Structural changes and grading mechanism of lignin during solid alkali-active oxygen extraction and grading.

Cooking with active oxygen and solid alkali (CAOSA) is an efficient pretreatment method for biomass. For better grading of the lignin yellow liquor, the different lignin fractions and the recovered solid alkali were obtained using a simultaneous acid-alkali graded separation method. The results indicated that the recovery rate of solid alkali was 67.25 %, and the grading of lignin components was characterized by smaller dispersion coefficients, and more stable properties and structure. Lignin fractions with low dispersion coefficients possess more key structures, including the Phenol hydroxyl group (ArOH), Methoxy (OMe), and ß-aryl ether (ß-O-4), and have better thermal properties. The low molecular weight L4 has the highest ArOH content (2.1 mmol/g), which provides better antioxidant properties. The CAOSA process destroyed the S-unit and prevented lignin from condensation. Furthermore, the CAOSA process protected carbohydrates, which could effectively prevent them from dehydrating and re-polymerizing into pseudo-lignin. This allowed the pulp to remain natural, which was beneficial for subsequent transformation and utilization. Overall, the efficient separation of biomass components and lignin grading method proposed by combining the CAOSA process with the acid-alkali grading separation method has a strong application prospect and provides a theoretical basis for the high-value utilization of biomass and lignin.

Elucidating the inhibiting mechanism of pseudo-lignin on the enzymatic digestibility of cellulose by surface plasmon resonance.

To explore the interaction mechanism of pseudo-lignin (PL) with cellulase and its influence on cellulose hydrolysis, different PLs were extracted from pretreated bamboo holocellulose (HC) using different organic solvents. Meanwhile, the real-time interaction of PL and cellulase was analyzed using surface plasmon resonance (SPR). The results showed that the extraction effect of the tetrahydrofuran and 1, 4-dioxane/water solution on PL was more effective than the ethanol/water solution. The inhibition of PL fraction obtained from HC by acid pretreatment with higher temperature showed less effect on Avicel's enzymatic hydrolysis. SPR analysis revealed that PL formed at higher pretreatment temperature had a lower dissociation rate after adsorption with cellulase. Besides, the binding affinity of PL (160 °C) to cellulase was much greater than that of PL obtained from 180 °C, indicating PL extracted at higher temperature treated biomass is more easily dissociated from cellulase after binding.

Efficient removal of surface-deposited pseudo-lignin and lignin droplets by isothermal phase separation during hydrolysis.

During the traditional autohydrolysis, formation and deposition of "pseudo-lignin" and lignin droplets on the surface of biomass had a detrimental effect on the subsequent biomass conversion. In this study, isothermal phase separation was introduced into autohydrolysis, and the effects of isothermal phase separation on the dissolution of components and enzymatic hydrolysis of bamboo were studied. The research showed that isothermal phase separation after autohydrolysis without cooling had an effective reduction in the deposition of "pseudo-lignin" and lignin droplets on the residues surface. After isothermal phase separation, the contents of sugar (14.05 g/L) and lignin (6.16 g/L) in pre-hydrolysates increased by 20% and 19% compared with control, respectively. Moreover, the efficient removal of "pseudo-lignin" and lignin droplets from cell wall surface could further promote the biological conversion of pretreated biomass (22% higher than that of control) during the subsequent enzymatic hydrolysis.

Enzymatic conversion of pretreated lignocellulosic biomass: A review on influence of structural changes of lignin.

The demands of energy sustainability drive efforts to bio-chemical conversion of biomass into biofuels through pretreatment, enzymatic hydrolysis, and microbial fermentation. Pretreatment leads to significant structural changes of the complex lignin polymer that affect yield and productivity of the enzymatic conversion of lignocellulosic biomass. Structural changes of lignin after pretreatment include functional groups, inter unit linkages and compositions. These changes influence non-productive adsorption of enzyme on lignin through hydrophobic interaction and electrostatic interaction as well as hydrogen bonding. This paper reviews the relationships between structural changes of lignin and enzymatic hydrolysis of pretreated lignocellulosic biomass. The formation of pseudo-lignin during dilute acid pretreatment is revealed, and their negative effect on enzymatic hydrolysis is discussed.

Conversion of cotton textile waste to clean solid fuel via surfactant-assisted hydrothermal carbonization: Mechanisms and combustion behaviors.

The cotton textile was an abundant energy resource while was otherwise treated as waste. In this work, surfactants were used as catalysts in the hydrothermal carbonization (HTC) to transform cotton textile waste (CTW) into clean solid fuel. Furthermore, the conversion mechanisms of hydrothermal products during surfactant-assisted HTC were preliminarily proposed. The results showed that Span 80 and sodium dodecylbenzenesulfonate facilitated the transformation of CTW into bio-oil, while Tween 80 was more conducive to the development of pseudo-lignin, which endowed hydrochars higher energy density and updated the fuel quality and combustion behavior. Therefore, the research presented an effective method to convert CTW to clean solid fuel through the HTC treatment combining with surfactants.

How Pseudo-lignin Is Generated during Dilute Sulfuric Acid Pretreatment.

Pseudo-lignin is generated from lignocellulose biomass during pretreatment with dilute sulfuric acid and has a significant inhibitory effect on cellulase. However, the mechanism of pseudo-lignin generation remains unclear. The following main points have been addressed to help elucidate the pseudo-lignin generation pathway. Cellulose and xylan were pretreated with sulfuric acid at different concentrations; aliquots were periodically collected; and the changes in the byproducts of the prehydrolysate were quantified. Milled wood lignin (MWL) mixed with cellulose and xylan was pretreated to evaluate the impact of lignin on pseudo-lignin generation. Furfural, 5-hydroxymethylfurfural, and MWL were pretreated as model compounds to investigate pseudo-lignin generation. The result indicated that the increasing acid concentration significantly promoted the generation of pseudo-lignin. When the acid concentration was increased from 0 to 1.00 wt %, pseudo-lignin was increased from 1.36 to 4.05 g. In addition, lignin promoted the pseudo-lignin generation through the condensation between lignin and the generated intermediates.

The mechanism of wet/dry torrefaction pretreatment on the pyrolysis performance of tobacco stalk.

In this work, the influence of dry/wet torrefaction with additives on the pyrolysis performance was investigated. The results showed that the content of phenols and ketones (62% and 42%) was improved and the content of acids decreased from 35% to 4% due to the increase of lignin content in torrefied char. Moreover, the content of aromatic hydrocarbon reached 22%. The mechanism showed that the conversion of "CO/CO" into states of "aromatic CC/CC", the removal of hemicellulose and the formation of pseudo-lignin during wet/dry torrefaction were the key factors for the enrichment of aromatic hydrocarbon. The research supplied an effective and original method for obtaining high value aromatic chemicals from the agricultural and forestry waste via the wet/dry torrefaction pretreatment combining with pyrolysis.

Effect of surfactant on hydrothermal carbonization of coconut shell.

The effect of surfactant on the hydrothermal carbonization performance and pseudo-lignin formation were investigated. Especially, the fuel properties and combustion characteristics of hydrochar and solid product were determined. Furthermore, the mechanism of surfactant acted in hydrothermal carbonization was also identified in this article. The results showed that surfactant improved the content of solid products, lignin, heavy bio-oil (HBO), H2 and CO. Moreover, sodium dodecylbenzenesulfonate promoted the increase of the surface area of hydrochar from 4.93 to 41.43 m2/g. The mechanism showed surfactant formed water/oil film around the hydrochar to prevent HBO from leaving the pore or surface of hydrochar and promoted the condensation and polymerization of 5-hydroxymethylfurfura (5-HMF) with hydroxymethylfurfura (HMF) to form pseudo-lignin. The HBO and pseudo-lignin were beneficial for improving integrated combustion characteristic index (SN) during combustion. The article provides a new method to promote hydrothermal carbonization (HTC) for obtaining high value hydrochar as fuels.

The influence of combined pretreatment with surfactant/ultrasonic and hydrothermal carbonization on fuel properties, pyrolysis and combustion behavior of corn stalk.

The surfactant/ultrasonic combined with hydrothermal carbonization (HTC) were performed to investigate the effect on fuel properties, pyrolysis and combustion behavior of hydrochar under different condition. The results showed that the C/H and O/C ratio of corn stalk (CS) + H2SO4 + tween was 1.1 and 0.29, which were close to coal, and the heat value reached 28.89 MJ/kg. HTC combined with ultrasonic/surfactant realized the complete separation of lignin with cellulose and hemicellulose in CS. Ultrasonic restricted the hydrolysis of lignin under alkaline condition and pseudo-lignin formation under acidic condition. Tween inhibited the formation and deposition of "pseudo-lignin". The thermogravimetric (TG) experiments displayed the tween combined with HTC improved the pyrolysis temperature and decreased activation energy as well as the combustion ignition temperature which showed better pyrolysis and combustion characteristics. The nth-order kinetic mode was fit with the TG datas. The mechanism of tween combined with HTC was also analyzed.

New Understandings of the Relationship and Initial Formation Mechanism for Pseudo-lignin, Humins, and Acid-Induced Hydrothermal Carbon.

The generation of pseudo-lignin as byproduct during the lignocellulose acidic pretreatment has been proposed for many years. However, the detailed formation mechanism is still unclear. Moreover, there is a lack of understanding in the initial reaction during the formation of humins (byproducts in furfural production) and acid-induced hydrothermal carbon (carbon material). In this work, the initial formation of these three substances were investigated. We first found the common feature of their formation process was that carbohydrate-hydrolyzed compounds could form black polymers by condensing in acidic media, but the difference was dependent on the reaction degree. Furthermore, the results revealed that oxidation was an accelerator for condensations during producing black polymers because oxidized compounds could enhance the acidity of the reaction system. However, condensations of oxidized compounds were more difficult to proceed. Meanwhile, during the initial stage, the dominating pathway was that furfural condensed with itself and isomerized xylose via aldol-condensation.

Comparison of catalytically non-productive adsorption of fungal proteins to lignins and pseudo-lignin using isobaric mass tagging.

Catalytically non-productive adsorption of fungal enzymes to pseudo-lignin (PL) was compared to adsorption to lignin preparations derived from different sources (SL, spruce; BL, birch; OL, beech) using different methods [steam pretreatment/enzymatic saccharification (SL, BL) and organosolv processing (OL)]. The protein adsorption to the SL was more extensive than the adsorption to the hardwood lignins, which was relatively similar to the adsorption to the PL. The adsorption patterns of 13 individual proteins were studied using isobaric mass tagging with TMTsixplex reagent and LC-MS/MS analysis. The results suggest that, on an average, adsorption of proteins equipped with carbohydrate-binding modules, such as the cellulases CBHI, EGII, and EGIV, was less dependent on the quality of the lignin/PL than adsorption of other proteins, such as ß-Xyl, Xyn-1, and Xyn-2, which are involved in xylan degradation.

Microbial biogas production from hydrolysis lignin: insight into lignin structural changes.

BACKGROUND: The emerging cellulosic bioethanol industry will generate huge amounts of lignin-rich residues that may be converted into biogas by anaerobic digestion (AD) to increase the output of energy carriers from the biorefinery plants. The carbohydrates fraction of lignocellulosic biomass is degradable, whereas the lignin fraction is generally considered difficult to degrade during AD. The objective of this study was to investigate the feasibility of biogas production by AD from hydrolysis lignin (HL), prepared by steam explosion (SE) and enzymatic saccharification of birch. A novel nylon bag technique together with two-dimensional nuclear magnetic resonance spectroscopy, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), and Fourier transform infrared (FTIR) spectroscopy was used to identify recalcitrant and degradable structures in the lignin during AD. RESULTS: The HL had a lignin content of 80% which included pseudo-lignin and condensed-lignin structures resulting from the SE pretreatment. The obtained methane yield from HL was almost twofold higher than the theoretical methane from the carbohydrate fraction alone, indicating that part of the lignin was converted to methane. Characterization of the undegradable material after AD revealed a substantial loss of signals characteristic for carbohydrates and lignin-carbohydrate complexes (LCC), indicating conversion of these chemical components to methane during AD. The ß-O-4' linkage and resinol were not modified as such in AD, but major change was seen for the S/G ratio from 5.8 to 2.6, phenylcoumaran from 4.9 to 1.0%, and pseudo-lignin and condensed-lignin were clearly degraded. Scanning electron microscopy and simultaneous thermal analysis measurements demonstrated changes in morphology and thermal properties following SE pretreatment and AD. Our results showed that carbohydrate, LCC, pseudo-lignin, and condensed-lignin degradation had contributed to methane production. The energy yield for the combined ethanol production and biogas production was 8.1 MJ fuel per kg DM of substrate (4.9 MJ/kg from ethanol and 3.2 MJ/kg from methane). CONCLUSION: This study shows the benefit of using a novel bag technique together with advanced analytical techniques to investigate the degradation mechanisms of lignin during AD, and also points to a possible application of HL produced in cellulosic bioethanol plants.

Comparison of [HSO4]-, [Cl]- and [MeCO2]- as anions in pretreatment of aspen and spruce with imidazolium-based ionic liquids.

BACKGROUND: Ionic liquids (ILs) draw attention as green solvents for pretreatment of lignocellulose before enzymatic saccharification. Imidazolium-based ILs with different anionic constituents ([HSO4]-, [Cl]-, [MeCO2]-) were compared with regard to pretreatment of wood from aspen and spruce. The objective was to elucidate how the choice of anionic constituent affected the suitability of using the IL for pretreatment of hardwood, such as aspen, and softwood, such as spruce. The investigation covered a thorough analysis of the mass balance of the IL pretreatments, the effects of pretreatment on the cell wall structure as assessed by fluorescence microscopy, and the effects of pretreatment on the susceptibility to enzymatic saccharification. Torrefied aspen and spruce were included in the comparison for assessing how shifting contents of hemicelluloses and Klason lignin affected the susceptibility of the wood to IL pretreatment and enzymatic saccharification. RESULTS: The glucose yield after IL pretreatment increased in the order [Cl]- < [HSO4]- < [MeCO2]- for aspen, but in the order [HSO4]- < [Cl]- < [MeCO2]- for spruce. For both aspen and spruce, removal of hemicelluloses and lignin increased in the order [Cl]- < [MeCO2]- < [HSO4]-. Fluorescence microscopy indicated increasingly disordered cell wall structure following the order [HSO4]- < [Cl]- < [MeCO2]-. Torrefaction of aspen converted xylan to pseudo-lignin and changed the glucose yield order to [HSO4]- < [Cl]- < [MeCO2]-. CONCLUSIONS: The acidity of [HSO4]- caused extensive hydrolysis of xylan, which facilitated pretreatment of xylan-rich hardwood. Apart from that, the degree of removal of hemicelluloses and lignin did not correspond well with the improvement of the enzymatic saccharification. Taken together, the saccharification results were found to mainly reflect (i) the different capacities of the ILs to disorder the cell wall structure, (ii) the recalcitrance caused by high xylan content, and (iii) the capacity of the [HSO4]--based IL to hydrolyze xylan.

Evaluation of the effect of hot-compressed water treatment on enzymatic hydrolysis of lignocellulosic nanofibrils with different lignin content using a quartz crystal microbalance.

Hot-compressed water (HCW) treatment is known to not only improve enzymatic hydrolysis efficiency of lignocellulosic biomass but to also generate insoluble lignin droplets, which retard enzymatic hydrolysis. In this study, the inhibitory effect of the lignin droplets was evaluated by monitoring the initial enzyme adsorption and degradation of lignocellulosic nanofibrils (LCNFs) using a quartz crystal microbalance (QCM). Lignin content was adjusted by the sodium chlorite-acetic acid method and divided into samples with high (24.9 wt%) and low (5.6 wt%) lignin content, which were then subjected to HCW treatment at various temperatures. The changes in lignin content were small with increasing HCW temperature, whereas hemicellulose content decreased, regardless of the initial lignin content. The formation of lignin droplets and pseudo-lignin-like products was confirmed in both LCNFs by atomic force microscopy (AFM) and was predominant in LCNFs with high lignin content treated at 200°C. QCM data showed that the enzyme adsorption amount in both LCNFs after HCW treatment was increased and was greater in LCNFs with low lignin content. Initial enzymatic degradation was substantially slowed in LCNFs with high lignin content, particularly after HCW treatment at temperatures higher than 180°C. These QCM results suggest that the steric hindrance of the deposited lignin is the primary mechanism by which the initial enzymatic hydrolysis is delayed. Biotechnol. Bioeng. 2016;113: 1441-1447. © 2015 Wiley Periodicals, Inc.

Steam explosion pretreatment of wheat straw to improve methane yields: investigation of the degradation kinetics of structural compounds during anaerobic digestion.

Wheat straw can serve as a low-cost substrate for energy production without competing with food or feed production. This study investigated the effect of steam explosion pretreatment on the biological methane potential and the degradation kinetics of wheat straw during anaerobic digestion. It was observed that the biological methane potential of the non steam exploded, ground wheat straw (276 l(N) kg VS(-1)) did not significantly differ from the best steam explosion treated sample (286 l(N) kg VS(-1)) which was achieved at a pretreatment temperature of 140°C and a retention time of 60 min. Nevertheless degradation speed was improved by the pretreatment. Furthermore it was observed that compounds resulting from chemical reactions during the pretreatment and classified as pseudo-lignin were also degraded during the anaerobic batch experiments. Based on the rumen simulation technique, a model was developed to characterise the degradation process.

Lignin removal and benzene-alcohol extraction effects on lignin measurements of the hydrothermal pretreated bamboo substrate.

Lignin content of hydrothermal pretreated bamboo chips was determined by the two methods: TAPPI standard method (222om-06) and TAPPI standard method without benzene-alcohol extraction (BAE). The results showed that including BAE resulted in lower Klason lignin (KL) and acid soluble lignin (ASL) measurements in the prehydrolyzed substrate, that is to say, BAE removed parts of KL and ASL. Therefore, the TAPPI standard method should be modified by omitting the BAE for lignin measurements of pretreated substrate. The following lignin removal analysis suggested that lignin was removed from the bamboo substrate during pretreatment by a combination of degradation reaction and deconstruction; thereafter the pseudo lignin generated in the hydrothermal pretreatment and condensation reaction between the lignin fragments accounted for the later KL increase.