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Kinetic Modeling of the Ignition of Droplets of Fast Pyrolysis Bio-oil: Effect of Initial Diameter and Fuel Composition.

ABSTRACT: Fast biomass pyrolysis is an effective and promising process for high bio-oil yields, and represents one of the front-end technologies to provide alternative, sustainable fuels as a replacement of conventional, fossil-based ones. In this work, the effect of droplet initial diameter on the evaporation and ignition of droplets of crude fast pyrolysis bio-oil (FPBO) and FPBO/ethanol blend (50% vol) at ambient pressure is discussed. The experimental tests were carried out in a closed single droplet combustion chamber equipped with optical accesses, using droplets with a diameter in the range of 0.9-1.4 mm. The collected experimental data show a significant effect of droplet diameter and initial fuel composition on the evaporation and combustion of the droplets. At the same time, 1-dimensional modeling of the evaporation and ignition of different droplets of crude FPBO and its blend with ethanol is performed to understand the complex physical and chemical effects. To this purpose, an 8-component surrogate was adopted, and a skeletal mechanism (170 species and 2659 reactions) was obtained through an established methodology. The comparison of numerical and experimental results shows that the model is able to capture the main features related to the heating phase of the droplet and the effect of fuel composition on droplet temperature and evaporation, particularly the increased reactivity following ethanol addition and the variation of diameter with time. Also, a sensitivity analysis highlighted the reactions controlling the autoignition of the droplets in the different conditions. It was found that the autoignition of pure FPBO droplets is governed by dimethyl furane (DMF), because of its high volatility and in spite of not being the most abundant species. On the other side, ethanol chemistry drives the gas-phase ignition in the case of the blended (50/50 v/v) mixtures, due to its higher volatility and reactivity.

SUBMITTER: Stagni A

PROVIDER: S-EPMC8154438 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Fast pyrolysis bio-oil (FPBO), a second-generation liquid bioenergy carrier, is currently entering the market. FPBO is produced from biomass through the fast pyrolysis process and contains a large number of constituents, of which a significant part is still unknown. Various analytical methods have been systematically developed and validated for FPBO in the past; however, reliable methods for characterization of acetaldehyde, formaldehyde, and furfural are still lacking. In this work, different analysis methods with (HS-GC/ECD, HPLC, UV/Vis) and without derivatization (GC/MSD, HPLC) for the characterization of these components were evaluated. Five FPBO samples were used, covering a range of biomass materials (pine wood, miscanthus, and bark), storage conditions (freezer and room temperature), and after treatments (none, filtration, and vacuum evaporation). There was no difference among the methods for the acetaldehyde analysis. A significant difference among the methods for the determination of formaldehyde and furfural was observed. Thus, more data on the accuracy of the methods are required. The precision of all methods was below 10% with the exception of the HPLC analysis of acetaldehyde with an RSD of 14%. The concentration of acetaldehyde in the FPBO produced from the three different biomasses and stored in a freezer after production ranged from 0.24 to 0.60 wt %. Storage at room temperature and vacuum evaporation both decreased significantly the acetaldehyde concentration. Furfural concentrations ranged from 0.11 to 0.36 wt % for the five samples. Storage and after treatment affected the furfural concentration but to a lesser extent than for acetaldehyde. Storage at room temperature decreased formaldehyde similarly to acetaldehyde; however, after vacuum-evaporation the concentration of formaldehyde did not change. Thus, the analysis results indicated that in FPBO the equilibrium of formaldehyde and methylene glycol is almost completely on the methylene glycol side, as in aqueous solutions. All three methods employed here actually measure the sum of free formaldehyde and methylene glycol (FAMG).

Project description:Carbonization of biomass can prepare carbon materials with excellent properties. In order to explore the comprehensive utilization and recycling of Caragana korshinskii biomass, 15 kinds of Caragana korshinskii biochar (CB) were prepared by controlling the oxygen-limited pyrolysis process. Moreover, we pay attention to the dynamic changes of microstructure of CB and the by-products. The physicochemical properties of CB were characterized by Scanning Electron Microscope (SEM), BET-specific surface area (BET-SSA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), and Gas chromatography-mass spectrometry (GC-MS). The optimal preparation technology was evaluated by batch adsorption application experiment of NO3-, and the pyrolysis mechanism was explored. The results showed that the pyrolysis temperature is the most important factor in the properties of CB. With the increase of temperature, the content of C, pH, mesoporous structure, BET-SSA of CB increased, the cation exchange capacity (CEC) decreased and then increased, but the yield and the content of O and N decreased. The CEC, pH, and BET-SSA of CB under each pyrolysis process were 16.64-81.4 cmol·kg-1, 6.65-8.99, and 13.52-133.49 m2·g-1, respectively. CB contains abundant functional groups and mesoporous structure. As the pyrolysis temperature and time increases, the bond valence structure of C 1s, Ca 2p, and O 1s is more stable, and the phase structure of CaCO3 is more obvious, where the aromaticity increases, and the polarity decreases. The CB prepared at 650 °C for 3 h presented the best adsorption performance, and the maximum theoretical adsorption capacity for NO3- reached 120.65 mg·g-1. The Langmuir model and pseudo-second-order model can well describe the isothermal and kinetics adsorption process of NO3-, respectively. Compared with other cellulose and lignin-based biomass materials, CB showed efficient adsorption performance of NO3- without complicated modification condition. The by-products contain bio-soil and tail gas, which are potential source of liquid fuel and chemical raw materials. Especially, the bio-oil of CB contains ?-d-glucopyranose, which can be used in medical tests and medicines.

Project description:IntroductionThe aggressive search for renewable energy resources and essential pyrosynthetic compounds has marked an exponential rise in the thermal degradation of biomass materials. Consequently, clean and sustainable transport fuels are increasingly desirable in a highly industrialized economy, for energy security and environmental protection. For this reason, biomass materials have been identified as promising alternatives to fossil fuels despite the challenges resulting from the possible formation of toxic nitrogen-based molecules during biomass degradation. In order to understand the free radical characteristic challenges facing the use of bio-oil, a brief review of the effects of free radicals in bio-oil is presented.MethodologyPyrolysis was conducted in a tubular flow quartz reactor at a residence time of 2 s at 1 atm. pressure, for a total pyrolysis time of 5 min. The thermal degradation of biomass components was investigated over the temperature range of 200 to 700 °C typically in 50 °C increments under two reaction conditions; pyrolysis in N2 and oxidative pyrolysis in 5% O2 in N2. The pyrolysate effluent was analysed using a Gas chromatograph hyphenated to a mass selective detector (MSD).ResultsThe yield of levoglucosan in the pyrolysis of cellulose in the entire pyrolysis temperature range was 68.2 wt % under inert conditions and 28.8 wt % under oxidative conditions. On the other hand, formaldehyde from pyrolysis of cellulose yielded 4 wt % while that from oxidative pyrolysis was 7 wt % translating to ⁓ 1.8 times higher than the yield from pyrolysis. Accordingly, we present for the first time dioxin-like and dibenzofuran-like nitrogenated analogues from an equimassic pyrolysis of cellulose and tyrosine. Levoglucosan and formaldehyde were completely inhibited during the equimassic pyrolysis of cellulose and tyrosine.ConclusionClearly, any small amounts of N-biomass components such as amino acids in cellulosic biomass materials can inhibit the formation of levoglucosan-a major constituent of bio-oil. Overall, a judicious balance between the production of bio-oil and side products resulting from amino acids present in plant matter should be taken into account to minimize economic losses and mitigate against negative public health concerns.

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Kinetic Modeling of the Ignition of Droplets of Fast Pyrolysis Bio-oil: Effect of Initial Diameter and Fuel Composition.

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