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Degumming is the dominant method to isolate cellulosic fibers in the textile industry. High content of lignin is the principle obstacle in bast-fibers degumming. In order to remove lignin efficiently, the treatment using steam explosion coupled with Fenton oxidation was conducted on kenaf bast in this study. The influence and mechanism of the combined treatment of steam explosion and Fenton oxidation were studied. Fiber microstructure, composition proportion and distribution, cellulose Segal crystallinity and polymerization as well as residual lignin structure were analyzed. The results showed that the pretreatment of steam explosion could sufficiently extract most of the hemicellulose from kenaf bast. Also, the Fenton oxidation followed by alkaline boiling could effectively remove the lignin from the fiber, especially from the fiber surface. The refined dry fibers produced only remained 8.82% of hemicellulose and 9.36% of lignin. And the whole treatment process didn’t change the cellulose crystalline structure but could gradually degrade hemicellulose, lignin and other amorphous gummy matter as well as disordered areas in cellulose, leading to the increase of fiber Segal crystallinity from 62.02 to 70.12%. Part of cellulose was damaged with the increase of degumming intensity, resulting in the decrease of the polymerization degree of cellulose. Meanwhile, the structure of residual lignin changed during the degumming stages of steam explosion, Fenton oxidation and alkaline boiling. All the results revealed that the treatment of combined steam explosion and Fenton oxidation is significantly effectual for isolating bast-fibers. [ABSTRACT FROM AUTHOR]

Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. [ABSTRACT FROM AUTHOR]

Biomass pyrolysis oil has been reported as a potential renewable biofuel precursor. Although several review articles focusing on lignocellulose pyrolysis can be found, the one that particularly focus on lignin pyrolysis is still not available in literature. Lignin is the second most abundant biomass component and the primary renewable aromatic resource in nature. The pyrolysis chemistry and mechanism of lignin are significantly different from pyrolysis of cellulose or entire biomass. Therefore, different from other review articles in the field, this review particularly focuses on the recent developments in lignin pyrolysis chemistry, mechanism, catalysts, and the upgrading of the bio-oil from lignin pyrolysis. Although bio-oil production from pyrolysis of biomass has been proven on commercial scale and is a very promising option for production of renewable chemicals and fuels, there are still several drawbacks that have not been solved. The components of biomass pyrolysis oils are very complicated and related to the properties of bio-oil. In this review article, the details about pyrolysis oil components particularly those from lignin pyrolysis processes will be discussed first. Due to the poor physical and chemical property, the lignin pyrolysis oil has to be upgraded before usage. The most common method of upgrading bio-oil is hydrotreating. Catalysts have been widely used in petroleum industry for pyrolysis bio-oil upgrading. In this review paper, the mechanism of the hydrodeoxygenation reaction between the model compounds and catalysts will be discussed and the effects of the reaction condition will be summarized. [ABSTRACT FROM AUTHOR]

Highlights: [•] Pyrolysis of SW kraft lignin and pine wood were examined. [•] Various NMR and GPC were used to characterize various pyrolysis oils. [•] Fast pyrolysis improved cleavage of methoxyl, aliphatic C C and carbonyl bonds. [•] Fast pyrolysis produced more PAH from lignin. [•] Molecular weight of fast pyrolysis oils increased by ∼100%. [Copyright &y& Elsevier]

Abstract: The hydrogenation of biomass pyrolysis oils to upgraded biofuels, especially the aliphatic compounds with a low boiling range has attracted significant research attention. However, compared with the water soluble phase of pyrolysis oils, the water insoluble parts are relatively difficult to upgrade due to the complex high molecular weight aromatic structures. To solve this problem, a two step hydrogenation of water insoluble pyrolysis oil (heavy oil) produced from pyrolysis of pine wood ethanol organosolv lignin (EOL) at 600°C for 30min was examined. Ru/C was used as the catalyst and water was used as the dispersant for the heavy oil and hydrogenation products. The carbon conversion yields for the first and second step hydrogenation are 35% and 33% (overall molar% of carbon content in the heavy oil), respectively. The products of first step of hydrogenation are primarily aromatic molecules which are produced from the hydrolytic cleavage of ether bond and methoxy groups in the heavy oils. Further hydrogenation was shown to covert the insoluble heavy oils (weight average molecular weight is 265g/mol) to the aliphatic alcohols and other aliphatic components which could be used as renewable gasoline. As far as we know, this is the first reported effort to upgrade water insoluble parts of lignin pyrolysis oil to the total aliphatic components by aqueous phase hydrogenation. [Copyright &y& Elsevier]

The torrefaction of Loblolly pine (Pinus taeda) was examined at 250 and 300 °C, to determine the effects of treatment temperatures on the chemical structure of the torrefied Loblolly pine. Solid-state cross-polarization/magic angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) spectroscopy was used to characterize the torrefied and native Loblolly pine. The NMR results indicate that aryl-ether bonds in lignin were cleaved during the torrefaction. The methyl carbons in hemicellulose acetyl groups were no longer present after the torrefaction at 250 °C for 4 h, which is consistent with HPLC carbohydrate analysis of the torrefied wood which indicated that the hemicellulose fraction of pine was completely absent, whereas the cellulose and lignin remained largely intact. Under these conditions the torrefied wood has a relatively high energy yield of 81.29% and a HHV of 24.06 MJ kg−1. After torrefaction at 300 °C for 4 h, the cellulose and hemicellulose in the wood were completely eliminated, the residue contains enriched amounts of carbonyl groups, aromatic carbons and methoxyl groups, which represent complex condensed aromatics, these aromatics units were linked with aliphatic C–O and C–C bonds and the product has a very high HHV of 32.34 MJ kg−1. [ABSTRACT FROM AUTHOR]

A common goal in present and future forestry, biofuels and biomaterials practices, is the need to valorize lignocellulose processes to maximize value and optimize autonomic economy. Consequently, a key focus of modern biorefining is the on-site utilization of all residual materials generating products of the highest possible value. The LignoBoost process, recently demonstrated on the pilot-scale at Kraft pulp mills, injects CO2 into pulping liquors which results in a lower solution pH and thereby precipitates lignin. The present paper compares and evaluates the pyrolysis of pulping liquor lignins precipitated by sulfuric acid (pH 3) and the aforementioned CO2 method (pH 10.5 and 9.5). The CO2 based process yielded lignin that showed superior pyrolysis properties including low gas formation and increased bio-oil yields, close to 40%, consisting primarily of low (∼150 g mol−1) molecular weight compounds. Subsequent NMR analysis showed that the oils exhibit favorable changes in functionalities, e.g. loss of aromatic and gain in aliphatic carbon percentages as well as decrease in carboxyl and methoxyl (oxygen containing) groups. Moreover, NMR results further confirmed previously hypothesized lignin pyrolysis reactions, while at the same time showed the potential of CO2 precipitated lignin for pyrolysis and subsequent liquid biofuel production. [ABSTRACT FROM AUTHOR]

Pyrolysis of raw pine bark, pine, and Douglas-Fir bark was examined. The pyrolysis oil yields of raw pine bark, pine, and Douglas-Fir bark at 500 °C were 29.18%, 26.67%, and 26.65%, respectively. Both energy densification ratios (1.32–1.56) and energy yields (48.40–54.31%) of char are higher than pyrolysis oils (energy densification ratios: 1.13–1.19, energy yields: 30.16–34.42%). The pyrolysis oils have higher heating values (~25 MJ/kg) than bio-oils (~20 MJ/kg) from wood and agricultural residues, and the higher heating values of char (~31 MJ/kg) are comparable to that of many commercial coals. The elemental analysis indicated that the lower O/C value and higher H/C value represent a more valuable source of energy for pyrolysis oils than biomass. The nuclear magnetic resonance results demonstrated that the most abundant hydroxyl groups of pyrolysis oil are aliphatic OH groups, catechol, guaiacol, and p-hydroxy-phenyl OH groups. The aliphatic OH groups are mainly derived from the cleavage of cellulose glycosidic bonds, while the catechol, guaiacol, and p-hydroxy-phenyl OH groups are mostly attributed to the cleavage of the lignin β–O-4 bond. Significant amount of aromatic carbon (~40%) in pyrolysis oils is obtained from tannin and lignin components and the aromatic C–O bonds may be formed by a radical reaction between the aromatic and aliphatic hydroxyl groups. In this study, a comprehensive analytical method was developed to fully understand and evaluate the pyrolysis products produced from softwood barks, which could offer valuable information on the pyrolysis mechanism of biomass and promote better utilization of pyrolysis products. [ABSTRACT FROM AUTHOR]

Background: Biological routes for utilizing both carbohydrates and lignin are important to reach the ultimate goal of bioconversion of full carbon in biomass into biofuels and biochemicals. Recent biotechnology advances have shown promises toward facilitating biological transformation of lignin into lipids. Natural and engineered Rhodococcus strains (e.g., R. opacus PD630, R. jostii RHA1, and R. jostii RHA1 VanA−) have been demonstrated to utilize lignin for lipid production, and co-culture of them can promote lipid production from lignin. Results: In this study, a co-fermentation module of natural and engineered Rhodococcus strains with significant improved lignin degradation and/or lipid biosynthesis capacities was established, which enabled simultaneous conversion of glucose, lignin, and its derivatives into lipids. Although Rhodococci sp. showed preference to glucose over lignin, nearly half of the lignin was quickly depolymerized to monomers by these strains for cell growth and lipid synthesis after glucose was nearly consumed up. Profiles of metabolites produced by Rhodococcus strains growing on different carbon sources (e.g., glucose, alkali lignin, and dilute acid flowthrough-pretreated poplar wood slurry) confirmed lignin conversion during co-fermentation, and indicated novel metabolic capacities and unexplored metabolic pathways in these organisms. Proteome profiles suggested that lignin depolymerization by Rhodococci sp. involved multiple peroxidases with accessory oxidases. Besides the β-ketoadipate pathway, the phenylacetic acid (PAA) pathway was another potential route for the in vivo ring cleavage activity. In addition, deficiency of reducing power and cellular oxidative stress probably led to lower lipid production using lignin as the sole carbon source than that using glucose. Conclusions: This work demonstrated a potential strategy for efficient bioconversion of both lignin and glucose into lipids by co-culture of multiple natural and engineered Rhodococcus strains. In addition, the involvement of PAA pathway in lignin degradation can help to further improve lignin utilization, and the combinatory proteomics and bioinformatics strategies used in this study can also be applied into other systems to reveal the metabolic and regulatory pathways for balanced cellular metabolism and to select genetic targets for efficient conversion of both lignin and carbohydrates into biofuels. [ABSTRACT FROM AUTHOR]

The pyrolytic behavior of several biomass components including cellulose, hemicellulose, lignin, and tannin, from two sources of waste biomass (i.e., pine bark and pine residues) were examined. Compared to the two aromatic-based components in the biomass, carbohydrates produced much less char but more gas. Surprisingly, tannin produced a significant amount of water-soluble products; further analysis indicated that tannin could produce a large amount of catechols. The first reported NMR chemical shift databases for tannin and hemicellulose pyrolysis oils were created to facilitate the HSQC analysis. Various C–H functional groups (>30 different C–H bonds) in the pyrolysis oils could be analyzed by employing HSQC-NMR. The results indicated that most of the aromatic C–H and aliphatic C–H bonds in the pyrolysis oils produced from pine bark and pine residues resulted from the lignin and tannin components. A preliminary study for a quantitative application of HSQC-NMR on the characterization of pyrolysis oil was also done in this study. Nevertheless, the concepts established in this work open up new methods to fully characterize the whole portion of pyrolysis oils produced from various biomass components, which can provide valuable information on the thermochemical mechanisms. [ABSTRACT FROM AUTHOR]

Efficient degumming is crucial for valorisation of bast fibres. However, severer conditions and high energy consumption hinder their practical application. This work developed a photocatalytic degumming method assisted by both ZnIn 2 S 4 catalysis and lignin autocatalysis at mild conditions. The method achieved high lignin removal rate (71.6%) and cellulose yield (94.8%) in degumming of hemp fibres, decreasing the major content of β-O-4 bond and β-β bond in lignin from 32.0% to 10.7% and 6.8% to 3.4%, respectively. The pretreated fibres possessed excellent breaking strength (4.46 cN/dtex) and fineness (6.83 dtex). Moreover, the pretreated fibres were readily hydrolysed by cellulase, improving the glucose concentration by 58.3% compared to the alkaline degumming. Furthermore, the synergistic action of ZnIn 2 S 4 and lignin on generation of free radicals was observed. Thus, this work explored the potential of photocatalysis degumming of bast fibres, and discovered the synergistic action of ZnIn 2 S 4 and lignin autocatalysis. [Display omitted] • A mild photocatalytic degumming for fractionation of bast fibres. • High lignin removal (71.6%) at low temperature (30 °C). • The degummed fibers possessed excellent physical and mechanical properties. • Increasing the glucose concentration by 58.3% in enzymatic hydrolysis. • The mechanism of the synergistic action of ZnIn 2 S 4 and lignin was proposed. [ABSTRACT FROM AUTHOR]

Hemp represents a valuable resource of natural fibers on account of its environment favorable characteristics and excellent fiber quality. To fabricate hemp fibers, the traditional alkaline boiling degumming is used in the industry, which consumes a lot of water and generates a substantial amount of wastewater. In the present study, a novel eco–friendly solid–state degumming method was developed by using ethanolamine (ETA). The ETA degumming exhibited a high lignin removal rate (87.5%) at a high solid loading (30%), decreasing water consumption by 33.3%. Moreover, the ETA solution was readily reused up to five times without purification. The degummed hemp fibers possessed commendable fitness (4.2 dtex) and breaking strength (3.75 cN/dtex) without change of the crystalline cellulose structure. Besides, the lignin in wastewater was confirmed to be aminated, which is beneficial to the potential valorization of the by–product. Thus, the solid–state ETA degumming method holds significant potential for the fabrication of hemp fibers. [Display omitted] • A novel eco-friendly solid–state degumming method by using ethanolamine. • A high lignin removal rate (87.5%) at a high solid loading (30%). • Ethanolamine solution was reused up to five times without purification. [ABSTRACT FROM AUTHOR]

Hemp fiber is a promising textile resource. Because hemp fibers contain high gum content, an efficient degumming method needs to be developed. This study proposed a novel cascade degumming process coupling organosolv pretreatment and alkali boiling. Glycolic acid was optimally selected as a pretreatment reagent. The cascade process achieved a high lignin removal rate (69.81%) and hemicellulose removal rate (84.83%). The degummed hemp fibers showed excellent properties (4.18 ± 0.99 cN/dtex and 8.34 ± 0.01 dtex). Moreover, the glycolic acid solution could be reused three times without purification. The glycolic acid pretreatment led to decreased consumption of alkali reagents by 96.15%. Furthermore, the effect of glycolic acid pretreatment on lignin removal was analyzed by chemical composition analysis, FTIR, XRD, TGA, GPC, and HSQC NMR analysis. These results indicate that the novel cascade degumming process is an efficient and eco-friendly degumming method. [Display omitted] • A novel cascade process for hemp fiber degumming. • Organosolv pretreatment promoted efficient removal of lignin and hemicellulose. • Glycolic acid can be reused without purification. • The mechanism of lignin removal in cascade degumming process was studied. [ABSTRACT FROM AUTHOR]

• A method for splitting kenaf using microwave combined with lactic acid was proposed. • Fibers have excellent dispersion and suffer minor damage. • The extracted lignin is less damaged and keeps its structural integrity. • Potential for biomass clean production due to low chemicals and time consumption. According to diverse application purposes, different scales of lignocellulosic fibers were obtained from biomass through various preparation conditions. However, the pollution in the fiber separation process restricted the development of the related industry. This research proposed clean fiber separation technology of kenaf bast that combined microwave and lactic acid treatment. The traditional sulfate method was also carried out for comparison. The raw kenaf bast and produced fibers were characterized with wet chemistry analyses, SEM, FTIR, GPC and NMR. The results showed that compared with the traditional method (lignin removal rate 88.3 %, cellulose Mw = 607 kg/mol), the new method had higher lignin removal capacity (94.68 %) and less damage to cellulose (Mw = 1174 kg/mol). TG and NMR analysis showed that the separated crude lignin had a high pyrolysis temperature (350℃), minor structural changes and better uniformity, which was close to natural lignin. In addition, it was calculated that the processing time of the new method was reduced by 82.3 %, which reduced energy loss and waste liquid pollution. This study proved that microwave-assisted lactic acid treatment could separate kenaf fibers efficiently with less damage and pollution. [ABSTRACT FROM AUTHOR]