Project description:Biomass is one of the most suitable options to be used as renewable energy source due to its extensive availability and its contribution to reduce greenhouse gas emissions. Pyrolysis of lignocellulosic biomass under appropriate conditions (slow heating rate and high temperatures) can produce a quality solid product, which could be applicable to several metallurgical processes as reducing agent (biocoke or bioreducer). Two woody biomass samples (olives and eucalyptus) were pyrolyzed to produce biocoke. These biocokes were characterized by means of proximate and ultimate analysis, real density, specific surface area, and porosity and were compared with three commercial reducing agents. Finally, reactivity tests were performed both with the biocokes and with the commercial reducing agents. Bioreducers have lower ash and sulfur contents than commercial reducers, higher surface area and porosity, and consequently, much higher reactivity. Bioreducers are not appropriate to be used as top burden in blast furnaces, but they can be used as fuel and reducing agent either tuyére injected at the lower part of the blast furnace or in non-ferrous metallurgical processes where no mechanical strength is needed as, for example, in rotary kilns.
Project description:BackgroundPretreatments are one of the main bottlenecks for the lignocellulose conversion process and the search for cheaper and effective pretreatment methodologies for each biomass is a complex but fundamental task. Here, we used a 2ν5-1 fractional factorial design (FFD) to optimize five pretreatment variables: milling time, temperature, double treatment, chemical concentration, and pretreatment time in acid-alkali (EA) and acid-organosolv (EO) pretreatments, applied to elephant grass leaves.ResultsFFD allowed optimization of the pretreatment conditions using a reduced number of experiments and allowed the identification of secondary interactions between the factors. FFD showed that the temperature can be kept at its lower level and that the first acid step can be eliminated in both pretreatments, without significant losses to enzymatic hydrolysis. EA resulted in the highest release of reducing sugars (maximum of 205 mg/g substrate in comparison to 152 mg/g in EO and 40 mg/g in the untreated sample), using the following conditions in the alkali step: [NaOH] = 4.5% w/v; 85 °C and 100 min after ball milling the sample. The factors statistically significant (P < 0.05) in EA pretreatment were NaOH concentration, which contributes to improved hydrolysis by lignin and silica removal, and the milling time, which has a mechanical effect. For EO samples, the statistically significant factors to improved hydrolysis were ethanol and catalyst concentrations, which are both correlated to higher cellulose amounts in the pretreated substrates. The catalyst is also correlated to lignin removal. The detailed characterization of the main hemicellulosic sugars in the solids after pretreatments revealed their distinct recalcitrance: glucose was typically more recalcitrant than xylose and arabinose, which could be almost completely removed under specific pretreatments. In EA samples, the removal of hemicellulose derivatives was very dependent on the acid step, especially arabinose removal.ConclusionThe results presented herewith contribute to the development of more efficient and viable pretreatments to produce cellulosic ethanol from grass biomasses, saving time, costs and energy. They also facilitate the design of enzymatic cocktails and a more appropriate use of the sugars contained in the pretreatment liquors, by establishing the key recalcitrant polymers in the solids resulting from each processing step.
Project description:The influence of catalysts on the compositions of char and pyrolysis oil obtained by pyrolysis of wood biomass with pulse current heating was studied. The effects of catalysts on product compositions were analyzed using GC-MS and TEM. The compositions of some aromatic compounds changed noticeably when using a metal oxide species as the catalyst. The coexistence or dissolution of amorphous carbon and iron oxide was observed in char pyrolyzed at 800 °C with Fe3O4. Pyrolysis oil compositions changed remarkably when formed in the presence of a catalyst compared to that obtained from the uncatalyzed pyrolysis of wood meal. We observed a tendency toward an increase in the ratio of polyaromatic hydrocarbons in the pyrolysis oil composition after catalytic pyrolysis at 800 °C. Pyrolysis of biomass using pulse current heating and an adequate amount of catalyst is expected to yield a higher content of specific polyaromatic compounds.
Project description:This paper studied the synergistic effects of catalyst mixtures on biomass catalytic pyrolysis in comparison with the single catalyst in a microwave reactor and a TGA. In general, positive synergistic effects were identified based on increased mass loss rate, reduced activation energy, and improved bio-oil quality compared to the case with a single catalyst at higher catalyst loads. 10KP/10Bento (a mixture of 10% K3PO4 and 10% bentonite) increased the mass loss rate by 85 and 45% at heating rates of 100 and 25°C/min, respectively, compared to switchgrass without catalyst. The activation energy for 10KP/10Bento and 10KP/10Clino (a mixture of 10% K3PO4 and 10% clinoptilolite) was slightly lower or similar to other catalysts at 30 wt.% load. The reduction in the activation energy by the catalyst mixture was higher at 100°C/min than 25°C/min due to the improved catalytic activity at higher heating rates. Synergistic effects are also reflected in the improved properties of bio-oil, as acids, aldehydes, and anhydrosugars were significantly decreased, whereas phenol and aromatic compounds were substantially increased. 30KP (30% K3PO4) and 10KP/10Bento increased the content of alkylated phenols by 341 and 207%, respectively, in comparison with switchgrass without catalyst. Finally, the use of catalyst mixtures improved the catalytic performance markedly, which shows the potential to reduce the production cost of bio-oil and biochar from microwave catalytic pyrolysis.
Project description:Graphene, a two-dimensional carbon allotrope with a honeycomb structure, has emerged as a material of immense interest in diverse scientific and technical domains. It is mainly produced from graphite by mechanical, chemical and electrochemical exfoliation. As renewable energy and source utilization increase, including bioenergy from forest and woody residues, processed, among other methods, by pyrolysis treatment, it can be expected that biochar production will increase too. Thus, its useful applications, particularly in obtaining high-added-value products, need to be fully explored. This study aims at presenting a comprehensive analysis derived from experimental data, offering insights into the potential of biomass pyrolysis-derived biochar as a versatile precursor for the controlled synthesis of graphene and its derivatives. This approach comprehended the highest energy output and lowest negative environmental footprint, including the minimization of both toxic gas emissions during processing and heavy metals' presence in the feedstock, toward obtaining biochar suitable to be modified, employing the Hummers and intercalation with persulfate salts methods, aiming at deriving graphene-like materials. Material characterization has revealed that besides morphology and structural features of the original wooden biomass, graphitized structures are present as well, which is proven clearly by Raman and XPS analyses. Electrochemical tests revealed higher conductivity in modified samples, implying their graphene-like nature.
Project description:BackgroundThe thermophilic anaerobic bacterium Clostridium thermocellum is a multifunctional ethanol producer, capable of both saccharification and fermentation, that is central to the consolidated bioprocessing (CBP) approach of converting lignocellulosic biomass to ethanol without external enzyme supplementation. Although CBP organisms have evolved efficient machinery for biomass deconstruction, achieving complete solubilization requires targeted approaches, such as pretreatment, to prepare recalcitrant biomass feedstocks for further biological digestion. Here, differences between how C. thermocellum and fungal cellulases respond to senescent switchgrass prepared by four different pretreatment techniques revealed relationships between biomass substrate composition and its digestion by the two biological approaches.ResultsAlamo switchgrass was pretreated using hydrothermal, dilute acid, dilute alkali, and co-solvent-enhanced lignocellulosic fractionation (CELF) pretreatments to produce solids with varying glucan, xylan, and lignin compositions. C. thermocellum achieved highest sugar release and metabolite production from de-lignified switchgrass prepared by CELF and dilute alkali pretreatments demonstrating greater resilience to the presence of hemicellulose sugars than fungal enzymes. 100% glucan solubilization and glucan plus xylan release from switchgrass were achieved using the CELF-CBP combination. Lower glucan solubilization and metabolite production by C. thermocellum was observed on solids prepared by dilute acid and hydrothermal pretreatments with higher xylan removal from switchgrass than lignin removal. Further, C. thermocellum (2% by volume inoculum) showed ~?48% glucan solubilization compared to <?10% through fungal enzymatic hydrolysis (15 and 65 mg protein/g glucan loadings) of unpretreated switchgrass indicating the effectiveness of C. thermocellum's cellulosome. Overall, C. thermocellum performed equivalent to 65 and better than 15 mg protein/g glucan fungal enzymatic hydrolysis on all substrates except CELF-pretreated substrates. CELF pretreatments of switchgrass produced solids that were highly digestible regardless of whether C. thermocellum or fungal enzymes were chosen.ConclusionsThe unparalleled comprehensive nature of this work with a comparison of four pretreatment and two biological digestion techniques provides a strong platform for future integration of pretreatment with CBP. Lignin removal had a more positive impact on biological digestion of switchgrass than xylan removal from the biomass. However, the impact of switchgrass structural properties, including cellulose, hemicellulose, and lignin characterization, would provide a better understanding of lignocellulose deconstruction.
Project description:Biochar is an engineered carbon-rich substance used for soil improvement, environmental management, and other diverse applications. To date, the understanding of how biomass affects biochar microstructure has been limited due to the complexity of analysis involved in tracing the changes in the physical structure of biomass as it undergoes thermochemical conversion. In this study, we used synchrotron x-ray micro-tomography to visualize changes in the internal structure of biochar from diverse feedstock (miscanthus straw pellets, wheat straw pellets, oilseed rape straw pellets, and rice husk) during pyrolysis by collecting a sequence of 3D scans at 50 °C intervals during progressive heating from 50 °C to 800 °C. The results show a strong dependence of biochar porosity on feedstock as well as pyrolysis temperature, with observed porosity in the range of 7.41-60.56%. Our results show that the porosity, total surface area, pore volume, and equivalent diameter of the largest pore increases with increasing pyrolysis temperature up to about 550 °C. The most dramatic development of pore structure occurred in the temperature range of 350-450 °C. This understanding is pivotal for optimizing biochar's properties for specific applications in soil improvement, environmental management, and beyond. By elucidating the nuanced variations in biochar's physical characteristics across different production temperatures and feedstocks, this research advances the practical application of biochar, offering significant benefits in agricultural, environmental, and engineering contexts.
Project description:BackgroundLignocellulose is the most abundant biomass on earth. However, biomass recalcitrance has become a major factor affecting biofuel production. Although cellulose crystallinity significantly influences biomass saccharification, little is known about the impact of three major wall polymers on cellulose crystallization. In this study, we selected six typical pairs of Miscanthus samples that presented different cell wall compositions, and then compared their cellulose crystallinity and biomass digestibility after various chemical pretreatments.ResultsA Miscanthus sample with a high hemicelluloses level was determined to have a relatively low cellulose crystallinity index (CrI) and enhanced biomass digestibility at similar rates after pretreatments of NaOH and H2SO4 with three concentrations. By contrast, a Miscanthus sample with a high cellulose or lignin level showed increased CrI and low biomass saccharification, particularly after H2SO4 pretreatment. Correlation analysis revealed that the cellulose CrI negatively affected biomass digestion. Increased hemicelluloses level by 25% or decreased cellulose and lignin contents by 31% and 37% were also found to result in increased hexose yields by 1.3-times to 2.2-times released from enzymatic hydrolysis after NaOH or H2SO4 pretreatments. The findings indicated that hemicelluloses were the dominant and positive factor, whereas cellulose and lignin had synergistic and negative effects on biomass digestibility.ConclusionsUsing six pairs of Miscanthus samples with different cell wall compositions, hemicelluloses were revealed to be the dominant factor that positively determined biomass digestibility after pretreatments with NaOH or H2SO4 by negatively affecting cellulose crystallinity. The results suggested potential approaches to the genetic modifications of bioenergy crops.
Project description:This study aims to develop a mathematical model to evaluate the energy required by pretreatment processes used in the production of second generation ethanol. A dilute acid pretreatment process reported by National Renewable Energy Laboratory (NREL) was selected as an example for the model's development. The energy demand of the pretreatment process was evaluated by considering the change of internal energy of the substances, the reaction energy, the heat lost and the work done to/by the system based on a number of simplifying assumptions. Sensitivity analyses were performed on the solid loading rate, temperature, acid concentration and water evaporation rate. The results from the sensitivity analyses established that the solids loading rate had the most significant impact on the energy demand. The model was then verified with data from the NREL benchmark process. Application of this model on other dilute acid pretreatment processes reported in the literature illustrated that although similar sugar yields were reported by several studies, the energy required by the different pretreatments varied significantly.
Project description:The diverse utilization of pyrolysis liquid is closely related to its chemical compositions. Several factors affect PA compositions during the preparation. In this study, multivariate statistical analysis was conducted to assess PA compositions data obtained from published paper and experimental data. Results showed the chemical constituents were not significantly different in different feedstock materials. Acids and phenolics contents were 31.96% (CI: 25.30-38.62) and 26.50% (CI: 21.43-31.57), respectively, accounting for 58.46% (CI: 46.72-70.19) of the total relative contents. When pyrolysis temperatures range increased to above 350 °C, acids and ketones contents decreased by more than 5.2-fold and 1.53-fold, respectively, whereas phenolics content increased by more than 2.1-fold, and acetic acid content was the highest, reaching 34.16% (CI: 25.55-42.78). Correlation analysis demonstrated a significantly negative correlation between acids and phenolics (r2 = -0.43, p < 0.001) and significantly positive correlation between ketones and alcohols (r2 = 0.26, p < 0.05). The pyrolysis temperatures had a negative linear relationship with acids (slope = -0.07, r2 = 0.16, p < 0.001) and aldehydes (slope = -0.02, r2 = 0.09, p < 0.05) and positive linear relationship with phenolics (slope = 0.04, r2 = 0.07, p < 0.05). This study provides a theoretical reference of PA application.