Tong-Qi Yuan

Understanding the chemical transformations of lignin during ionic liquid pretreatment

Unveiling the fundamental chemistry of lignin under ionic liquid (IL) pretreatment will facilitate the understanding of biomass recalcitrance involved in pretreatment processes. To examine in greater detail the chemical transformations of lignin under different IL pretreatment conditions without competing reactions from plant polysaccharides, the IL pretreatment of the isolated poplar alkaline lignin (hardwood lignin) under varying IL pretreatment conditions (i.e., 110–170 °C, 1–16 hours) was performed in an appropriate manner. The structural transformations of the lignin have been investigated by elemental analysis, 2D-HSQC spectra, quantitative 13C-NMR spectra, 31P NMR, and GPC analysis. Results revealed that a decrease of aliphatic OH and an increase in phenolic hydroxyl groups occurred in lignin as the pretreatment proceeded. The increased phenolic OH was mainly as a result of cleavage of β-O-4′ linkages, while the reduced aliphatic OH is probably attributed to the dehydration reaction. The cleavage of β-O-4′ linkages, degradation of β–β′ and β-5′ linkages obviously happened at high temperatures and resulted in the decrease of molecular weights. In addition, IL pretreatment selectively degraded the G-type lignin fractions and the condensation reaction took place more easily at S units than G units. Moreover, the demethoxylation preferentially occurred in G units, especially at higher temperatures. It is believed that investigating the fundamental chemistry of lignin during IL pretreatments would be beneficial to optimize and control the pretreatment process.

Combination of biological pretreatment with liquid hot water pretreatment to enhance enzymatic hydrolysis of Populus tomentosa

A novel stepwise pretreatment of combination of fungal treatment with liquid hot water (LHW) treatment was conducted to enhance the enzymatic hydrolysis of Populus tomentosa. The results showed that lignin and cellulose increased with the elevating temperature, while significant amount of hemicellulose was degraded during the LHW pretreatment. A highest hemicellulose removal of 92.33% was observed by combination of Lenzites betulina C5617 with LHW treatment at 200°C, which was almost 2 times higher than that of sole LHW treatment at the same level. Saccharification of poplar co-treated with L. betulina C5617 and LHW at 200°C resulted in a 2.66-fold increase of glucose yield than that of sole LHW treatment, and an increase (2.25-fold) of glucose yield was obtained by the combination of Trametes ochracea C6888 with LHW. The combination pretreatment performed well at accelerating the enzymatic hydrolysis of poplar wood.

Structural elucidation of lignin polymers of Eucalyptus chips during organosolv pretreatment and extended delignification.

Effective delignification of lignocelluloses is a very important to guarantee the economic feasibility of organosolv-based biorefinery. Eucalyptus chips were successively subjected to organosolv pretreatment (AEOP) and extended delignification (ED) process in the present study. The effects of delignification processes were scientifically evaluated by component analysis, SEM, and CP-MAS NMR techniques. It was found that the integrated process of organosolv pretreatment and subsequent delignification resulted in an effective delignification. The fundamental chemistry of the lignin obtained after these processes was thoroughly investigated by FT-IR, multidimensional NMR ((31)P-, (13)C-, and 2D-HSQC NMR), and GPC techniques. It was observed that an extensive cleavage of aryl ether linkages, ethoxylation, and some condensation reactions occurred in AEOP process, while α-oxidation mainly took place in alkaline hydrogen peroxide (AHP) process. It is believed that better understanding the fundamental chemistry of lignin facilitates the optimization of the delignification process. More importantly, well-defined of lignin polymers will facilitate their value-added applications in current and future biorefineries.

Fractionation of bamboo culms by autohydrolysis, organosolv delignification and extended delignification: Understanding the fundamental chemistry of the lignin during the integrated process

Bamboo (Phyllostachys pubescens) was successfully fractionated using a three-step integrated process: (1) autohydrolysis pretreatment facilitating xylooligosaccharide (XOS) production (2) organosolv delignification with organic acids to obtain high-purity lignin, and (3) extended delignification with alkaline hydrogen peroxide (AHP) to produce purified pulp. The integrated process was comprehensively evaluated by component analysis, SEM, XRD, and CP-MAS NMR techniques. Emphatically, the fundamental chemistry of the lignin fragments obtained from the integrated process was thoroughly investigated by gel permeation chromatography and solution-state NMR techniques (quantitative (13)C, 2D-HSQC, and (31)P-NMR spectroscopies). It is believed that the integrated process facilitate the production of XOS, high-purity lignin, and purified pulp. Moreover, the enhanced understanding of structural features and chemical reactivity of lignin polymers will maximize their utilizations in a future biorefinery industry.

Structural elucidation of whole lignin from Eucalyptus based on preswelling and enzymatic hydrolysis

The structural elucidation of whole lignin in the plant cell wall is extremely important for providing a representative lignin to understand the molecular characteristics of lignin in plants, and develop lignin-based polymers and green chemicals under the current biorefinery scenario. However, research in this area still lack methodologies for effectively isolating whole lignin from the plant cell wall. In this study, an effective method based on mild alkaline preswollen (4% NaOH, 25 °C, 24 h) and enzymatic hydrolysis for the isolation of “swollen residual enzyme lignin, SREL” from Eucalyptus wood was proposed. SREL was investigated as compared to the corresponding cellulolytic enzyme lignin (CEL) and alkali lignin (AL). Observably, the yield of SREL (95%) was significantly higher than that of the corresponding CEL (20%) and AL (12%). The isolated lignin has been comparatively investigated by a combination of elemental analysis, 2D HSQC NMR, 31P-NMR, analytical pyrolysis, and GPC techniques. The major lignin linkages (β-O-4′, β–β′, β-5′, etc.) were thoroughly assigned and the frequencies of the major lignin linkages were quantitatively compared. Further experiments demonstrated that a transformation from cellulose I to cellulose II occurred during alkaline preswelling of the ball-milled Eucalyptus wood, which resulted in the efficient enzymatic hydrolysis of the substrates, thus yielding a representative lignin sample (SREL). However, the alkaline preswelling treatment has little effect on the lignin structures (typical substructures); it only tends to yield syringyl-rich lignin macromolecules as compared to CEL. Furthermore, the effective method gives us a panoramic image to understand the intrinsic structural features of whole lignin from other lignocellulosic biomasses and helps to develop more effective plant deconstruction or depolymerization strategies in the current biorefinery and catalytic conversion process.

Unraveling the structural characteristics of lignin in hydrothermal pretreated fibers and manufactured binderless boards from Eucalyptus grandis

BackgroundEucalyptus grandis is one of the most abundant biomass from plantation in many parts of the world. The binderless board were manufactured from hydrothermal pretreated fibers of Eucalyptus wood and characterized for the chemical analyses and mechanical strengths in order to assess the mechanism of self-bonding. To make clear the self-bonding mechanism of these binderless boards, the structural characteristics of cellulolytic enzyme lignin (CEL) isolated from Eucalyptus wood, its hydrothermal pretreated fibers, and binderless boards were thoroughly investigated by chemical and spectroscopic methods.ResultsThe result revealed that hydrothermal pretreatment and hot pressing process could change cellulose crystalline structures by disrupting inter/intra hydrogen bonding of cellulose chains. During the hydrothermal pretreatment of Eucalyptus wood, acid-catalyzed cleavage of β-O-4′ linkages and ester bonds were the major mechanisms of lignin cleavage. This degradation pathway led to a more condensed lignin which has a high average molecular weight and more phenolic hydroxyl groups than the control. The hot pressing process resulted in the binderless boards with reduced lignin contents and decreased the glass transition temperature, thus making the lignin more accessible to the fiber surface. CEL isolated from the binderless boards showed an increased syringyl to guaiacyl propane (S/G) ratio but a lower molecular weight than those of the untreated Eucalyptus wood and the hydrothermal pretreated fibers.ConclusionsBased on the finding of this study, it is suggested that the combination of hydrothermal pretreatment and hot pressing process is a good way for conditioning hardwood sawdust for the production of binderless boards. The thermal softening of lignin, rich in phenolic hydroxyl groups, and increased condensed lignin structure contributed to the self-bonding formation of lignocellulosic materials.

Synergistic benefits of ionic liquid and alkaline pretreatments of poplar wood. Part 1: Effect of integrated pretreatment on enzymatic hydrolysis

An environmentally friendly pretreatment process was developed to fractionate hemicelluloses and lignin from poplar wood by ionic liquid (IL) pretreatment coupled with mild alkaline extraction. Hemicellulosic and lignin fractions were obtained in high yields, amounting to 59.3% and 74.4%, respectively, which can served as raw materials for production of value-added products. The yield of glucose for the integrated pretreated poplar wood was 99.2%, while it was just 19.2% for the untreated material. The synergistic benefits of the removal of lignin and hemicelluloses, the increase of the cellulose surface area, and the conversion of cellulose fibers from the cellulose I to the cellulose II crystal phase resulted in the high glucose yield for the integrated pretreated substrate. Therefore, the IL based biorefining strategy proposed can integrate biofuels production into a biorefinery scheme in which the major components of poplar wood can be converted into value-added products.

Homogeneous Esterification of Poplar Wood in an Ionic Liquid under Mild Conditions: Characterization and Properties

Wood meal was completely dissolved under constant conditions (130 °C, 6 h) in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), and the various factors and potential mechanism of the homogeneous esterification of wood in this reaction medium were mainly studied. The physicochemical properties of the esterified wood were also investigated. It has been shown that highly substituted wood esters could be obtained by reacting wood dissolved in [C(4)mim]Cl with octanoyl chloride in the presence of triethylamine as a neutralizer. The weight percent gain was arranged from 121.5% to 297.4%. All reactions were performed under mild conditions, low excess of reagent, and a short reaction time compared to the heterogeneous chemical modification. Meanwhile, characterization of the derivatives confirmed that the homogeneous esterification was successfully processed. It was also found that thermal stability and morphological properties of the esterified wood were significantly different from those in previous reports. Octanoylation of wood meal in the [C(4)mim]Cl homogeneous system reduced the initial temperature of their thermal degradation and decreased the thermal stability compared to those in unmodified wood meal. Furthermore, the fibrillar appearance of wood meal changed into a relatively more homogeneous macrostructure of the esterfied wood. All these results suggested that homogeneous esterification of poplar wood in [C(4)mim]Cl would enhance the compatibility and improve the processability of wood with synthetic polymers.

Hydrothermal degradation of lignin: Products analysis for phenol formaldehyde adhesive synthesis

Corncob lignin was treated with pressurized hot water in a cylindrical autoclave in current investigation. With the aim of investigating the effect of reaction temperature and retention time on the distribution of degradation products, the products were divided into five fractions including gas, volatile organic compounds, water-soluble oil, heavy oil, and solid residue. It was found that hydrothermal degradation of corncob lignin in pressurized hot water produced a large amount of phenolic compounds with lower molecular weight than the raw lignin. Some phenolic and benzene derivatives monomers such as vanillin, 2-methoxy-phenol, 2-ethyl-phenol, p-xylene, and 1, 3-dimethyl-benzene were also identified in the degradation products. The products were further analyzed by GC-MS, GPC, 2D-HSQC, and (31)P-NMR to investigate their suitability for partial incorporation into phenol formaldehyde adhesive as a substitution of phenol. The results indicated that the reaction temperature had more effect on the products distribution than the retention time. The optimal condition for heavy oil production appeared at 290 °C with retention time 0 min. The compounds of heavy oil had more active sites than the raw lignin, suggesting that the heavy oil obtained from hydrothermal degradation of lignin is a promising material for phenol formaldehyde adhesive synthesis.

Manufacture and application of lignin-based carbon fibers (LCFs) and lignin-based carbon nanofibers (LCNFs)

Environmental issues and constantly diminishing petroleum resources are considerable barriers inhibiting modernization, and vast efforts have been exerted to address these problems. Carbon fibers (CFs) are carbon materials with high mechanical strength and functionality for applications in construction, electronics, transportation, and aviation. Currently, most CFs are produced from polyacrylonitrile, a petroleum-based, unsustainable, and non-renewable chemical of relatively high price. Interestingly, lignin is an inexpensive, highly accessible, and renewable resource. It has been utilized to fabricate lignin-based carbon fibers (LCFs), which have met rapid development during the past two decades. In this review, LCFs are generalized by focusing on their steps of manufacture. Resource types and corresponding pretreatments ensure the processability of spinning and thermal treatments. Fibers are formed via spinning methods, including melt-spinning, wet-spinning, dry-spinning, and electrospinning. The next step is the most significant process of stabilization, in which fibers are oxidized, crosslinked, and thermally stabilized for pyrolysis. Subsequent to carbonization and/or additional processes (activation and graphitization), LCFs are obtained. Each step can influence the terminal performance of LCFs, which is discussed in detail. Recently produced LCFs of sub-micron size, also known as lignin-based carbon nanofibers (LCNFs), are detailed. Furthermore, attributed to the excellent performance and low cost of LCFs and LCNFs, they have been applied in various fields, predominantly for electronic devices such as batteries and supercapacitors. Our review is concluded with opinions on the potential for further advancement of this promising material.