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Analytical pyrolysis of hot water pretreated forest biomass

Fast pyrolysis is a promising technology to promote wood biomass utilization. This thermochemical process produces mainly a liquid bio-oil. Currently, a direct application of bio-oil as fuel is limited due to its poor physicochemical properties. Pressurized Hot Water Treatment (PHWT) has been applied on white spruce and trembling aspen whole wood chips prior to production of pyrolysis oil. The effect of PHWT and the influence of the fast pyrolysis parameters on the bio-oil composition and products distribution were investigated by analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS), it was carried out at two heating rates (100 C/min and 1000 C/min) and in temperature ranges from 350 C to 500 C for trembling aspen and from 400 C to 550 C for white spruce. The pyrolysis products were identified to belong to eleven chemical groups: syringyl derivatives, guaiacyl derivatives, other phenolics, anhydrosugars, low molecular weight acids, fatty acids, furans, pyrans, ketones, aldehydes and alcohols. The results of the analytical pyrolysis indicate that the higher yield is obtained from pretreated than from untreated biomass. The effect of the pretreatment is more important for the 1000 C/min heating rate than for 100 C/min. The composition analysis revealed that the higher peak area% of anhydrosugar were obtained from PHWT biomass at 1000 C/min while the phenols were the major constituents of the pyrolysis products obtained at lower, 100 C/min heating rate. It is also demonstrated that the acids are still found in pyrolysis products even after pretreatment. The Py-GC/MS results obtained in this study indicate that pretreatment affected the hardwood and softwood in quite different ways.

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A kinetic study of lignin pyrolysis over base catalyst during steam exploded depolymerization

As an effective method for comprehensive utilization of lignin, steam explosion coupled with base catalysis (SEBC) pretreatment was applied into lignin depolymerization in this paper. The pyrolytic behavior characteristics of raw lignin (RL) and SEBC pretreated lignin (SL) were investigated by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analytical technology. Pyrolysis of RL and SL was performed on a TG analyzer at multiple heating rates of 20, 60, 80, and 100 C/min up to 720 C to obtain the thermal behavior of lignin substrates. TGA results showed that the pyrolysis process of the two lignin samples has similar characteristics, and the main pyrolysis temperature range of both substrates is from 200 C to 500 C. A total loss weight of 44% and 47% at the heating rate of 20 C/min for RL and SL was observed respectively. Derivative thermogravimetric (DTG) also showed that two major decomposition reaction stages (drying stage and degradation stage) took place at a specific heating rate for RL, while three major pyrolytic reaction stages for SL (drying stage, fast degradation stage, and slow degradation stage). The heating rate mainly influences the primary pyrolysis stage of substrate, while the maximum weight loss rate and corresponding temperature would change with increasing of heating rate. At a temperature above 200 C, the pyrolysis of substrate was clearly accelerated, and all DTG curves indicated that the temperature corresponding to maximum pyrolytic rate shifted to higher temperature range with higher heating rate. The effect of steam explosion coupled with base catalysis is obvious. Based on Py-GC/MS results, it promoted the degradation of compounds from high molecular weight to low molecular weight, even accelerated cracking reactions of oxygenated products, e.g., phenol for SL’s prominent product, instead of 2-methoxy-4-ethylphenol for RL’s. Assuming that the thermal decomposition obeys first-order reaction, kinetic parameters of RL and SL pyrolysis were determined with two methods proposed by Kissinger and Ozawa. Both methods gave analogous values of activation energy and frequency factor for RL’s two pyrolytic stages and SL’s three pyrolytic stages, respectively. This study gave further confirmation that the SEBC pretreatment process could transform lignin biomass into an intermediate feedstock with favorable properties for thermo-chemical applications.

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TG-FTIR and Py-GC/MS analysis on pyrolysis and combustion of pine sawdust

Pyrolysis and combustion of pine sawdust have been investigated by using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry (TG-FTIR) analysis in this paper. Pyrolysis-gas chromatography and mass spectrometry (Py-GC/MS) analysis was employed to characterize subsequently the structure and composition of evolving gas in pine sawdust pyrolysis process. TG results showed that both pyrolysis and combustion of pine sawdust presented three weight loss stages, respectively. The apparent activation energy of pyrolysis reaction is 108.18 kJ mol-1 in temperature of 239-394 C, while under combustion process which is 128.43 kJ mol-1 and 98.338 kJ mol-1 in 226-329 C and 349-486 C, respectively. The evolving gaseous products during the pyrolysis and combustion infrared spectrums such as H2O, CH4, CO, CO2, phenol and alkane were found. Py-GC/MS results indicated that the main compounds of pine sawdust thermal decomposition were small molar gases, acetaldehyde, acetic acid, anhydride with formic and acetic anhydride. And possible formation pathways for main pyrolysis products were tentatively presented.

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The comparison of chemical liquid deposition and acid dealumination modified ZSM-5 for catalytic pyrolysis of pinewood using pyrolysis-gas chromatography/mass spectrometry

Catalyst deactivation is the main reason for low petrochemical yield in catalytic fast pyrolysis (CFP) of biomass. ZSM-5 catalysts modified by chemical liquid deposition (CLD) and acid dealumination (AD) were prepared to improve petrochemical yields for CFP of pinewood. The results showed that CLD by SiO2 led to the coverage of strong acid sites, while AD favored the removal of superficial acid sites. CFP of pinewood showed that the relative area ratio of BTX was boosted by 37.2% and 30.4% over modified ZSM-5 catalysts by CLD and AD, respectively. The yield of indenes and naphthalenes which were important precursors of heavy coke decreased sharply. Considering environmental cost and catalytic performance, CLD seems to be a preferable modification method over ZSM-5 in the catalytic pyrolysis of biomass for petrochemicals.

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Effect of methyl jasmonate on the aroma of Sangiovese grapes and wines

Methyl jasmonate (MeJA) was applied in a vineyard on leaves and grape clusters of cv Sangiovese to test its ability to stimulate the production of aromas and identify the main genes involved in the biosynthetic pathways switched on by the elicitor. MeJA application led to a delay in grape technological maturity and a significant increase in the concentration of several berry aroma classes (about twice the total aroma: from around 3 to 6 mug/g of berry). Of these, monoterpenes showed the most significant increase. An analysis of the expression of terpenoid biosynthesis genes confirmed that the MeJA application activated the related biosynthetic pathway. The expression of all the TPS genes analyzedwas higher in samples treated with MeJA. Also the wines produced by microvinification of Sangiovese treated and untreated grapes showed a rise in the aroma concentration as in berries, with an important impact on longevity and sensorial characters of wines.

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Pyrolysis of poplar wood sawdust by TG-FTIR and Py-GC/MS

Pyrolysis of certain poplar wood sawdust (PWS) was studied by thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR). Different heating rates were applied with final temperature of 950 C and about 80% loss weight was observed at the heating rate of 20-80 C/min. The temperature trend of evolving gaseous products of PWS was also investigated. Following experimental research on pyrolysis of PWS was carried out on a pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS). Associated with the analysis results of TG-FTIR and Py-GC/MS for the pyrolytic products, PWS undergoes in three consecutive stages, corresponding to (1) moisture evaporation, (2) thermal decomposition, and (3) further carbonization. The main pyrolysis sections and the maximum weight loss rates are similar for different heating rates. Carbonyls, including aldehydes and ketones, are the main volatile products, in addition to phenols, furans, benzenes, acids, and so on. As the main gaseous products, CO, CO2, CH4 are released out greatly. Furthermore, possible pyrolysis mechanisms of cellulose, hemicellulose and lignin in biomass including PWS were also proposed. All of the results and findings would help further understanding of thermal behavior of PWS and its thermo-chemical utilization for fuels and chemicals.

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O-Quinone Methides via Oxone-Mediated Benzofuran Oxidative Dearomatization and Their Intramolecular Cycloaddition with Carbonyl Groups: An Expeditious Construction of the Central Tetracyclic Core of Integrastatins, Epicoccolide A, and Epicocconigrone A

The intramolecular cycloaddition of o-quinone methides (o-QMs) with a carbonyl group has been envisaged and executed successfully in the context of constructing the complex and rare [6,6,6,6]-tetracyclic core found in the integrastatins, epicoccolide A, and epicocconigrone A. These transient o-QMs were generated easily from the oxidative dearomatization of the corresponding C2-(aryl)benzofuran by employing Oxone in acetone-water at rt. The subsequent cycloaddition with the carbonyl (or conjugated olefin) present on the C2-aryl group was spontaneous.

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Benzofuran – Wikipedia,
Benzofuran | C8H2118O – PubChem