Direct catalytic conversion of bagasse fibers to furan building blocks in organic and ionic solvents

The applications of lignocellulosic wastes to produce a wide variety of products, including biochemicals, biomaterials, and biofuels, can be an effective solution for utilizing these valuable waste materials. In this study, the production of furan building blocks from bagasse fibers was investigated by treating unbleached fibers with NMMO, [Bmim]Cl, and TMAH at different temperatures using AlCl_{3} and CrCl_{2} as the catalysts. The resulted liquors were extracted with CH_{2}Cl_{2} to obtain furan rich fraction. Analysis of extracted fractions with GC/MS indicates the production of various furanic compounds due to catalytic solvolysis with different solvents at elevated temperatures. 2(3H)-Furanone and 2-methyl-THF were the main products of catalytic treatment of bagasse fibers with NMMO. Treatment by [Bmim]Cl resulted in 2,5-dihydro furanone as the dominant product at elevated temperatures. Furan carboxylic acid methyl ester and 2,5-furan dicarboxylic acid dimethyl ester were the main TMAH reaction products with unbleached fibers. The results indicate that the type of solvent affects the solvolysis rate and dehydration of cellulose to furanic compounds. Moreover, increasing the temperature led to an increase in the formation of the furanic compounds

Comparative Production of Bio-Oil from In Situ Catalytic Upgrading of Fast Pyrolysis of Lignocellulosic Biomass

Catalytic upgrading of fast pyrolysis bio-oil from two different types of lignocellulosic biomass was conducted using an H-ZSM-5 catalyst at different temperatures. A fixed-bed pyrolysis reactor has been used to perform in situ catalytic pyrolysis experiments at temperatures of 673, 773, and 873 K, where the catalyst (H-ZSM-5) has been mixed with wood chips or lignin, and the pyrolysis and upgrading processes have been performed simultaneously. The fractionation method has been employed to determine the chemical composition of bio-oil samples after catalytic pyrolysis experiments by gas chromatography with mass spectroscopy (GCMS). Other characterization techniques, e.g., water content, viscosity, elemental analysis, pH, and bomb calorimetry have been used, and the obtained results have been compared with the non-catalytic pyrolysis method. The highest bio-oil yield has been reported for bio-oil obtained from softwood at 873 K for both non-catalytic and catalytic bio-oil samples. The results indicate that the main effect of H-ZSM-5 has been observed on the amount of water and oxygen for all bio-oil samples at three different temperatures, where a significant reduction has been achieved compared to non-catalytic bio-oil samples. In addition, a significant viscosity reduction has been reported compared to non-catalytic bio-oil samples, and less viscous bio-oil samples have been produced by catalytic pyrolysis. Furthermore, the obtained results show that the heating values have been increased for upgraded bio-oil samples compared to non-catalytic bio-oil samples. The GCMS analysis of the catalytic bio-oil samples (H-ZSM-5) indicates that toluene and methanol have shown very similar behavior in extracting bio-oil samples in contrast to non-catalytic experiments. However, methanol performed better for extracting chemicals at a higher temperature

Characterization of fast pyrolysis bio-oil from hardwood and softwood lignin

The depletion of fossil fuel reserves and the increase of greenhouse gases (GHG) emission have led to moving towards alternative, renewable, and sustainable energy sources. Lignin is one of the significant, renewable and sustainable energy sources of biomass and pyrolysis is one of the most promising technologies that can convert lignocellulosic biomass to bio-oil. This study focuses on the production and characterization of bio-oil from hardwood and softwood lignin via pyrolysis process using a bench-scale batch reactor. In this study, a mixed solvent extraction method with different polarities was developed to fractionate different components of bio-crude oil into three fractions. The obtained fractions were characterized by using gas chromatography and mass spectrometry (GCMS). The calculated bio-oil yields from Sigma Kraft lignin and Chouka Kraft lignin were about 30.2% and 24.4%, respectively. The organic solvents, e.g., toluene, methanol, and water were evaluated for chemical extraction from bio-oil, and it was found that the efficiency of solvents is as follows: water <methanol <toluene. In both types of the bio-oil samples, phenolic compounds were found to be the most abundant chemical groups which include phenol, 2-methoxy, 2-methoxy-6-methylphenol and phenol, 4-ethyl-2-methoxy that is due to the structure and the originality of lignin, which is composed of phenyl propane units with one or two methoxy groups (O-CH3) on the aromatic ring

Recent Insights into Lignocellulosic Biomass Pyrolysis:A Critical Review on Pretreatment, Characterization, and Products Upgrading

Pyrolysis process has been considered to be an efficient approach for valorization of lignocellulosic biomass into bio-oil and value-added chemicals. Bio-oil refers to biomass pyrolysis liquid, which contains alkanes, aromatic compounds, phenol derivatives, and small amounts of ketone, ester, ether, amine, and alcohol. Lignocellulosic biomass is a renewable and sustainable energy resource for carbon that is readily available in the environment. This review article provides an outline of the pyrolysis process including pretreatment of biomass, pyrolysis mechanism, and process products upgrading. The pretreatment processes for biomass are reviewed including physical and chemical processes. In addition, the gaps in research and recommendations for improving the pretreatment processes are highlighted. Furthermore, the effect of feedstock characterization, operating parameters, and types of biomass on the performance of the pyrolysis process are explained. Recent progress in the identification of the mechanism of the pyrolysis process is addressed with some recommendations for future work. In addition, the article critically provides insight into process upgrading via several approaches specifically using catalytic upgrading. In spite of the current catalytic achievements of catalytic pyrolysis for providing high-quality bio-oil, the production yield has simultaneously dropped. This article explains the current drawbacks of catalytic approaches while suggesting alternative methodologies that could possibly improve the deoxygenation of bio-oil while maintaining high production yield

Comparative Production of Bio-Oil from In Situ Catalytic Upgrading of Fast Pyrolysis of Lignocellulosic Biomass

Catalytic upgrading of fast pyrolysis bio-oil from two different types of lignocellulosic biomass was conducted using an H-ZSM-5 catalyst at different temperatures. A fixed-bed pyrolysis reactor has been used to perform in situ catalytic pyrolysis experiments at temperatures of 673, 773, and 873 K, where the catalyst (H-ZSM-5) has been mixed with wood chips or lignin, and the pyrolysis and upgrading processes have been performed simultaneously. The fractionation method has been employed to determine the chemical composition of bio-oil samples after catalytic pyrolysis experiments by gas chromatography with mass spectroscopy (GCMS). Other characterization techniques, e.g., water content, viscosity, elemental analysis, pH, and bomb calorimetry have been used, and the obtained results have been compared with the non-catalytic pyrolysis method. The highest bio-oil yield has been reported for bio-oil obtained from softwood at 873 K for both non-catalytic and catalytic bio-oil samples. The results indicate that the main effect of H-ZSM-5 has been observed on the amount of water and oxygen for all bio-oil samples at three different temperatures, where a significant reduction has been achieved compared to non-catalytic bio-oil samples. In addition, a significant viscosity reduction has been reported compared to non-catalytic bio-oil samples, and less viscous bio-oil samples have been produced by catalytic pyrolysis. Furthermore, the obtained results show that the heating values have been increased for upgraded bio-oil samples compared to non-catalytic bio-oil samples. The GCMS analysis of the catalytic bio-oil samples (H-ZSM-5) indicates that toluene and methanol have shown very similar behavior in extracting bio-oil samples in contrast to non-catalytic experiments. However, methanol performed better for extracting chemicals at a higher temperature

Valorization of bagasse alkali lignin to water-soluble derivatives through chemical modification

Black liquor is the by-product of the pulping process where the lignin, hemicellulose, and extractive materials are separated from wood to produce paper pulp. As one of the primary lignin sources, black liquor is considered an important energy source from biomass to produce biofuels and value-added chemicals. However, soda alkaline lignin has limited industrial applications due to its insolubility in water and lack of reactivity. Therefore, chemical modification is essential to enhance its industrial applications. In this study, alkali lignin from bagasse was modified through sulfonation, sulfomethylation, and amination processes using different reaction conditions. The structural analysis of obtained products was investigated by FTIR and 1H-NMR. The molecular weight distribution and thermal stability of the water-soluble products were analyzed using gel permeation chromatography (GPC) and thermogravimetric analysis (TGA), respectively. The elemental analysis was used to measure the elements (CHNSO) of the obtained water-soluble derivatives. The chemical structure analysis of the samples with FTIR and 1HNMR confirmed the modification processes. The results indicate that modification led to increased water solubility and a decrease in the precipitation pH of lignin samples, due to the introduction of sulfonate and amin functunal groups on lignin. In addition, the molecular weight and thermal stability of modified lignins were increased due to the presence of sulfonate and amine groups compared to unmodified lignin. Graphical abstract: [Figure not available: see fulltext.]