinski W. (2013) Effect of sawdust addition and composting of feedstock on renewable energy and biochar production from pyrolysis of anaerobically digested pig manure, Biomass and Bioenergy

F. MelliganM.H.B. HayesW. KwapinskiJ.J. Leahy (2013) A study of hydrogen pressure during hydropyrolysis of Miscanthus x giganteus and online catalytic vapour upgrading with Ni on ZSM-5, Journal of Analytical and Applied Pyrolysis

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Hydropyrolysis, coupled with a secondary catalytic reactor was used as a method of producing a bio-oil from Miscanthus x giganteus with low levels of oxygenated compounds and high yields of saturated hydrocarbons. This study used analytical Pyrolysis-gas chromatography/mass spectroscopy for the analysis of products from the pyrolysis of Miscanthus. Hydropyrolysis was carried out at 600 °C, and the pyrolysis vapours then passed through a secondary reactor, which contained a 10% Ni on ZSM-5 catalyst. The hydrogen pressure for the separate reactions ranged from atmospheric pressure up to 30 bar. The results indicate that both hydrogen pressure and the incorporation of the Ni/ZSM-5 catalysts play an important role in the production of saturated hydrocarbons through the hydrogenation, dehydration and decarboxylation of oxygenated compounds. Also, in the absence of the catalyst the concentration of ethanoic acid can be significantly reduced with the increase in hydrogen pressure, and completely eliminated at 20 bar.

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Hayes, D. J. M. (2013) Mass and Compositional Changes, Relevant to Biorefining, in Miscanthus x giganteus Plants over the Harvest Window , Bioresource Technology 142:591–602

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Miscanthus plants were sampled from several plantations in Ireland over the harvest window (October-April). These were separated into their anatomical components and the loss of leaves monitored. Three distinct phases were apparent: there was minimal loss in the “Early” (October to early December) and “Late” (March and April) phases, and rapid leaf loss in the interim period. Samples were analysed for constituents relevant to biorefining. Changes in whole-plant composition included increases in glucose and Klason lignin contents and decreases in ash and arabinose contents. These changes arose mostly from the loss of leaves, but there were some changes over time within the harvestable plant components. Although leaves yield less biofuel than stems, the added biomass provided by an early harvest (31.9 to 38.4%) meant that per hectare biofuel yields were significantly greater (up to 29.3%) than in a late harvest. These yields greatly exceed those from first generation feedstocks.


Lynch, D., Henihan, A.M., Bowen, B., Lynch, D., McDonnell, K., Kwapinski, W.Leahy, J.J. (2013) Utilisation of poultry litter as an energy feedstock, Biomass and Bioenergy 49:197-204

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This paper examines poultry litter (PL) as a resource in fuel quality terms and illustrates how the small scale application of fluidised bed technology solves both energy and waste problems, while producing a nutrient rich ash. PL was found to have a higher heating value (HHV) of 18 GJ/t on a dry basis (db). On an as received basis (ar), it had an ash mass fraction of 9% and the elemental phosphorous content of the ash was 110 g/kg.The resultant mineral matter can be utilised as a nutrient substitute for mineral fertiliser.

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Lynch, D., Henihan, A.M., Kwapinski, W., Zhang, L., Leahy, J.J. (2013) Ash Agglomeration and Deposition during Combustion of Poultry Litter in a Bubbling Fluidized-Bed Combustor, Energy and Fuels

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In this study, we have characterized the ash resulting from fluidized bed combustion of poultry litter as being dominated by a coarse fraction of crystalline ash composed of alkali-Ca-phosphates and a fine fraction of particulate K2SO4 and KCl. Bed agglomeration was found to be coating-induced with two distinct layers present. The inner layer (0.05–0.09 mm thick) was formed due to the reaction of gaseous potassium with the sand (SiO2) surface forming K-silicates with low melting points. Further chemical reaction on the surface of the bed material strengthened the coating forming a molten glassy phase. The outer layer was composed of loosely bound, fine particulate ash originating from the char. Thermodynamic equilibrium calculations showed slag formation in the combustion zone is highly temperature-dependent, with slag formation predicted to increase from 1.8 kg at 600 °C to 7.35 kg at 1000 °C per hour of operation (5.21 kg of ash). Of this slag phase, SiO2 and K2O were the dominant phases, accounting for almost 95%, highlighting the role of K-silicates in initiating bed agglomeration. The remaining 5% was predicted to consist mainly of Al2O3, K2SO4, and Na2O. Deposition downstream in the low-temperature regions was found to occur mostly through the vaporization–condensation mechanism, with equilibrium decreasing significantly with decreasing temperatures. The dominant alkali chloride-containing gas predicted to form in the combustion zone was KCl, which corresponds with the high KCl content in the fine baghouse ash.

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Haverty, D.Dussan, K.Piterina, A. V.Leahy J. J.Hayes, M. H. B. (2012) Autothermal, single-stage, performic acid pretreatment of Miscanthus x giganteus for the rapid fractionation of its biomass components into a lignin/hemicellulose-rich liquor and a cellulase-digestible pulp, Bioresource Technology 109:173-177

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A novel approach to the performic acid pulping of biomass enables effective delignification and fractionation in a time frame not achieved heretofore. An autothermal decomposition reaction was triggered when 100 mg/L Fe2(SO4)3 in 4.0 M NaOH was added to 5% or 7.5% H2O2 in aqueous formic acid containing chipped Miscanthus x giganteus. Peroxy-decomposition resulted in pressures of 19 and 35 bar in the 5% and 7.5% peroxide liquors and reduced the lignin content in the resulting pulps to <6% within 140 and 30 min, respectively. Solubilised lignin was available for recovery from the liquor by subsequent dilution with water. Hemicellulose removal to the liquor was 68% and 89% for the 5% and 7.5% peroxide solutions. Crystalline cellulose yields were >99% and >95% and the rate of glucose release from cellulase digestion of the pulps in 24 h was more than 20-fold that for the raw Miscanthus

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Melligan, F.Dussan, K., Auccaise, R., Novotny, E. H., Leahy, J. J.Hayes, M. H. B.Kwapinski, W. (2012) Characterisation of the products from pyrolysis of residues after acid hydrolysis of MiscanthusBioresource Technology 108:258-263

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Platform chemicals such as furfural and hydroxymethylfurfural are major products formed during the acid hydrolysis of lignocellulosic biomass in second generation biorefining processes. Solid hydrolysis residues (HR) can amount to 50 wt.% of the starting biomass materials. Pyrolysis of the HRs gives rise to biochar, bio-liquids, and gases. Time and temperature were variables during the pyrolysis of HRs in a fixed bed tubular reactor, and both parameters have major influences on the amounts and properties of the products. Biochar, with potential for carbon sequestration and soil conditioning, composed about half of the HR pyrolysis product. The amounts (11–20 wt.%) and compositions (up to 77% of phenols in organic fraction) of the bio-liquids formed suggest that these have little value as fuels, but could be sources of phenols, and the gas can have application as a fuel.


Hayes, D. J. M. (2012) Development of near infrared spectroscopy models for the quantitative prediction of the lignocellulosic components of wet Miscanthus samples, Bioresource Technology 119:393-405

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Miscanthus samples were scanned over the visible and near infrared wavelengths at several stages of processing (wet-chopped, air-dried, dried and ground, and dried and sieved). Models were developed to predict lignocellulosic and elemental constituents based on these spectra. The dry and sieved scans gave the most accurate models; however the wet-chopped models for glucose, xylose, and Klason lignin provided excellent accuracies with root mean square error of predictions of 1.27%, 0.54%, and 0.93%, respectively. These models can be suitable for most applications. The wet models for arabinose, Klason lignin, acid soluble lignin, ash, extractives, rhamnose, acid insoluble residue, and nitrogen tended to have lower R2 values (0.80+) for the validation sets and the wet models for galactose, mannose, and acid insoluble ash were less accurate, only having value for rough sample screening. This research shows the potential for online analysis at biorefineries for the major lignocellulosic constituents of interest.

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Bulushev, D.A.Jia, L., Beloshapkin, S., Ross, J.R.H. (2012) Improved hydrogen production from formic acid on a Pd/C catalyst doped by potassium, Chemical Communications 48:4184-4186

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The rate of hydrogen production from vapour-phase formic acid decomposition can be increased by 1–2 orders of magnitude by doping a Pd/C catalyst with potassium ions. Surface potassium formate and/or bicarbonate species could be involved in the rate-determining step of this reaction.


Bulushev, D.A., Beloshapkin, S.,, Plyusnin, P.E., Shubin, Y.V., Bukhtiyarov, V.I., Korenev, S.V., Ross, J.R.H. (2012) Vapour phase formic acid decomposition over PdAu/gamma-Al2O3 catalysts: Effect of composition of metallic particles, Journal of Catalysis

Collins, M. N., Dalton, E., Schaller, B., Leahy, J. J., Birkinshaw, C. (2012) Crystal morphology of strained ultra high molecular weight polyethylenes, Polymer Testing 31:629-637

Girisuta B., Kalogiannis, K. G., Dussan, K.Leahy, J. J.Hayes, M. H. B., Stefanidis, S. (2012) An integrated process for the production of platform chemicals and diesel miscible fuels by acid-catalyzed hydrolysis and downstream upgrading of the acid hydrolysis residues with thermal and catalytic pyrolysis, Bioresource Technology 126:92-100

Hayes, Thomas M., Michael H.B. Hayes, Roger S. Swift (2012) Detailed investigation of organic matter components in extracts and in drainage waters from a soil under long-term cultivation, Organic Geochemistry 52:13-21

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Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, ?13C, ?15N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS 13C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.


Li Z.Wnetrzak R.Kwapinski W.Leahy J.J. (2012) Synthesis and characterisation of sulfated TiO2 nanorods and ZrO2/TiO2 nanorod composites for the esterification of bio-oil model organic acid, ACS Applied Materials & Interfaces 4:4499-4505

Linhares C.R., Lemke J., Auccaise R., Duó D.A., Ziolli R.L., Kwapinski W., Novotny E.H. (2012) Reproducing the organic matter model of anthropogenic dark earth of Amazonia and testing the ecotoxicity of functionalized charcoal compounds, Agropecuária Brasileira 47:693-698

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The objective of this work was to obtain organic compounds similar to the ones found in the organic matter of anthropogenic dark earth of Amazonia (ADE) using a chemical functionalization procedure on activated charcoal, as well as to determine their ecotoxicity. Based on the study of the organic matter from ADE, an organic model was proposed and an attempt to reproduce it was described. Activated charcoal was oxidized with the use of sodium hypochlorite at different concentrations. Nuclear magnetic resonance was performed to verify if the spectra of the obtained products were similar to the ones of humic acids from ADE. The similarity between spectra indicated that the obtained products were polycondensed aromatic structures with carboxyl groups: a soil amendment that can contribute to soil fertility and to its sustainable use. An ecotoxicological test with Daphnia similis was performed on the more soluble fraction (fulvic acids) of the produced soil amendment. Aryl chloride was formed during the synthesis of the organic compounds from activated charcoal functionalization and partially removed through a purification process. However, it is probable that some aryl chloride remained in the final product, since the ecotoxicological test indicated that the chemical functionalized soil amendment is moderately toxic.


Melligan, FergusKarla Dussan, Ruben Auccaise, Etelvino H Novotny, James J LeahyMichael H.B. HayesWitold Kwapinski (2012) Characterisation of the products from pyrolysis of residues after acid hydrolysis of Miscanthus, Bioresource Technology 108:258-263

Click for abstract
Platform chemicals such as furfural and hydroxymethylfurfural are major products formed during the acid hydrolysis of lignocellulosic biomass in second generation biorefining processes. Solid hydrolysis residues (HR) can amount to 50 wt.% of the starting biomass materials. Pyrolysis of the HRs gives rise to biochar, bio-liquids, and gases. Time and temperature were variables during the pyrolysis of HRs in a fixed bed tubular reactor, and both parameters have major influences on the amounts and properties of the products. Biochar, with potential for carbon sequestration and soil conditioning, composed about half of the HR pyrolysis product. The amounts (11-20 wt.%) and compositions (up to 77% of phenols in organic fraction) of the bio-liquids formed suggest that these have little value as fuels, but could be sources of phenols, and the gas can have application as a fuel.


Melligan, F.J.J. LeahyW. KwapinskiM.H.B. Hayes (2012) Hydro-pyrolysis of biomass and on-line catalytic vapour upgrading with Ni-ZSM and Ni-MCM-41, Energy and Fuels 26:6080-6090

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A catalyst reactor coupled with analytical pyrolysis gas chromatography/mass spectroscopy (Py-GC/MS) was used to carry out online analysis of the product vapors from the fast pyrolysis of Miscanthus x giganteus, Scots pine, and mahogany. Pyrolysis was carried out in both an inert atmosphere of He gas and in a highly reducing atmosphere of H2. Significant changes in the vapor compositions were achieved with the use of H2 as the carrier gas. The most notable of these were the increases in the hydrocarbon compositions. The roles of ZSM-5, Ni/ZSM-5, MCM-41, and of Ni/MCM-41 catalysts on the compositions of the pyrolysis vapors were investigated. Lower amounts of the higher molecular weight phenolic compounds and larger amounts of the lighter phenols were observed in the presence of Ni supported on ZSM-5 and MCM-41. This effect was more evident for the 10% than for the 2.5% Ni loadings. Overall, the results both from the use of H2 as the carrier gas and from all the catalysts demonstrates significant improvements in the composition of the vapors. However, this resulted in the lowering of the quantities of condensable products.


Novotny E.H., Auccaise R., Velloso M.H.R., Corrêa J.C., Higarashi M.M., Abreu V.M.N., Rocha J.D., Kwapinski W. (2012) Characterization of phosphate structures in biochar from swine bones, Pesquisa Agropecuária Brasileira 47:672-676

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The objective of this work was to develop an alternative methodology to study and characterize the phosphate crystalline properties, directly associated with solubility and plant availability, in biochar from swine bones. Some phosphate symmetry properties of pyrolyzed swine bones were established, using solid state nuclear magnetic resonance spectroscopy, principal component analysis, and multivariate curve resolution analysis, on four pyrolyzed samples at different carbonization intensities. Increasing carbonization parameters (temperature or residence time) generates diverse phosphate structures, increasing their symmetry and decreasing the crossed polarizability of the pair 1H-31P, producing phosphates with, probably, lower solubility than the ones produced at lower carbonization intensity. Additionally, a new methodology is being developed to study and characterize phosphate crystalline properties directly associated with phosphate solubility and availability to plants.


Piterina, AV, J.Barlett , J.T. Pembroke (2012) Phylogenetic Analysis of the Bacterial Community in a full scale Autothermal Thermophilic Aerobic Digester (ATAD) treating mixed domestic sludge, Water Research 46:2488-2504

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The bacterial community associated with a full scale autothermal thermophilic aerobic digester (ATAD) treating sludge, originating from domestic wastewater and destined for land spread, was analysed using a number of molecular approaches optimised specifically for this high temperature environment. 16S rDNA genes were amplified directly from sludge with universally conserved and Bacteria-specific rDNA gene primers and a clone library constructed that corresponded to the late thermophilic stage (t = 23 h) of the ATAD process. Sequence analyses revealed various 16S rDNA gene sequence types reflective of high bacterial community diversity. Members of the bacterial community included ?- and ?-Proteobacteria, Actinobacteria with High G + C content and Gram-Positive bacteria with a prevalence of the Firmicutes (Low G + C) division (class Clostridia and Bacillus). Most of the ATAD clones showed affiliation with bacterial species previously isolated or detected in other elevated temperature environments, at alkaline pH, or in cellulose rich environments. Several phylotypes associated with Fe(III)- and Mn(IV)-reducing anaerobes were also detected. The presence of anaerobes was of interest in such large scale systems where sub-optimal aeration and mixing is often the norm while the presence of large amounts of capnophiles suggest the possibility of limited convection and entrapment of CO(2) within the sludge matrix during digestion. Comparative analysis with organism identified in other ATAD systems revealed significant differences based on optimised techniques. The abundance of thermophilic, alkalophilic and cellulose-degrading phylotypes suggests that these organisms are responsible for maintaining the elevated temperature at the later stages of the ATAD process.


Troy S.M., Nolan T., Kwapinski W.Leahy J.J., Healy M.G., Lawlora P.G. (2012) Effect of sawdust addition on composting of separated raw and anaerobically digested pig manure, Journal of Environmental Management 111:70-77

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Manures need the addition of carbon-rich bulking agents to conserve N during composting, which increases the cost of the composting process. The recommended proportion of manure/sawdust, based on a carbon (C):nitrogen (N) ratio, is approximately 3:2. Two composting experiments were conducted to determine the impact of varying the proportion of sawdust to either separated raw, or separated anaerobically digested pig manures. To determine stability and maturity of the final compost, oxygen uptake rate (OUR) and germination index (GI) tests were conducted. For both experiments, three treatments were employed: manure-only (Treatment A), manure/sawdust mixed 4:1, fresh weight (Treatment B), and manure/sawdust mixed 3:2, fresh weight (Treatment C). The mixtures were composted in tumblers for 56 days with regular turning. The composting material was tested over the study duration for temperature, pH, water content, organic matter, C:N ratio and bulk density. For both Treatments B and C, the GI indicated low levels of phytotoxicity, and OUR values were lower than the recommended Irish threshold of 13 mmol O(2) kg OM(-1) h(-1), indicating that a high quality compost was produced. The proportion of sawdust to separated manure used can be reduced to make a cost saving, while still producing a stable end-product: 60% less sawdust is required to compost at a manure-to-sawdust ratio of 4:1 compared to the previously recommended ratio of 3:2.


Kolodynska, D., Wnetrzak, R.Leahy, JJHayes, MHBKwapinski, W, Hubicki, Z. (2012) Kinetic and adsorptive characterization of biochar in metal ions removal, Chemical Engineering Journal 197:295-305

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Kinetic and adsorption studies on the removal of metal ions such as Cu(II), Zn(II), Cd(II) and Pb(II) ions in the biochar (BC) samples have been carried out. The effects of several experimental parameters have been investigated using the batch adsorption technique at different temperature. The effectiveness of Cu(II), Zn(II), Cd(II) and Pb(II) ions removal increases with the increasing initial concentration of biochar and metal ion, pH as well as phase contact time. The maximum adsorption was found in the pH range 5.0–6.0. The kinetics of adsorption was found to be pseudo second order with intraparticle diffusion as one of the rate determining steps. Adsorption studies were also performed at different temperatures and modelled with the Langmuir and Freundlich adsorption isotherms.


Bulushev,D.A. Ross,J.R.H. (2011) Catalysis for conversion of biomass to fuels via pyrolysis and gasification: a review, Catalysis Today 171(1):1–13

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A current aim of society is to produce fuels from non-food biomass and catalysis is central to achieving this aim. Catalytic steam-reforming of biomass gives synthesis gas and this can be further transformed to give transport fuels using catalysis. Biofuels and fuel additives can also be obtained by catalytic upgrading of bio-oil produced by non-catalytic pyrolysis of biomass. This upgrading can be performed by low temperature esterification with alcohols (followed by water separation) or by high temperature gasification, cracking or hydrotreating processes. Upgraded bio-oil can also be obtained by pyrolysis of biomass in the presence of catalysts. This review considers recent trends in the chemistry of these processes for biofuel production and the catalysts used.

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Bulushev,D.ARoss,J.R.H. (2011) Vapour phase hydrogenation of olefins by formic acid over a Pd/C catalyst, Catalysis Today 163(1):42-46

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It has been found that ethylene and propylene could be effectively hydrogenated by formic acid vapour over a Pd/carbon catalyst at low temperatures (<440 K). Surface hydrogen formation from formic acid is the rate-determining step for this hydrogenation reaction. Interaction of this hydrogen with the olefins is then fast. The conversion of formic acid in the presence of either of the olefins at any temperature is higher than in their absence. This has been explained by a much lower surface hydrogen concentration in the presence of the olefins. Direct experiments have confirmed that hydrogen inhibits the formic acid decomposition. Water vapour addition has a small positive effect on the decomposition of formic acid as well as on the hydrogenation of the olefins with formic acid. Catalysts consisting of gold supported on carbon or titania are both active in the production of hydrogen from formic acid. However, in contrast to the Pd/C catalyst, neither gives hydrogenation of the olefins with this acid.

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Melligan, F., Auccaise, R., Novotny, E. H., Leahy, J. J.Hayes, M. H. B. (2011) Pressurised pyrolysis of Miscanthus using a fixed bed reactor, Bioresource Technology 102(3):3466–3470

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Miscanthus x giganteus was pyrolysed, in a fixed bed reactor in a constant flow of dinitrogen gas, at a rate of 13 °C/min from ambient to 550 °C, then held for 25 min at this temperature. The pressures employed ranged from atmospheric to 26 bar. The major compounds identified in the bio-oil were water, phenol, and phenol derivatives. The water contents impact on the usefulness of the bio-oil as a fuel. However, the phenols could provide useful platform chemicals and products. The properties of the char were determined using elemental analyses, surface area measurements using the Brunauer–Emmett–Teller equation, a calorimetric bomb, Scanning Electron Microscopy, and solid state 13C NMR spectroscopy. The chars were highly carbonised, especially at the higher pressures, and provided thermally stable materials. Pressure impacted greatly on the surface area. Char formed at atmospheric pressure had a surface area of 162 m2/g, whereas that from the highest pressure applied was only 0.137 m2/g


Nagaraja,B.M.Bulushev,D.A., Beloshapkin,S., Ross,J.R.H.  (2011) Effect of potassium on the activity and stability of Ni-MgO-ZrO2 catalysts for the dry reforming of methane to give synthesis gas, Catalysis Today

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It has been found that the addition of 0.5wt.% potassium to a catalyst consisting of 8wt.% Ni supported on a MgO–ZrO2 support prepared by co-precipitation improved both the activity and stability of this material for the dry reforming of methane. Increasing the content of potassium caused a decrease in the catalytic activity but the stabilities of the resultant catalysts were still higher than those for the undoped catalyst. The BET surface areas of the catalysts increased with potassium content.


Bulushev,D.A. , Beloshapkin,S., Ross,J.R.H. (2010) Hydrogen from formic acid decomposition over Pd and Au catalysts, Catalysis Today 154(1-2):7-12

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Vapour phase decomposition of formic acid has been studied systematically over a range of catalysts: 1.0 and 10 wt.% Pd/C, 0.8 wt.% Au/C and 1.0 wt.% Au/TiO2. The mean metal particle size of these materials was estimated by HRTEM and turnover frequencies were calculated using these data. The Au/C catalyst was the least active and the Pd/C catalysts were the most active for the formic acid decomposition reaction. At about 400 K, these Pd catalysts gave up to 0.04 moles of H2 per minute per gram of Pd, with a selectivity of 95–99%. The H2 selectivity for these catalysts was found to be only weakly dependent on the reaction temperature and the formic acid conversion. The Au/TiO2 catalyst showed only a moderate selectivity to H2 formation (<70%). The selectivity of this catalyst was improved considerably by the introduction of water vapour. This improvement derived from the high activity of the catalyst for the water–gas shift reaction.

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Kwapinski, W.Byrne, C. M. P.Kryachko, E., Wolfram, P., Adley, C., Novotny, E., Hayes, M. H. B. (2010) Biochar from Biomass and Waste, Waste and Biomass Valorization 1(2):177-189

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There is an increasing realisation that biomass and organic wastes are valuable feedstocks for second generation biorefining processes that give rise to platform chemicals to substitute for dwindling petrochemical resources, and for pyrolysis processes that produce syngas, bio-oil, and biochar from biomass, organic wastes, and the biorefining residuals of the future. The experimental work described has focused on physical properties and compositions of biochars produced from miscanthus (Miscanthus × giganteus), willow (Salix spp) and pine (Pinus sylvestris) at 500°C and at 400, 500, and 600°C in the case of the miscanthus. Although the morphologies of the cell structures were maintained in the pyrolysis, the surface area of the miscanthus biochar was greatly increased by heating at 600°C for 60 min. Nuclear magnetic resonance spectra showed the disappearance of evidence for the carbohydrate and lignin plant components as the pyrolysis temperature was raised, and the compositions of miscanthus biochars after heating for 10 and for 60 min at 600°C were very similar and composed of fused aromatic structures and with no traces of the aliphatic components in the starting materials. In greenhouse and growth chamber experiments the growth of maize (Zea mays L) seedlings was found to be inhibited by soil amendments with biochar from miscanthus formed at 400°C for 10 min, but stimulated by miscanthus char formed at 600°C for 60 min. In the course of discussion the relevance of the results obtained is related to the roles that soil amendments with biochar can have on soil fertility, carbon sequestration, on the emissions of greenhouse gases from soil, on fertilizer requirements, and on waste management. It is clear that biochar soil amendments can have definite agronomic and environmental benefits, but it will be essential to have clear guidelines for biochar production from various feedstocks and under varying pyrolysis parameters. It will be equally important to have a classification system for biochars that clearly indicate the product compositions that will meet acceptable standards. A case can be made for sets of standard biochars from different substrates that meet the required criteria.


Byrne, C. M. P.Hayes, M.H.B.,  Kumar, R., Novotny, E.H., Lanigan, G., Richards, K.G., Fay, D., Simpson, A.J. (2010) Compositional changes in the hydrophobic acids fraction of drainage water from different land management practices, Water Research 44(15):4379-4390

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Dissolved organic matter (DOM) can play a key role in many environmental processes, including carbon cycling, nutrient transport and the fates of contaminants and of agrochemicals. Hydrophobic acids (Ho), the major components of the DOM, were recovered from the drainage waters from well-drained (WDS) and poorly-drained (PDS) Irish grassland soils in lysimeters, amended with N fertiliser (F) and with bovine urine (U) and were studied using 1D and 2D solution-state Nuclear Magnetic Resonance (NMR) spectroscopy. The Diffusion Edited (DE) (1)H NMR spectra indicated that the Ho consisted largely of larger molecules, or of molecules that formed rigid aggregates, and the 1D and the 2D (Heteronuclear Multiple Quantum Coherence - HMQC, the Total Correlation Spectroscopy - TOCSY, and the Nuclear Overhauser Effect - NOESY) spectra indicated that the samples were composed of lignin residues, carbohydrates, protein/peptides, and aliphatic components derived from plant waxes/cuticular materials and from microbial lipids. The F amendments increased the concentrations of Ho in the waters by 1.5 and 2.5 times those in the controls in the cases of WDS and PDS, respectively. The lignin-derived components were increased by 50% and 300% in the cases of the Ho from the WDS and PDS, respectively. Applications of F + U decreased the losses of Ho, (compared to the F amendments alone) and very significantly decreased those of the lignin-derived materials, indicating that enhanced microbial activity from U gave rise to enhanced metabolism of the Ho components, and especially of lignin. In contrast the less biodegradable aliphatic components containing cuticular materials increased as the result of applications of F + U. This study helps our understanding of how management practices influence the movement of C between terrestrial and aquatic environments.

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Hayes, D. J.Hayes, M. H. B. (2009) The role that lignocellulosic feedstocks and various biorefining technologies can play in meeting Ireland’s biofuel targets, Biofpr 3(5):500-520

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This paper considers the contribution that biorefineries, through the production of second-generation biofuels from lignocellulosic feedstocks, can make in the Republic of Ireland to the mandated 10% transport biofuel quotient for 2020. An emphasis is placed on the avoidance of land-use conflict issues and, hence, on the prioritization of waste/residue utilization before dedicated energy crops are grown. It is concluded that up to 5.3% of the 2010 demand for biofuels can be met from the utilization of feasible quantities of wastes and residues in near-term biorefining technologies and that 5% of the 2020 petrol and diesel demand can be met via processing a similar quantity of waste in advanced biorefining processes based on consolidated bioprocessing micro-organisms and syngas-reforming catalysts. The remaining biofuel requirements for 2020 can be met by processing energy crops. Between 1.4% and 15.9% of the agricultural area of Ireland is required for the production of these crops, depending on the particular feedstock and technology employed. The production of a high-yielding Miscanthus crop that is harvested directly after senescence will place the minimum requirement on Irish land.

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Hayes, D. J. (2008) An Examination of Biorefining Processes, Catalysts and Challenges, Catalysis Today 145(1-2):138-151

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Biofuels offer the potential to substitute for a large proportion of fossil fuels, however it is considered that the utilisation of lignocellulosic biomass, via second-generation biorefining technologies, will be necessary for this to be achieved economically and sustainably. The lignocellulosic matrix is complex and recalcitrant to conversion but research in biorefining is advancing rapidly and commercial facilities are expected in the near-term. These facilities will either employ hydrolytic mechanisms to break apart the structural polysaccharides of the biomass, or thermochemical procedures to dehydrate and volatilise the feedstock. Catalysts serve vital roles in both approaches: acids and enzymes facilitate the hydrolysis of cellulose; while metal and biological catalysts can alter the volatilisation profiles of biomass or reform the gases that are liberated in the thermochemical process. Each potential biorefining technology currently has its own drawbacks and advantages and it is likely that a range of procedures will be needed in order to fully exploit the values of very diverse ranges of lignocellulosic feedstocks.

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Novotny, E. H.,  deAzevedo, E. R., Bonagamba, T. J., Cunha, T. J. F., Madari, B. E.,  Benites, V. M., Hayes, M. H. B. (2007) Studies of the compositions of humic acids from Amazonian Dark Earth soils, Environ. Sci. Technol. 41(2):400-405

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The compositions of humic acids (HAs) isolated from cultivated and forested “Terra Preta de Índio” or Amazonian Dark Earth soils (anthropogenic soils) were compared with those from adjacent non-anthropogenic soils (control soils) using elemental and thermogravimetric analyses, and a variety of solid-state nuclear magnetic resonance techniques. The thermogravimetric index, which indicates the molecular thermal resistance, was greater for the anthropogenic soils than for the control soils suggesting polycyclic aromatic components in the former. The cultivated anthropogenic soils were more enriched in C and depleted in H than the anthropogenic soils under forest, as the result of the selective degradation of aliphatic structures and the possible enrichment of H-deficient condensed aromatic structures. The combination of variable amplitude cross-polarization (VACP) and chemical shift anisotropy with total suppression of spinning sidebands experiments with composite ? pulses could be used to quantify the aromaticity of the HAs from the anthropogenic soils. From principal component analysis, using the VACP spectra, it was possible to separate the different constituents of the HAs, such as the carboxylated aromatic structures, from the anthropogenic soils and plant derived compounds. The data show that the HAs from anthropogenic soils have high contents of aryl and ionisable oxygenated functional groups, and the major functionalities from adjacent control soils are oxygenated functional groups from labile structures (carbohydrates, peptides, and with evidence for lignin structures). The anthropogenic soils HAs can be considered to be more recalcitrant, and with more stable reactive functional groups which may, in part, explain their more sustainable fertility due to the organic matter contribution to the soil cation exchange capacity.

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Hayes, M. H. B. (2006) Biochar and biofuels for a brighter future, Nature 443:144
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Novotny, E. H., Hayes, M. H. B., deAzevedo, E. R., Bonagamba, T. J. (2006) Characterisation of black carbon-rich samples by 13C solid-state nuclear magnetic resonance, Naturwissenschaften 93(9):447-450

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There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de Índio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. 13C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, 1H-13C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the ? pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp—variable amplitude CP (VACP)—VACP/MAS pulse sequence, and composite ? pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.

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Book Chapters

Untitled Document

Hayes, D.J.M.  (2013) Biomass composition and its relevance to biorefining, The Role of Catalysis for the Sustainable Production of Biofuels and Bio-chemicals, K. Triantafyllidis, A. Lappas, M. Stoker, Elsevier B. V. 27-65

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Biomass feedstocks for the production of biofuels and chemicals vary greatly in their chemical compositions. These differences affect which technologies are used for processing. First generation technologies focus on the conversion of sugars, starches, and oils whilst second generation technologies process lignocellulose. While the conversion in first generation processes is relatively facile, the processing of lignocellulose is hindered by the complexity of the biomass matrix. Lignocellulosic feedstocks, however, tend to be significantly less costly, in economic, environmental, and energy terms, to produce. The effects of the various constituents on the conversion of biomass by either hydrolytic or thermochemical means are discussed, as are the logistical considerations needed when sourcing feedstocks. Biomass can be classified as a specifically grown energy crop, an agricultural residue, or a waste resource. Several examples of lignocellulosic feedstocks are discussed for each of these types and representative chemical data for a variety of materials presented.


Hayes, D. J.Hayes, M. H. B., Daly, M. M. (2006) Operação inovadora de biorrefino para produção de oleos combustiveis e de quimico-platforma a partir de carboidratos de biomassa e de residuos diversos,  Usos alternativos da palhada residual da produção de sementes para pastagens, F. H. D. de Souza, E. B. Pott, O. Primavesi, A. C. C. Bernardi, EMBRAPA, Sao Carlos, SP, Brazil:161-191

Hayes, D. J., Fitzpatrick, S. W., Hayes, M. H. B.Ross, J. R. H. (2005) The Biofine Process: Production of levulinic acid, furfural and formic acid from lignocellulosic feedstocks, Biorefineries: Industrial Processes and Products, B. Kamm, P. R. Gruber , M. Kamm, Wiley, Weinheim, Germany 1:139-164
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Conference Proceedings

Untitled Document

Cheng, R.R. , R. MylotteR. McInerney, Y.M. Tzou, M.H.B. Hayes (2012) A comparison of the compositional differences between humic fractions isolated by the IHSS and exhaustive extraction procedures, Functions of Natural Organic Matter in Changing Environment. Proc. 16th IHSS International Conference (Hangzhou), J. Xu, J. Wu, Y. He:78-80

Hayes, M.H.B. (2012) Relationships between biochar and soil humic substances, Functions of Natural Organic Matter in Changing Environment. Proc. 16th IHSS International Conference (Hangzhou), J. Xu, J. Wu, Y. He:540-542

Hayes, M.H.B., Swift, R. S. (2012) Lumping or splitting: Holistic or fractionation approaches in studies of humic substances, Functions of Natural Organic Matter in Changing Environment. Proc. 16th IHSS International Conference (Hangzhou), J. Xu, J. Wu, Y. He:31-33

Melligan F.Leahy J. J.Hayes M.H.B.Kwapinski W. (2012) Hydro-pyrolysis of biomass and on-line catalytic vapour upgrading with Ni-ZSM-5 and Ni-MCM-41, COST UBIOCHEM, 3rd Workshop, Thessaloniki Greece, 1-3 November:17

Mylotte, R.C.M.P. Byrne, R.R. Cheng, C. Dalton, M.H.B. Hayes. (2012) Studies of humic substances from sediments in Galway Bay, Ireland, Functions of Natural Organic Matter in Changing Environment. Proc. 16th IHSS International Conference (Hangzhou):72-74

Piterina, A.V.Hayes, M.H.B. (2012) Classification of biochars by their mutagenicity using the Salmonella/microsome mutagenicity assay, Prooeedgs 4th International Biochar Conference (Beijing, China, Sept 17-21), G. Li:38-41

Piterina, A.V.Hayes, M. H. B. (2012) Influence of the addition of herbaceous biochar on the metabolic profiles of the maize rhizosphere microbial community. The BIOLOGECO, GP andGN plates technique, Prooeedgs 4th International Biochar Conference (Beijing, China, Sept 17-21), G. Li:74-77

Piterina, A.V.M.H.B. Hayes (2012) Influence of herbaceous biochar on root architecture, infection patterns and diversityof AMF symbionts during establishment stage (14 days) of maize growth, Prooeedgs 4th International Biochar Conference (Beijing, China, Sept 17-21), G. Li:143-146

Piterina AV, Chipman, K, Leahy, JJPembroke JTM.H.B. Hayes (2012) Method development and validation for in-vitro screening of mutagenic activity of biochars obtained from pyrolysis biorefinery processes in Salmonella typhimurium tester strains, Society for General Microbiology Spring Conference, Dublin, March 2012 :77

Piterina, A.V.J.T. Pembroke (2012) Advances in environmental microbiology and biotechnology of autothermophilic wastewater treatment peocesses, Society for General Microbiology Spring Conference, Dublin:77

Piterina, A.V.Pembroke J.T., McGloughlin, T., Beloshapkin, S., Kennedy, B., D. Haverty (2012) Technological challenges and advances in delivery of temperature sensitive biologically active materials (enzymes, cells, biotherapeutics, phades) and polymers on metal surfaces in biotechnological, diagnostic, medical device and sensor industries, Society for General Microbiology Spring Conference, Dublin, March 2012:86

Hayes, D. J. (2004) Oil substitutes utilising humic precursors: The development of a carbohydrate economy, Humic Substances and Soil and Water Environment,  L. Martin-Neto, EMBRAPA, Sao Carlos, SP, Brazil:11-13


Presentations

Untitled Document

Lynch, D., Henihan, A.M., Kwapinski, W.Leahy, J.J. (2013) Closing the loop – on-farm fluidised bed combustion of poultry litter , 9 th International Conference on Renewable Resources and Biorefineries , Antwerp, Belgium, 5 – 7 June, 2013
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Bulushev, D.A.Jia, L., Beloshapkin, S., Ross, J.R.H. (2012) Hydrogen from Decomposition of Biomass Derived Formic Acid over Pd/C Catalysts Doped by Alkali Metals, Advances in catalysis for biomass utilisation, Thessaloniki, Greece, July 2012

Hayes, D. J. M.  (2012) DIBANET, An integrated approach for making the best use of biomass, 1st Iberoamerican Congress on Biorefineries, Los Cabos, Mexico, Oct 24-26
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Hayes, D. J. M. (2012) Feedstock evaluation and development of rapid analytical methods, DIBANET and SMART CHP Networking Day, Thessaloniki, Greece, 31st Oct
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Hayes, M.H.B. (2012) Production of platform chemicals in the DIBANET Project using novel pre-treatment methods and acid hydrolysis, Congress of Bioenergy, Xi’an, China, April 27th

Hayes, M.H.B. (2012) Relationships between biochar and soil humic substances, 16th IHSS International Conference, Hangzhou, China, Sept 10-14th

Hayes, M.H.B. (2012) Platform chemicals and fuel additives from lignocellulosic biomass, CREES International Symposium, Dublin City University, June 4-6

Ross, J.R.H.Jia, L., Beloshapkin, S., Bulushev, D. A. (2012) Hydrogen from biomass: The catalytic decomposition of formic acid, 244th ACS National Meeting, Philadelphia, USA , August 2012

Bulushev, D.A.Jia, L., Beloshapkin, S., Ross, J. R. H. (2012) Heterogeneous Catalysts for Effective Hydrogen Production from Biomass Derived Formic Acid, 15th World Congress of Catalysis, Munich, Germany, July 2012

Bulushev, D.A.Jia, L., Beloshapkin, S., Ross, J.R.H. (2012) Effective hydrogen production from biomass derived formic acid on K-doped Pd/C catalysts, 243rd ACS National Meeting, San Diego, USA, March 2012

Fox A., Cullen R., Kwapinski, W., Schmalenberger A. (2012) Bacterial mobilization of sulfur and phosphorous in biochar amended soils, 14th International Symposium on Microbial Ecology “The Power of the Small”, Copenhagen, Denmark, 19-24 August 2012

Hayes, D. J. M. (2012) Collaboration in Biorefinery Research Between Europe and Latin America, III Latin American Congress Biorefineries, Pucon, Chile, 19-21 Nov
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M.H.B. HayesC.M.P. Byrne (2012) Characterization of Biochar from Pyrolysis of Miscanthus x giganteus, Its Effect on Plant Growth and Its Potential for Carbon Sequestration, Eurosoil Conference, Bari, Italy, July 2-6

Leahy J. J., Xue G., Kwapinska M.Kwapinski W (2012) Torrefaction of Miscanthus x giganteus, International Workshop of Biomass Torrefaction for Energy, Ecole des Mines d'Albi, Albi France, 10-11 May 2012

Melligan F.Leahy J.J.Hayes M.H.B.Kwapinski W. (2012) Py–GC/MS of Miscanthus with Ni-ZSM-5 and Ni-MCM-41 under a hydrogen atmosphere, 19th International Symposium on Analytical and Applied Pyrolysis, Linz, Austria, 21-25 May

Piterina, A.VJ.T. Pembroke (2012) Tapping the bioenergy potential of Rhodococcus opacus, SEI Energy 2012, Dublin, March 2012

Wnetrzak R.Leahy J.J., Peters K., Jensen L.S., Kwapinski W. (2012) Energy production potentials from pyrolysis of pig manure, 4th International Symposium on Energy from Biomass and Waste , San Servolo, Venice, Italy, Nov. 12-15

Hayes, M. H. B. (2011) Second Generation Biorefining, CHEMRAWN XIX, Kuala Lumpur, Malaysia, Sept. 28 2011
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Swift, R., Hayes, M. H. B. (2011) Biochar Produced by Pyrolysis and its Effects on Plant Growth and Carbon Sequestration, CHEMRAWN XIX, Kuala Lumpur, Malaysia, Sept. 28 2011
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Hayes, M. H. B. (2011) Biochar Characterization, International Biochar Initiative Conference, Newcastle, England, Sept 8-11, 2008

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"Biochar Characterization" - A keynote presentation by Prof. Michael Hayes at the 2008 Conference for the International Biochar Initiative (Sept 8-11, 2008). This presentation covers the advanced biochar and terra preta characterisation techniques that have been developed at Carbolea.



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Hayes, D. J. M. (2011) Analysis of Lignocellulosic Feedstocks for Biorefineries with a Focus on The Development of Near Infrared Spectroscopy as a Primary Analytical Tool, PhD Viva Presentation, University of Limerick, 24 Aug 2011
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Hayes, D. J. M. (2011) NIRS Analysis of Wet Miscanthus Samples - Development of NIRS as a Primary Analytical Tool, COST FP0901 Meeting, Paris, France, 26 Jan 2011
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Hayes, D. J. M. (2010) Introduction to the Biorefinery Concept, DIBANET Networking Day, Rio de Janeiro, Brazil, Dec 13 2010
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Hayes, D. J. M. (2010) Biomass Research at Carbolea, University of Limerick, Globe Forum, Dublin, Ireland, Nov 18th 2010
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Byrne, C. M. P. (2010) Biochar from Biorefinery Residuals, 3rd International Biochar Conference: IBI, Rio de Janeiro, Brazil, Sep. 12 – 15, 2010
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Hayes, D. J. M. (2010) Pyrolysis and the Production and Utilisation of Biochar, EPA Waste to Resource Conference, Dublin, Ireland, Sep. 27th 2010
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Byrne, C. M. P. (2010) Biochar from Miscanthus and its Effects on Plant Growth, 2nd Annual UK Biochar Conference, Rothamsted Research, England, 28th-29th April 2010
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Hayes, D. J. M. (2010) Ion Chromatography Analysis of Lignocellulosic Biomass for Evaluation of Biofuel Yields, Dionex Users Group, Dublin, Ireland, Nov 18th 2010
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Hayes, D. J. (2010) European feedstocks, DIBANET Networking Day, Rio de Janeiro, Brazil, Dec 13 2010
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Hayes, D. J. (2010) Conventional methods of biomass analysis, DIBANET Summer School, Rio de Janeiro, Brazil, Dec 14th 2010
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Hayes, D. J. (2010) Rapid biomass analysis methods, DIBANET Summer School, Rio de Janeiro, Brazil, Dec 14th 2010
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Hayes, D. J. M. (2009) The New Generation of Biofuels: How Europe and Latin America can Work Together, CONEIAP XIX, Cali, Colombia, July 1st 2009

Hayes, M. H. B. (2009) DIBANET - The Production of Sustainable Diesel Miscible Biofuels from the Residues and Wastes of Europe and Latin America, Tailor Made Fuels from Biomass, University of Aachen, Germany, June 24th 2009
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Hayes, M. H. B. (2009) Second Generation Biorefining for Sustainable Indigenous Industries for Ireland, Feasta "New Emergency Conference", Dublin, Ireland, June 11th 2009
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Posters

Untitled Document

Barbara Schaller, Teresa Curtin (2013) Direct Catalytic Conversion of Bio-Methane to Methanol, EuropaCat - XI. European Congress on Catalysis, Lyon, September 1st -6th 2013

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The Biofuel directive of the European Commission requires that a minimum of 10 % of the transport sector should be covered by alternative fuels by 2020. Methanol is a flexible key component for several alternative fuels. The objective of this project is to develop a new catalytic method for the direct catalytic conversion of methane to methanol. Copper and iron catalysts supported by zeolites seem to be relatively promising for this partial catalytic oxidation reaction. Since methane is very symmetric, it has an extreme high C-H bond stability, which requires high activation energies. Stopping the oxidation and releasing the formed methanol from the catalyst are still challenging problems.

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Barbara Schaller, Teresa Curtin (2013) Direct Catalytic Conversion of Bio-Methane to Methanol, Environ 2013, Galway, January 30th - 1st February 2013
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Hayes, D. J. M.Leahy, J. J.Hayes, M. H. B. (2012) Analysis of European Biomass Feedstocks and Development of Near Infrared Spectroscopy as a Rapid Analytical Tool, DIBANET Networking Conference, Thessaloniki, Greece, Oct 31st
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Barbara Schaller, Teresa Curtin (2012) Direct catalytic conversion of Bio-Methane to Methanol and higher Alcohols, 64th Irish Universities Chemistry Research Colloquium, University of Limerick, June 14th - 15th 2012
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Dussan, K. (2011) Peroxyformic Acid Pretreatment of Miscanthus x giganteusSeventh Edition of the International Conference on Renewable Resources and Biorefineries, Bruges, Belgium, 8 – 10 June 2011
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Byrne, C. M. P.Hayes, M. H. B., Simpson, A. J. (2010) Changes in dissolved organic matter losses from soils under different management, 15th Meeting of the International Humic Substances Society “Humic Substances and the Maintenance of Ecosystem Services”, Tenerife, Canary Islands, Spain 27th
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Mylotte, R. (2010) Study of Estuarine Sediments in Galway Bay, Ireland, 15th Meeting of the International Humic Substances Society “Humic Substances and the Maintenance of Ecosystem Services”, Tenerife, Canary Islands, Spain 27th
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Byrne, C. M. P. (2009) DIBANET - Development of Integrated Biomass Approaches Network, IRCSET 2009 Symposium - Innovation Fuelling the Smart Society, Dublin, 25 Sep 2009
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Melligan, F. (2009) Pyrolysis of Biomass to Produce Bio-Oil, IRCSET 2009 Symposium - Innovation Fuelling the Smart Society, Dublin, 25 Sep 2009
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Kryachko, E. (2009) Enhancements of Soil Fertility from Biochar Amendments, IRCSET 2009 Symposium - Innovation Fuelling the Smart Society, Dublin, 25 Sep 2009
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Kwapinski, W. (2009) Biomass Pyrolysis and Gasification and Their Applications, IRCSET 2009 Symposium - Innovation Fuelling the Smart Society, Dublin, 25 Sep 2009
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Hayes, D. J. (2009) Analysis of Biomass Feedstocks and Evaluation of Suitability for Biorefining and Pyrolysis, IRCSET 2009 Symposium - Innovation Fuelling the Smart Society, Dublin, 25 Sep 2009
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Videos

Untitled Document

Hayes, D. J. M. (2012) Feedstock evaluation and development of rapid analytical methods, DIABNET Networking Event, Thessaloniki, Greece, 31st Oct 2012

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Haverty, D. (2012) Levulinic Acid Reactor and Process Development, DIBANET Networking Day, Thessaloniki, Greece, 31 Oct 2012

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Hayes, M. H. B. (2009) Second Generation Biorefining for Sustainable Indigenous Industries for Ireland, Feasta "New Emergency Conference", Dublin, Ireland

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In this presentation, biorefining processes are outlined, with discussion of acid versus enzymatic hydrolysis for lignocellulose biorefinery feedstocks. The products of high temperature/high pressure biorefining processes yielding furfural, levulinic acid, formic acid, and biorefinery residuals are illustrated, and the extents to which the chemical products can provide platform chemicals and fuel additives are discussed. Emphasis is given to pyrolysis products (gases, bio-oil and biochar) of the residuals, and of the potential to upgrade the bio-oil to fuel additive products, and to the uses of the biochar in soil amendment processes. The presentation can be downloaded here and a video of it can be watched here or below.

   



Byrne, C. M. P. (2009) Carbon Cycles and Sinks, Feasta "New Emergency Conference", Dublin, Ireland

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Corinna examined the policies needed to get Irish land to absorb CO2 rather than release it. She reviewed the role that biochar could play in reducing nitrous oxide and methane emissions and building up the fertility and carbon content of the soil. A video of it the presentation be watched here or below.

   




Reports

Untitled Document

Hayes, D. J. M. (2012) Review of Biomass Feedstocks and Guidelines of Best Practice, DIBANET WP2 Report:150 pages

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This document is the result of the evaluation of biomass feedstocks, from Europe and Latin America, that took place as part of the DIBANET project. That project is co-financed from the 7 th Framework Programme for Research and Technological Demonstration of the European Union. (Title: Enhancing international cooperation between the EU and Latin America in the field of biofuels; Grant Agreement No: 227248-2).

The work in Task 2.1 of Work Package 2 (WP2) at DIBANET partners UL, CTC, and UNICAMP involved evaluating, on a number of levels, potential feedstocks for utilisation in the DIBANET acid-hydrolysis process (WP3). In the early stage of the project a wide number of feedstocks were examined and relevant secondary compositional data were sought from the literature. Selected feedstocks were analysed at the laboratories of UL, CTC, and UNICAMP and, from these, a limited number of feedstocks were subjected to more in-depth analysis/evaluation.

Work at UL focused on Miscanthus, cereal straws, and waste papers. The wet-chemical and spectroscopic analysis that was carried out on a wide number of Miscanthus samples have allowed for in-depth understandings to be reached regarding the changes in lignocellulosic composition, and potential biomass/biofuel yields that could be realised over the harvest window. Straws present much less chemical variation but have enough structural carbohydrates to warrant their processing in the DIBANET technology. Waste papers can have amongst the highest total carbohydrate contents of any of the feedstocks studied.

Work at CTC focused on the residues of the sugarcane industry – sugarcane bagasse and sugarcane trash (field residues from harvesting). A large number of samples were collected from a variety of sugar mills and plantations. It has been seen that there can be a significant variation in the composition of different bagasse samples, particularly with regards to the ash content. Sugarcane trash has lower total carbohydrates contents than bagasse but is still a suitable feedstock for DIBANET.

Work at UNICAMP focused on the evaluation of residues from the banana, coffee, and coconut industries. It was found that these also have potential for utilisation in the DIBANET process, however the value of the residues for this end-use is dependent on which part of the plant is utilised. For instance, coffee husks have sufficient structural carbohydrates to allow for decent yields of levulinic acid, formic acid, and furfural in DIBANET, however the leaves of the coffee plant do not. Leaves from the banana plant are also of less value for DIBANET than the other parts of the plant (e.g. stem).

A major output of this Deliverable is the downloadable electronic database that contains all of the WP2 analytical data obtained during the course of the project. It contains analytical data and predicted biorefining yields for a total of 1,281 samples. It can be obtained, free of charge, from the DIBANET website and will be a valuable tool for stakeholders in biorefining projects.

This document presents the data and evaluations that were made regarding biomass feedstocks, and also puts forward “guidelines of best practice” in terms of making the best use of these resources. A shortened version of this document can also be downloaded from the DIBANET website.

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Hayes, D. J. (2012) Protection of NIR Calibration Equations and their Application for Biomass Analysis, DIBANET WP2 Report:71 pages

Kwapinski W.Leahy J.J. (2012) Feasibility study for the construction of a pilot/commercial - scale pyrolysis unit, Report for the Foundation for the Economics of Sustainability (FEASTA):38 pages

Hayes, D. J. M. (2011) Analysis of Lignocellulosic Feedstocks for Biorefineries with a Focus on The Development of Near Infrared Spectroscopy as a Primary Analytical Tool, PhD Thesis:832 pages (over 2 volumes)

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The 2 volumes of the thesis can also be downloaded separately.

Volume 1, Volume 2, Viva Presentation

Abstract:

The processing of lignocellulosic materials in modern biorefineries will allow for the production of transport fuels and platform chemicals that could replace petroleum-derived products. However, there is a critical lack of relevant detailed compositional information regarding feedstocks relevant to Ireland and Irish conditions. This research has involved the collection, preparation, and the analysis, with a high level of precision and accuracy, of a large number of biomass samples from the waste and agricultural sectors. Not all of the waste materials analysed are considered suitable for biorefining; for example the total sugar contents of spent mushroom composts are too low. However, the waste paper/cardboard that is currently exported from Ireland has a chemical composition that could result in high biorefinery yields and so could make a significant contribution to Ireland’s biofuel demands.

Miscanthus was focussed on as a major agricultural feedstock. A large number of plants have been sampled over the course of the harvest window (October to April) from several sites. These have been separated into their anatomical fractions and analysed. This has allowed observations to be made regarding the compositional trends observed within plants, between plants, and between harvest dates. Projections are made regarding the extents to which potential chemical yields may vary. For the DIBANET hydrolysis process that is being developed at the University of Limerick, per hectare yields of levulinic acid from Miscanthus could be 20% greater when harvested early compared with a late harvest.

The wet-chemical analysis of biomass is time-consuming. Near infrared spectroscopy (NIRS) has been developed as a rapid primary analytical tool with separate quantitative models developed for the important constituents of Miscanthus, peat, and (Australian) sugarcane bagasse. The work has demonstrated that accurate models are possible, not only for dry homogenous samples, but also for wet heterogeneous samples. For glucose (cellulose) the root mean square error of prediction (RMSEP) for wet samples is 1.24% and the R2 for the validation set (R_val^2) is 0.931. High accuracies are even possible for minor analytes; e.g. for the rhamnose content of wet Miscanthus samples the RMSEP is 0.03% and the R_val^2 is 0.845. Accurate models have also been developed for pre-treated Miscanthus samples and are discussed. In addition, qualitative models have been developed. These allow for samples to be discriminated for on the basis of plant fraction, plant variety (giganteus/non-giganteus), harvest-period (early/late), and stand-age (one-year/older).

Quantitative NIRS models have also been developed for peat, although the heterogeneity of this feedstock means that the accuracies tend to be lower than for Miscanthus. The development of models for sugarcane bagasse has been hindered, in some cases, by the limited chemical variability between the samples in the calibration set. Good models are possible for the glucose and total sugars content, but the accuracy of other models is poorer. NIRS spectra of Brazilian bagasse samples have been projected onto these models, and onto those developed for Miscanthus, and the Miscanthus models appear to provide a better fit than the Australian bagasse models.

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Hayes, D. J. (2007) State of Play in The Biorefining Industry:109 pages

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Currently, on a commercial scale, all biofuels are being produced by “firstgeneration” technologies. These require expensive and high-maintenance starch/sucrose/oil-based crops as their feedstocks. Such crops tend to be detrimental to the soil and have poor energy ratios (some researchers even propose that the entire production-cycle for ethanol sourced from corn in the USA may consume more fossil energy than is present in the final product).

Mass-scale penetration of economical biofuels will only become feasible when lower value cellulosic feedstocks can be utilised. These can include: waste materials, such as cellulosic municipal solid waste; agricultural residues, such as straw; and highyielding low-maintenance energy crops, such as miscanthus and switchgrass. In order to derive value-added chemicals and fuels from these resources the lignocellulose matrix needs to be broken up and converted. Such technologies can be called “secondgeneration” and encompass the principle of a biorefinery, in that each chemical fraction is utilised for a specific end-product.

There are many potential mechanisms for lignocellulosic fractionation, the two main ones being: hydrolysis of the polysaccharides to their monomeric constituents (or their derivatives); and liquefaction (either direct or indirect) of biopolymers to basic elements, which are then recombined into chemicals and fuels.

Generally, hydrolysis schemes require the feedstock to be pretreated to a state more amenable for polysaccharide breakdown. There are many possible means of doing this: a few examples include the utilisation of steam explosion, supercritical CO2, ammonia treatment, or acids. Following pretreatment there are many ways in which polysaccharides can be hydrolysed, for example with concentrated/dilute acids, steam, enzymes, or with solvents. After hydrolysis the end-product is often in a state suitable for fermentation to ethanol (or potentially other useful chemicals such as butanol). The hydrolysis mechanism does not usually result in significant chemical alteration of the lignin biopolymer, which typically remains as a solid and can be used for heat generation or as a gasification feedstock. Technologies for producing value-added chemical derivatives of lignin are not yet well developed.

Direct liquefaction (which may also be termed pyrolysis, thermochemical conversion or thermal depolymerisation), involves the use of heat and pressure to produce an oil or chemicals (as well as non-condensable gases and a char material). Indirect liquefaction involves gasification of biomass to basic gaseous elements (CO and H2), which are then reformed to synthetic chemicals and fuels. Given that biopolymers are more extensively deconstructed than in hydrolysis schemes, particularly in gasification, end products can be less dependent on the molecular composition of biopolymers than on their elemental composition meaning that biofuel synthesis from lignin becomes feasible.
While there are no commercial biorefineries in full-scale operation, there are several pilot plants operational and many more companies promoting plans for large-scale lignocellulosic fuel production. This document attempts to summarise all the biorefining companies and technologies that are researchable under the public domain (there is therefore no evaluation of companies such as Convertech). Where sufficient process data or history is available, the company will be evaluated for its technology and/or future plans. Particular relevance will be paid to the likelihood of commercial biofuel/biochemical production in the near future. The document will be split into five sections:
(1) Companies that appear to be closest to commercial deployment of a true “second-generation” facility.
(2) Companies that are planning pilot-facilities in the short term, or commercial facilities in the longer term.
(3) Companies/organisation engaged in more basic biorefinery research. This also includes notes on research being conducted at various universities around the world.
(4) Companies involved in the development of enzymes and organisms for enzymatic-hydrolysis and fermentation.
(5) Companies involved in the genetic-engineering/breeding of plants.

It has not been possible to devote equal amounts of time and thought to each technology since the publicly available data on them vary greatly. In many instances, there has been virtually no information provided about a company’s technology. This could be because the company prefers to keep its process secret and feels no need to publish it on the public domain. It could also, however, be because there are inherent flaws with the process or that the claims promoted on press-releases/websites would appear extravagant or dishonest given a thorough examination of the technology. While the burgeoning biorefining sector offers huge investment and production potential, it also offers the prospect for “cowboy-schemes” and stock-market manipulations as was seen with the dot com bubble. It is not always easy to spot which companies are engaged in such activities given that presentation and marketing are usually their best assets but where the scientific claims seem outlandish or illogical I have made note. It is probable that established companies, which have revenue streams in other sectors, are more likely to be honest and reliable in their claims for new processes and technologies. Recently-formed companies could be considered to be more risky and their claims, potentially, more off-the-mark given that they may require private investment or favourable market trading. It is highly unlikely that all of the dozens of companies mentioned here will operate successfully and profitably, but there represents such a wide spread of technologies and market strategies that several should persevere into the developing carbohydrate economy which looks set to dominate the transport and chemical sectors in the 21 st century.

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Hayes, D. J. (2004) An Examination of Irish Feedstocks for Biorefineries, PhD Transfer Thesis:298 pages
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Hayes, D. J. (2000) Energy analysis, with the determination of energy ratios, for the generation of electricity from energy crops, Undergraduate Thesis

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Energy crops have been said to be one of the more viable of current renewable energy technologies because of high load factors and minimal environmental effects. There are concerns that the energy consumed in producing the crop is too high when compared with the usable energy gained. In this dissertation the technique of energy analysis was used to systematically analyse all energy aspects of coppice production, supply, and electricity generation in order to calculate an energy ratio (defined as the energy out divided by the energy put in). For a scheme to be viable the ratio must be above one. An EXCEL spreadsheet model was developed to calculate the ratio and to accommodate changes in parameters. Standard data involved an 8MW generating capacity plant and a radius for possible crop production of 50km. A 320km 2 section of an ordinance survey map was scanned in to the SEMPER image-processing program and a viable level of afforestation was calculated, based on land features and their exclusion zones.

In the standard scenario an energy ratio of 20.41 before generation and of 4.94 after was obtained. It was found that the ratio and the energy yield were highly sensitive to the efficiency of the conversion plant, the expected yield of the crop, and the levels of chemical fertiliser inputs. The sensitivity was significantly less for other factors. Fertilisation by waste sludge products was found to yield significant improvements in the energy budget. The standard scenario had an afforestation level of less than 0.5%. Data from the SEMPER study suggested practical levels of afforestation of over 9.5%. Such levels had a positive effect on energy ratios and yields.

The results indicated that perceptions of the inefficiencies of energy crops have been wrong and that the capabilities for ratio improvements could be realised through a wellorganised system structure and likely advances in the future in field and plant efficiencies.

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Patents

Untitled Document

Haverty, D. (2012) Lignocellulose processing, Patent Application #PCT/IE2012/000014


 

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