Biomass Pyrolysis Solids as Reducing Agents: Comparison with Commercial Reducing Agents.
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ABSTRACT: 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:Thermogravimetric and calorimetric analyses are applied to study how washing modifies the pyrolysis rates and heats of five samples of potato plant stems. Hot (553 K) water or dilute (hydrochloric) acid washing of powdered samples causes a reduction in the alkali content by about 62-78 or 97-99%. The feedstock variability is highly reduced, especially for dilute acid treatment. The char yields drastically decrease up to 42-50%, with increases in the peak rates and corresponding temperatures of up to 20-60% and 50-60 K, respectively. Overall, these characteristic parameters closely approach the beech wood values used for comparison. The shape of the rate curves also testifies the dissolution of nonstructural organic components (pectin, starch, and protein) essentially to the advantage of holocellulose. The ratios between activation energy and order of the global devolatilization reaction increase from about 62-98 kJ/mol (no treatment) to 78-104 kJ/mol (hot water) and 113-124 kJ/mol (dilute acid) (versus 141 kJ/mol for wood). Following washing, the strong exothermic character of the crop residues (global reaction heats from -560 to -180 J/g) is lost. The pyrolysis becomes nearly thermally neutral after hot water washing (heats from -106 to -25 J/g). Furthermore, dilute acid washing makes the process shift from exothermic to endothermic with heats around 70-270 J/g (versus 238 J/g of wood).
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: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:Catalytic fast pyrolysis (CFP) of biomass is a versatile thermochemical process for producing a biogenic oil that can be further upgraded to sustainable transportation fuels, chemicals, and materials. CFP oil exhibits reduced oxygen content and improved thermal stability compared to noncatalytic fast pyrolysis oil. However, some level of reactive oxygenates remain in CFP oils, and reactions between these species can result in molecular weight growth and increased viscosity, leading to the potential for challenges during transportation, storage, and downstream processing. Previous research has provided considerable insight into the reactivity of noncatalytic fast pyrolysis oils, but CFP oils have yet to be studied in a similar fashion. Consequently, the degree of catalytic upgrading that is necessary to effectively stabilize CFP oils has yet to be established, and little is known about the mechanistic details underlying the process. The current study addresses this knowledge gap by controlling the CFP reaction conditions to systematically vary the oxygen content of the resulting oil. Accelerated thermal reactivity studies were then performed, and the CFP oils were analyzed using gas chromatography-mass spectrometry (GC-MS), Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), gel permeation chromatography (GPC), and viscometry to evaluate the impact of heating on their physical and chemical properties. The results revealed that short chain carbonyls, anhydrosugars, and lignin derivatives with conjugated vinyl groups likely play a role in the thermal reactivity of CFP oils. Additionally, experiments performed across a wide variety of feedstocks revealed relatively low thermal reactivity for CFP oils with oxygen contents of <20 wt %. However, above this threshold value, the thermal reactivity grew exponentially as a function of oxygen content, resulting in large increases in viscosity and molecular weight. These results serve to deepen the mechanistic understanding of CFP oil thermal reactivity and help inform the development of quality specifications for catalytic upgrading to effectively stabilize CFP oils.
Project description:Iron--EDTA was shown to catalyse OH. production from H2O2 and ascorbate by a mechanism largely independent of superoxide. When ascorbate and superoxide were both present, the ascorbate mechanism was more important than superoxide as a source of OH., and would appear to be more significantly biologically.
Project description:Simultaneous saccharification and fermentation (SSF) is effective for minimizing sugar inhibition during high solids fermentation of biomass solids to ethanol. However, fungal enzymes used during SSF are optimal between 50 and 60 °C, whereas most fermentative yeast, such as Saccharomyces cerevisiae, do not tolerate temperatures above 37 °C. Kluyveromyces marxianus variant CBS 6556 is a thermotolerant eukaryote that thrives at 43 °C, thus potentially serving as a promising new host for SSF operation in biorefineries. Here, we attempt to leverage the thermotolerance of the strain to demonstrate the application of CBS 6556 in a high solids (up to 20 wt% insoluble solid loading) SSF configuration to understand its capabilities and limitations as compared to a proven SSF strain, S. cerevisiae D5A. For this study, we first pretreated hardwood poplar chips using Co-Solvent Enhanced Lignocellulosic Fractionation (CELF) to remove lignin and hemicellulose and to produce cellulose-enriched pretreated solids for SSF. Our results demonstrate that although CBS 6556 could not directly outperform D5A, it demonstrated similar tolerance to high gravity sugar solutions, superior growth rates at higher temperatures and higher early stage ethanol productivity. We discovered that CBS 6556's membrane was particularly sensitive to higher ethanol concentrations causing it to suffer earlier fermentation arrest than D5A. Cross-examination of metabolite data between CBS 6556 and D5A and cell surface imaging suggests that the combined stresses of high ethanol concentrations and temperature to CBS 6556's cell membrane was a primary factor limiting its ethanol productivity. Hence, we believe K. marxianus to be an excellent host for future genetic engineering efforts to improve membrane robustness especially at high temperatures in order to achieve higher ethanol productivity and titers, serving as a viable alternative to D5A.
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.
Project description:This work analyzes the catalytic effects induced by alkali and alkaline earth metals (AAEMs) on pyrolysis kinetics. To this end, thermogravimetric analyses (TGA) were carried out with raw beech wood and samples impregnated with NaCl, KCl and MgCl2 at four heating rates (5, 10, 15 and 30 °C/min). Obtained results showed that AAEM compounds promote the decomposition of biomass by reducing the initial and peak pyrolysis temperatures. More specifically, the catalytic effect of the alkaline earth metal was shown to be stronger than that of alkali metals. To further interpret the obtained trends, a kinetic modeling of measured data was realized using two isoconversional methods (the Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) models). With a view to identifying a suitable reaction model, model fitting and master plot methods were considered to be coupled with the isoconversional modeling approaches. The 3-D diffusion reaction model has been identified as being well suited to properly simulate the evolution of the conversion degree of each sample as a function of the temperature. Furthermore, the kinetic parameters derived from the present modeling work highlighted significant decreases of the activation energies when impregnating wood with AAEM chlorides, thus corroborating the existence of catalytic effects shifting the decomposition process to lower temperatures. A survey of the speculated pathways allowing to account for the impact of AAEMs on the thermal degradation of woody biomass is eventually proposed to better interpret the trends identified in this work.