Progress in upscaling Miscanthus biomass production for the European bio-economy with seed-based hybrids

Funded by UK's Biotechnology and Biological Sciences Research Council (BBSRC) Department for Environment, Food and Rural Affairs (DEFRA). Grant Number: LK0863 BBSRC strategic programme Grant on Energy Grasses & Bio-refining. Grant Number: BBS/E/W/10963A01 OPTIMISC. Grant Number: FP7-289159 WATBIO. Grant Number: FP7-311929 Innovate UK/BBSRC ‘MUST’. Grant Number: BB/N016149/1

Fast pyrolysis of biomass for energy and fuels

Bioenergy is now accepted as having the potential to provide the major part of the projected renewable energy provisions of the future as biofuels in the form of gas, liquid or solid fuels or electricity and heat. There are three main routes to providing these biofuels — thermal conversion, biological conversion and physical conversion — all of which employ a range of chemical reactor configurations and process designs. This paper focuses on fast pyrolysis from which the liquid, often referred to as bio-oil, can be used on-site or stored or transported to centralised and/or remote user facilities for utilisation for example as a fuel, or further processing to biofuels and/or chemicals. This offers the potential for system optimisation, much greater economies of scale and exploitation of the concepts of biorefineries. The technology of fast pyrolysis is described, particularly the reactors that have been developed to provide the necessary conditions to optimise performance. The primary liquid product is characterised, as well as the secondary products of electricity and/or heat, liquid fuels and a considerable number of chemicals. The main technical and non-technical barriers to the market deployment of the various technologies are identified and briefly discussed.

Dynamic Life Cycle Assessment Modeling Approaches for Transboundary Energy Feedstocks

The rise of the twenty-first century has seen the further increase in the industrialization of Earth’s resources, as society aims to meet the needs of a growing population while still protecting our environmental and natural resources. The advent of the industrial bioeconomy – which encompasses the production of renewable biological resources and their conversion into food, feed, and bio-based products – is seen as an important step in transition towards sustainable development and away from fossil fuels. One sector of the industrial bioeconomy which is rapidly being expanded is the use of biobased feedstocks in electricity production as an alternative to coal, especially in the European Union.

As bioeconomy policies and objectives increasingly appear on political agendas, there is a growing need to quantify the impacts of transitioning from fossil fuel-based feedstocks to renewable biological feedstocks. Specifically, there is a growing need to conduct a systems analysis and potential risks of increasing the industrial bioeconomy, given that the flows within it are inextricably linked. Furthermore, greater analysis is needed into the consequences of shifting from fossil fuels to renewable feedstocks, in part through the use of life cycle assessment modeling to analyze impacts along the entire value chain.

To assess the emerging nature of the industrial bioeconomy, three objectives are addressed: (1) quantify the global industrial bioeconomy, linking the use of primary resources with the ultimate end product; (2) quantify the impacts of the expaning wood pellet energy export market of the Southeastern United States; (3) conduct a comparative life cycle assessment, incorporating the use of dynamic life cycle assessment, of replacing coal-fired electricity generation in the United Kingdom with wood pellets that are produced in the Southeastern United States.

To quantify the emergent industrial bioeconomy, an empirical analysis was undertaken. Existing databases from multiple domestic and international agencies was aggregated and analyzed in Microsoft Excel to produce a harmonized dataset of the bioeconomy. First-person interviews, existing academic literature, and industry reports were then utilized to delineate the various intermediate and end use flows within the bioeconomy. The results indicate that within a decade, the industrial use of agriculture has risen ten percent, given increases in the production of bioenergy and bioproducts. The underlying resources supporting the emergent bioeconomy (i.e., land, water, and fertilizer use) were also quantified and included in the database.

Following the quantification of the existing bioeconomy, an in-depth analysis of the bioenergy sector was conducted. Specifically, the focus was on quantifying the impacts of the emergent wood pellet export sector that has rapidly developed in recent years in the Southeastern United States. A cradle-to-gate life cycle assessment was conducted in order to quantify supply chain impacts from two wood pellet production scenarios: roundwood and sawmill residues. For reach of the nine impact categories assessed, wood pellet production from sawmill residues resulted in higher values, ranging from 10-31% higher.

The analysis of the wood pellet sector was then expanded to include the full life cycle (i.e., cradle-to-grave). In doing to, the combustion of biogenic carbon and the subsequent timing of emissions were assessed by incorporating dynamic life cycle assessment modeling. Assuming immediate carbon neutrality of the biomass, the results indicated an 86% reduction in global warming potential when utilizing wood pellets as compared to coal for electricity production in the United Kingdom. When incorporating the timing of emissions, wood pellets equated to a 75% or 96% reduction in carbon dioxide emissions, depending upon whether the forestry feedstock was considered to be harvested or planted in year one, respectively.

Finally, a policy analysis of renewable energy in the United States was conducted. Existing coal-fired power plants in the Southeastern United States were assessed in terms of incorporating the co-firing of wood pellets. Co-firing wood pellets with coal in existing Southeastern United States power stations would result in a nine percent reduction in global warming potential.

Overview on bio-based building material made with plant aggregate

Global warming, energy savings, and life cycle analysis issues are factors that have contributed to the rapid expansion of plant-based materials for buildings, which can be qualified as environmental-friendly, sustainable and efficient multifunctional materials. This review presents an overview on the several possibilities developed worldwide about the use of plant aggregate to design bio-based building materials. The use of crushed vegetal aggregates such as hemp (shiv), flax, coconut shells and other plants associated to mineral binder represents the most popular solution adopted in the beginning of this revolution in building materials. Vegetal aggregates are generally highly porous with a low apparent density and a complex architecture marked by a multi-scale porosity. These geometrical characteristics result in a high capacity to absorb sounds and have hygro-thermal transfer ability. This is one of the essential characteristics which differ of vegetal concrete compared to the tradition mineral-based concretes. In addition, the high flexibility of the aggregates leads to a non-fragile elasto-plastic behavior and a high deformability under stress, lack of fracturing and marked ductility with absorbance of the strains ever after having reached the maximum mechanical strength. Due to the sensitivity to moisture, the assessment of the durability of vegetal concrete constitutes one of the next scientific challenging of bio-based building materials.

Essential scientific mapping of the value chain of thermochemical converted second-generation bio-fuels

As the largest contributor to renewable energy, biomass (especially lignocellulosic biomass) has significant potential to address atmospheric emission and energy shortage issues. The bio-fuels derived from lignocellulosic biomass are popularly referred to as second-generation bio-fuels. To date, several thermochemical conversion pathways for the production of second-generation bio-fuels have shown commercial promise; however, most of these remain at various pre-commercial stages. In view of their imminent commercialization, it is important to conduct a profound and comprehensive comparison of these production techniques. Accordingly, the scope of this review is to fill this essential knowledge gap by mapping the entire value chain of second-generation bio-fuels, from technical, economic, and environmental perspectives. This value chain covers i) the thermochemical technologies used to convert solid biomass feedstock into easier-to-handle intermediates, such as bio-oil, syngas, methanol, and Fischer-Tropsch fuel; and ii) the upgrading technologies used to convert intermediates into end products, including diesel, gasoline, renewable jet fuels, hydrogen, char, olefins, and oxygenated compounds. This review also provides an economic and commercial assessment of these technologies, with the aim of identifying the most adaptable technology for the production of bio-fuels, fuel additives, and bio-chemicals. A detailed mapping of the carbon footprints of the various thermochemical routes to second-generation bio-fuels is also carried out. The review concludes by identifying key challenges and future trends for second-generation petroleum substitute bio-fuels.

Análise de um queimador infravermelho funcionando com combustível híbrido : GLP/Bio-óleo

Biomass is considered the largest renewable energy source that can be used in an environmentally sustainable. From the pyrolysis of biomass is possible to obtain products with higher energy density and better use properties. The liquid resultant of this process is traditionally called bio-oil. The use of infrared burners in industrial applications has many advantages in terms of technical-operational, for example, uniformity in the heat supply in the form of radiation and convection, with a greater control of emissions due to the passage of exhaust gases through a macroporous ceramic bed. This paper presents a commercial infrared burner adapted with an ejector proposed able to burn a hybrid configuration of liquefied petroleum gas (LPG) and bio-oil diluted. The dilution of bio-oil with absolute ethanol aimed to decrease the viscosity of the fluid, and improving the stability and atomization. It was introduced a temperature controller with thermocouple modulating two stages (low heat / high heat), and solenoid valves for fuels supply. The infrared burner has been tested, being the diluted bio-oil atomized, and evaluated its performance by conducting energy balance. The method of thermodynamic analysis to estimate the load was used an aluminum plate located at the exit of combustion gases and the distribution of temperatures measured by thermocouples. The dilution reduced the viscosity of the bio-oil in 75.4% and increased by 11% the lower heating value (LHV) of the same, providing a stable combustion to the burner through the atomizing with compressed air and burns combined with LPG. Injecting the hybrid fuel there was increase in the heat transfer from the plate to the environment in 21.6% and gain useful benefit of 26.7%, due to the improved in the efficiency of the 1st Law of Thermodynamics of infrared burner

Pirólise termoquímica de pós da fibra de coco seco em um reator de cilindro rotativo para produção de bio-óleo

This master thesis aims at developing a new methodology for thermochemical degradation of dry coconut fiber (dp = 0.25mm) using laboratory rotating cylinder reactor with the goal of producing bio-oil. The biomass was characterized by infrared spectroscopy with Fourier transform FTIR, thermogravimetric analysis TG, with evaluation of activation energy the in non-isothermal regime with heating rates of 5 and 10 °C/min, differential themogravimetric analysis DTG, sweeping electron microscopy SEM, higher heating value - HHV, immediate analysis such as evaluated all the amounts of its main constituents, i.e., lignin, cellulose and hemicelluloses. In the process, it was evaluated: reaction temperature (450, 500 and 550oC), carrier gas flow rate (50 and 100 cm³/min) and spin speed (20 and 25 Hz) to condensate the bio-oil. The feed rate of biomass (540 g/h), the rotation of the rotating cylinder (33.7 rpm) and reaction time (30 33 min) were constant. The phases obtained from the process of pyrolysis of dry coconut fiber were bio-oil, char and the gas phase non-condensed. A macroscopic mass balance was applied based on the weight of each phase to evaluate their yield. The highest yield of 20% was obtained from the following conditions: temperature of 500oC, inert gas flow of 100 cm³/min and spin speed of 20 Hz. In that condition, the yield in char was 24.3%, non-condensable gas phase was 37.6% and losses of approximately 22.6%. The following physicochemical properties: density, viscosity, pH, higher heating value, char content, FTIR and CHN analysis were evaluated. The sample obtained in the best operational condition was subjected to a qualitative chromatographic analysis aiming to know the constituents of the produced bio-oil, which were: phenol followed by sirigol, acetovanilona and vinyl guaiacol. The solid phase (char) was characterized through an immediate analysis (evaluation of moisture, volatiles, ashes and fixed carbon), higher heating value and FTIR. The non-condensing gas phase presented as main constituents CO2, CO and H2. The results were compared to the ones mentioned by the literature.

Conversão térmica e termocatalítica à baixa temperatura do óleo de girassol para obtenção de bio-óleo

The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel

Desenvolvimento de uma unidade pirolítica com reator de cilindro rotativo: obtenção de bio-óleo

The demand for alternative sources of energy drives the technological development so that many fuels and energy conversion processes before judged as inadequate or even non-viable, are now competing fuels and so-called traditional processes. Thus, biomass plays an important role and is considered one of the sources of renewable energy most important of our planet. Biomass accounts for 29.2% of all renewable energy sources. The share of biomass energy from Brazil in the OIE is 13.6%, well above the world average of participation. Various types of pyrolysis processes have been studied in recent years, highlighting the process of fast pyrolysis of biomass to obtain bio-oil. The continuous fast pyrolysis, the most investigated and improved are the fluidized bed and ablative, but is being studied and developed other types in order to obtain Bio-oil a better quality, higher productivity, lower energy consumption, increased stability and process reliability and lower production cost. The stability of the product bio-oil is fundamental to designing consumer devices such as burners, engines and turbines. This study was motivated to produce Bio-oil, through the conversion of plant biomass or the use of its industrial and agricultural waste, presenting an alternative proposal for thermochemical pyrolysis process, taking advantage of particle dynamics in the rotating bed that favors the right gas-solid contact and heat transfer and mass. The pyrolyser designed to operate in a continuous process, a feeder containing two stages, a divisive system of biomass integrated with a tab of coal fines and a system of condensing steam pyrolytic. The prototype has been tested with sawdust, using a complete experimental design on two levels to investigate the sensitivity of factors: the process temperature, gas flow drag and spin speed compared to the mass yield of bio-oil. The best result was obtained in the condition of 570 oC, 25 Hz and 200 cm3/min, temperature being the parameter of greatest significance. The mass balance of the elementary stages presented in the order of 20% and 37% liquid pyrolytic carbon. We determined the properties of liquid and solid products of pyrolysis as density, viscosity, pH, PCI, and the composition characterized by chemical analysis, revealing the composition and properties of a Bio-oil.

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Sustainable Energy Production in the United States: Life Cycle Assessment of Biofuels and Bioenergy

The United States of America is making great efforts to transform the renewable and abundant biomass resources into cost-competitive, high-performance biofuels, bioproducts, and biopower. This is the key to increase domestic production of transportation fuels and renewable energy, and reduce greenhouse gas and other pollutant emissions. This dissertation focuses specifically on assessing the life cycle environmental impacts of biofuels and bioenergy produced from renewable feedstocks, such as lignocellulosic biomass, renewable oils and fats. The first part of the dissertation presents the life cycle greenhouse gas (GHG) emissions and energy demands of renewable diesel (RD) and hydroprocessed jet fuels (HRJ). The feedstocks include soybean, camelina, field pennycress, jatropha, algae, tallow and etc. Results show that RD and HRJ produced from these feedstocks reduce GHG emissions by over 50% compared to comparably performing petroleum fuels. Fossil energy requirements are also significantly reduced. The second part of this dissertation discusses the life cycle GHG emissions, energy demands and other environmental aspects of pyrolysis oil as well as pyrolysis oil derived biofuels and bioenergy. The feedstocks include waste materials such as sawmill residues, logging residues, sugarcane bagasse and corn stover, and short rotation forestry feedstocks such as hybrid poplar and willow. These LCA results show that as much as 98% GHG emission savings is possible relative to a petroleum heavy fuel oil. Life cycle GHG savings of 77 to 99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion for electricity, depending on the biomass feedstock and combustion technologies used. Transportation fuels hydroprocessed from pyrolysis oil show over 60% of GHG reductions compared to petroleum gasoline and diesel. The energy required to produce pyrolysis oil and pyrolysis oil derived biofuels and bioelectricity are mainly from renewable biomass, as opposed to fossil energy. Other environmental benefits include human health, ecosystem quality and fossil resources. The third part of the dissertation addresses the direct land use change (dLUC) impact of forest based biofuels and bioenergy. An intensive harvest of aspen in Michigan is investigated to understand the GHG mitigation with biofuels and bioenergy production. The study shows that the intensive harvest of aspen in MI compared to business as usual (BAU) harvesting can produce 18.5 billion gallons of ethanol to blend with gasoline for the transport sector over the next 250 years, or 32.2 billion gallons of bio-oil by the fast pyrolysis process, which can be combusted to generate electricity or upgraded to gasoline and diesel. Intensive harvesting of these forests can result in carbon loss initially in the aspen forest, but eventually accumulates more carbon in the ecosystem, which translates to a CO2 credit from the dLUC impact. Time required for the forest-based biofuels to reach carbon neutrality is approximately 60 years. The last part of the dissertation describes the use of depolymerization model as a tool to understand the kinetic behavior of hemicellulose hydrolysis under dilute acid conditions. Experiments are carried out to measure the concentrations of xylose and xylooligomers during dilute acid hydrolysis of aspen. The experiment data are used to fine tune the parameters of the depolymerization model. The results show that the depolymerization model successfully predicts the xylose monomer profile in the reaction, however, it overestimates the concentrations of xylooligomers.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.

Acetic acid ketonization over Fe3O4/SiO2 for pyrolysis bio-oil upgrading

A family of silica supported, magnetite nanoparticle catalysts was synthesized and investigated for continuous flow acetic acid ketonization as a model pyrolysis bio-oil upgrading reaction. Physicochemical properties of Fe3O4/SiO2 catalysts were characterized by HRTEM, XAS, XPS, DRIFTS, TGA and porosimetry. Acid site densities were inversely proportional to Fe3O4 particle size, although acid strength and Lewis character were size invariant, and correlated with the specific activity for vapor phase acetic ketonization to acetone. A constant activation energy (~110 kJ.mol-1), turnover frequency (~13 h-1) and selectivity to acetone of 60 % were observed for ketonization across the catalyst series, implicating Fe3O4 as the principal active component of Red Mud waste.

Análisis crítico a los agro(bio)combustibles

Industry, governments, and scientists that promote biofuels think these will become an alternative to oil, which is running out. These new fuels are supposed to help in containing climate change through greenhouse gas emission reduction, increasing farmers´ incomes, and promoting rural development. However, rigorous research and analyses undertaken by serious ecologists and social scientists suggests that the current boom in biofuels industry will be disastrous for farmers, the natural environment, the preservation of biodiversity, and particularly for poor consumers.