Production and characterization of bio-oils from fast pyrolysis of tobacco processing wastes in an ablative reactor under vacuum.
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ABSTRACT:
SUBMITTER: Khuenkaeo N
PROVIDER: S-EPMC8284650 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (?30%) and carbohydrate (?27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (?35%) and aromatic (?30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (?82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.
| S-EPMC5027642 | biostudies-literature
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).
| S-EPMC8607318 | biostudies-literature
Project description:Fast-pyrolysis bio-oils (FPBOs) obtained from lignocellulosic biomass are gaining attention as sustainable fuels for various applications, including the transport sector and power production. A significant fraction of bio-oils is constituted by nitrogen-containing compounds (N fuels) that should be considered when developing surrogate models for FPBOs. Moreover, the content of N fuels in FPBOs is expected to strongly contribute to the production of nitrogen oxides (NO x ) directly from fuel-bound nitrogen (fuel NO x ), in addition to the thermal NO x formation pathways typical of high-temperature combustion conditions. This work investigates the pyrolysis and combustion chemistry of pyrrole (C4H5N), a candidate reference fuel component for FPBO surrogate models. Speciation measurements in an atmospheric pressure jet-stirred reactor have been performed for both pyrolysis and oxidation conditions. Pyrolysis experiments have been performed for 1% pyrrole/helium mixtures over the temperature range T = 925-1200 K. Oxidation experiments were carried out for 1% pyrrole/oxygen/helium mixtures at three equivalence ratios (φ = 0.5, 1.0, and 2.0) over the temperature range T = 700-1200 K. These new data significantly extend the number of experimental targets for kinetic model validation available at present for pyrrole combustion. After a thorough revision of previous theoretical and kinetic modeling studies, a preliminary kinetic model is developed and validated by means of comparison to new experimental data and those previously reported in the literature. The rate of production and sensitivity analyses highlight important pathways deserving further investigations for a better understanding of pyrrole and, more in general, N fuel combustion chemistry. A critical discussion on experimental challenges to be faced when dealing with pyrrole is also reported, encouraging further experimental investigation with advanced diagnostics.
| S-EPMC8161689 | biostudies-literature
Project description:In this study, soybean straw (SS) as a promising source of glycolaldehyde-rich bio-oil production and extraction was investigated. Proximate and ultimate analysis of SS was performed to examine the feasibility and suitability of SS for thermochemical conversion design. The effect of the co-catalyst (CaCl2 + ash) on glycolaldehyde concentration (%) was examined. Thermogravimetric-Fourier-transform infrared (TG-FTIR) analysis was applied to optimize the pyrolysis temperature and biomass-to-catalyst ratio for glycolaldehyde-rich bio-oil production. By TG-FTIR analysis, the highest glycolaldehyde concentration of 8.57% was obtained at 500 °C without the catalyst, while 12.76 and 13.56% were obtained with the catalyst at 500 °C for a 1:6 ratio of SS-to-CaCl2 and a 1:4 ratio of SS-to-ash, respectively. Meanwhile, the highest glycolaldehyde concentrations (%) determined by gas chromatography-mass spectrometry (GC-MS) analysis for bio-oils produced at 500 °C (without the catalyst), a 1:6 ratio of SS-to-CaCl2, and a 1:4 ratio of SS-to-ash were found to be 11.3, 17.1, and 16.8%, respectively. These outcomes were fully consistent with the TG-FTIR results. Moreover, the effect of temperature on product distribution was investigated, and the highest bio-oil yield was achieved at 500 °C as 56.1%. This research work aims to develop an environment-friendly extraction technique involving aqueous-based imitation for glycolaldehyde extraction with 23.6% yield. Meanwhile, proton nuclear magnetic resonance (1H NMR) analysis was used to confirm the purity of the extracted glycolaldehyde, which was found as 91%.
| S-EPMC8675037 | biostudies-literature
Project description:A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.
| S-EPMC4550300 | biostudies-literature
Project description:Fast pyrolysis bio-oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom- and energy-efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid (PrSO3 H) silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. The incorporation of macropores (200?nm) enhances the activity of mesoporous SBA-15 architectures (post-functionalized by hydrothermal saline-promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5?% (C3 ) to 110?% (C12 ). Macroporous-mesoporous PrSO3 H/SBA-15 also provides a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast-pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57?%, as determined by GC×GC-time-of-flight mass spectrometry (GC×GC-ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components.
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Project description: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.
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Project description:Thermal degradation of nylon-6 tennis string nylon wastes in inert nitrogen and air atmospheres was investigated by means of multiple heating-rate thermogravimetric analyses. The results obtained under the heating rates of 5-20 K/min are compared in terms of degradation feature and specific temperature for two atmospheres. Using nonisothermal data, kinetic analysis was thoroughly conducted using various isoconversional model-free methods, including Starink, Madhusudanan-Krishnan-Ninan, Tang, Coats-Redfern, and Flynn-Wall-Ozawa methods. With these kinetic analysis methods, the activation energy over the entire degradation process was successfully calculated. By means of the model-fitting master-plots method, the first-order chemical reaction model was determined to be the most appropriate mechanism function for describing pyrolysis and oxidative thermal degradation of nylon-6 waste. Using kinetic parameters, satisfactory matching against experimental data resulted using the Coats-Redfern method for both cases. Furthermore, thermodynamic parameters such as changes in entropy, enthalpy, and Gibbs free energy during thermal degradation processes were evaluated.
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Project description:Peracetylated Neu5Ac2en methyl ester, an intermediate in the synthesis of the influenza neuraminidase inhibitor Relenza, has been synthesized in high yields from peracetylated Neu5Ac methyl ester by flash vacuum pyrolysis. Mechanistic evidence including deuterium labeled studies and DFT (B3LYP) calculations suggest this transformation proceeds via an intramolecular syn-elimination.
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Project description:A novel anaerobic digestion configuration, the upflow multi-layer anaerobic reactor (UMAR), was developed to treat high-solids organic wastes. The UMAR was hypothesized to form multi-layer along depth due to the upflow plug flow; use of a recirculation system and a rotating distributor and baffles aimed to assist treating high-solids influent. The chemical oxygen demand (COD) removal efficiency and methane (CH4 ) production rate were 89% and 2.10 L CH4 /L/d, respectively, at the peak influent COD concentration (110.4 g/L) and organic loading rate (7.5 g COD/L/d). The 454 pyrosequencing results clearly indicated heterogeneous distribution of bacterial communities at different vertical locations (upper, middle, and bottom) of the UMAR. Firmicutes was the dominant (>70%) phylum at the middle and bottom parts, while Deltaproteobacteria and Chloroflexi were only found in the upper part. Potential functions of the bacteria were discussed to speculate on their roles in the anaerobic performance of the UMAR system. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1226-1234, 2017.
| S-EPMC6585729 | biostudies-literature