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Sugarcane bagasse is a large-volume agriculture residue that is generated on a ~540 million metric tons per year basis globally1,2 with the top-three producing countries in Latin America being Brazil (~181 million metric ton yr−1),3 Mexico (ܾ15 million metric ton yr−1),4 and Colombia (ܾ7 million metric ton yr−1),5 respectively.6 Given sustainability concerns and the need to maximize the utilization of bioresources, the use of sugarcane bagasse is receiving significant attention in biorefining applications, as it is a promising resource for the conversion to biofuels and biopower. This review provides a comprehensive review of bagasse and its chemical constituents and on-going research into its utilization as a feedstock for cellulosic ethanol and electricity generation. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd [ABSTRACT FROM AUTHOR]

Lignocellulosic materials such as wood, grass, and agricultural and forest residues are promising alternative energy resources that can be utilized to produce ethanol. The yield of ethanol production from native lignocellulosic material is relatively low due to its native recalcitrance, which is attributed to, in part, lignin content/structure, hemicelluloses, cellulose crystallinity, and other factors. Pretreatment of lignocellulosic materials is required to overcome this recalcitrance. The goal of pretreatment is to alter the physical features and chemical composition/structure of lignocellulosic materials, thus making cellulose more accessible to enzymatic hydrolysis for sugar conversion. Various pretreatment technologies to reduce recalcitrance and to increase sugar yield have been developed during the past two decades. This review examines the changes in lignocellulosic structure primarily in cellulose and hemicellulose during the most commonly applied pretreatment technologies including dilute acid pretreatment, hydrothermal pretreatment, and alkaline pretreatment. [ABSTRACT FROM AUTHOR]

Abstract: Dilute acid pretreatment (DAP) is commonly employed prior to enzymatic deconstruction of cellulose to increase overall sugar and subsequent ethanol yields from downstream bioconversion processes. Typically optimization of pretreatment is evaluated by determining hemicellulose removal, subsequent reactivity towards enzymatic deconstruction, and recoverable polysaccharide yields. In this study, the affect of DAP on the supramolecular and ultrastructure of lignocellulosic biomass was evaluated. A series of dilute acidic pretreatments, employing ∼0.10–0.20 mol/m3 H2SO4 at ∼160–180 °C, for varying residence times were conducted on both Populus and switchgrass samples. The untreated and pretreated biomass samples were characterized by carbohydrate and lignin analysis, gel permeation chromatography (GPC) and 13C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. GPC analysis shows a reduction in the molecular weight of cellulose and change in its polydispersity index (PDI) with increasing residence time, indicating that pretreatment is actually degrading the cellulose chains. 13C CPMAS and non-linear line-fitting of the C4 region in the carbon spectrum of the isolated cellulose not only showed that the crystallinity index increases with residence time, but that the lateral fibril dimension (LFD) and lateral fibril aggregate dimension (LFAD) increase as well. [Copyright &y& Elsevier]

The cover image, by Arthur J. Ragauskas and Tais Lacerda Bezerra, is based on the Review A review of sugarcane bagasse for second-generation bioethanol and biopower production, DOI: . Photo Courtesy: NREL image gallery and USDA/ARS image gallery. [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]

In order to obtain accurate information about the ultrastructure of cellulose from native biomass by 13C cross polarization magic angle spinning (CP/MAS) NMR spectroscopy the cellulose component must be isolated due to overlapping resonances from both lignin and hemicellulose. Typically, cellulose isolation has been achieved via holocellulose pulping to remove lignin followed by an acid hydrolysis procedure to remove the hemicellulose components. Using 13C CP/MAS NMR and non-linear line-fitting of the cellulose C4 region, it was observed that the standard acid hydrolysis procedure caused an apparent increase in crystallinity of ∼10% or less on the cellulose isolated from Populus holocellulose. We have examined the effect of the cellulose isolation method, particularly the acid treatment time for hemicellulose removal, on cellulose ultrastructural characteristics by studying these effects on cotton, microcrystalline cellulose (MCC) and holocellulose pulped Populus. 13C CP/MAS NMR of MCC indicated that holocellulose pulping and acid hydrolysis has little effect on the crystalline ultrastructural components of cellulose. Although any chemical method to isolate cellulose from native biomass will invariably alter substrate characteristics, especially those related to regions accessible to solvents, we found those changes to be minimal and consistent in samples of typical crystallinity and lignin/hemicellulose content. Based on the rate of the hemicellulose removal, as determined by HPLC-carbohydrate analysis and magnitude of cellulose ultrastructural alteration, the most suitable cellulose isolation methodology utilizes a treatment of 2.5 M HCl at 100 °C for a standard residence time between 1.5 and 4 h. However, for the most accurate crystallinity results this residence time should be determined empirically for a particular sample. [ABSTRACT FROM AUTHOR]

Background: Hydroxycinnamoyl CoA: shikimate hydroxycinnamoyl transferase (HCT) is a central enzyme of the so-called "esters" pathway to monolignols. As originally envisioned, HCT functions twice in this pathway, to form coumaroyl shikimate and then, in the "reverse" direction, to convert caffeoyl shikimate to caffeoyl CoA. The discovery of a caffeoyl shikimate esterase (CSE) that forms caffeic acid directly from caffeoyl shikimate calls into question the need for the reverse HCT reaction in lignin biosynthesis. Loss of function of HCT gives severe growth phenotypes in several dicot plants, but less so in some monocots, questioning whether this enzyme, and therefore the shikimate shunt, plays the same role in both monocots and dicots. The model grass Brachypodium distachyon has two HCT genes, but lacks a classical CSE gene. This study was therefore conducted to evaluate the utility of HCT as a target for lignin modification in a species with an "incomplete" shikimate shunt. Results: The kinetic properties of recombinant B. distachyon HCTs were compared with those from Arabidopsis thaliana, Medicago truncatula, and Panicum virgatum (switchgrass) for both the forward and reverse reactions. Along with two M. truncatula HCTs, B. distachyon HCT2 had the least kinetically unfavorable reverse HCT reaction, and this enzyme is induced when HCT1 is down-regulated. Down regulation of B. distachyon HCT1, or co-down-regulation of HCT1 and HCT2, by RNA interference led to reduced lignin levels, with only modest changes in lignin composition and molecular weight. Conclusions: Down-regulation of HCT1, or co-down-regulation of both HCT genes, in B. distachyon results in less extensive changes in lignin content/composition and cell wall structure than observed following HCT down-regulation in dicots, with little negative impact on biomass yield. Nevertheless, HCT down-regulation leads to significant improvements in biomass saccharification efficiency, making this gene a preferred target for biotechnological improvement of grasses for bioprocessing. [ABSTRACT FROM AUTHOR]

[Display omitted] • A waste-derived electrocatalyst P-CoNiO 2 @NC is firstly constructed. • P-CoNiO 2 @NC exhibits a superior HER performance in both acid and alkaline condition. • Waste-derived carbon substrates boost the catalytic activity of the P-doped dual 3d TMOs. Carbon substrate support is a promising approach to facilitate catalytic activity of non-noble metal catalysts in hydrogen evolution reactions (HER). Here, we report a waste-derived electrocatalyst P-CoNiO 2 @NC synthesized under mild condition. It exhibits outstanding HER performance in both acid (η 10 = 64.6 mV) and alkaline (η 10 = 96.4 mV) condition with good stability. Especially, it begins to outperform commercial Pt/C when the current density is over 74 mA/cm2 in acid electrolyte and 29 mA/cm2 in alkaline electrolyte. Moreover, the waste-derived carbon substrate could effectively promote HER activity of other dual 3d TMOs such as Fe and Co, Fe and Ni. The improved HER activity originates from electron transfer, electronic structure adjustment and optimization of intermediates adsorption according to X -ray photoelectron spectroscopy and density functional theory calculations. This work provides a new insight for converting wastes into value-added products and a sustainable and friendly strategy to facilitate hydrogen energy production. [ABSTRACT FROM AUTHOR]

Co-processing of plastic and biomass wastes to produce high-quality fuel has been attracting considerable interest in energy recovery. This work employed Box-Behnken Design (BBD) to optimize yield and properties of oil from supercritical methanol (scMeOH) co -liquefaction of rice straw (RS) and linear low-density polyethylene (LLDPE). Three independent variables of reaction temperature (270, 300, and 330°C), holding time (60, 90, and 120 mins), and RS/LLDPE mass ratio (0.15, 0.50, and 0.85) were selected for experiments. A maximum oil yield of 34.17 wt% was achieved at 303°C, 96 mins, and RS/LLDPE ratio of 0.59 according to BBD. Temperature and RS/LLDPE ratio dominated the oil yield and synergistic effects during co-liquefaction, whereas time was an insignificant factor. Optimum oil from co-liquefaction contained substantial hydrocarbons content of 32.91% compared to that from single RS-derived oil of 7.77%. Solid product obtained at the optimum condition could be used as solid fuel, due to its relatively high HHV of 43.08 MJ/kg compared to the other solid fuels (13.90–32.14 MJ/kg). This work provides a deep understanding of the co-processing of solid biomass and plastic wastes. [Display omitted] • Co-liquefaction of RS with LLDPE in supercritical methanol was studied. • Optimization of parameters was conducted using RSM-BBD. • Temperature and RS/LLDPE ratio were key design variables for oil production. • Co-liquefaction synergistically enhanced the oil yield at specific conditions. • Interaction between LLDPE and methanol was clarified. [ABSTRACT FROM AUTHOR]

Ionic liquids are of potential interest in the processing of lignocellulosic biomass. In this study, the ionic liquid co-solvent system of 1- methylimidazole (MIM) and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc) was used to solvate LignoBoost lignin fractionated from black liquor obtained from a kraft paper mill. Lignin ethanol-precipitated (LEP) and ethanol-soluble (LES) fractions were characterized via gel permeation chromatography (GPC) and 13C- and 31P-nuclear magnetic resonance spectroscopy (NMR) to determine structural characteristics and their relationship to polymer solubility in the system. Polymer integrity and solubility were optimal at ~20% lignin loading (w/w). Results showed that LEPs were generally of higher apparent molecular weight (Mw) and enriched with condensed/aliphatic ether linkages and aliphatic hydroxyls. The LESs had a lower apparent Mw and were enriched with carboxylic and phenolic groups. This newly gained knowledge on lignin fractionation and aggregation in the present solvent system provides future opportunities for tuning fractionation/extraction to suit a specific biomass-derived product, e.g., carbon fibers. [ABSTRACT FROM AUTHOR]

Background Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultra structural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultra structure, which might ultimately have large implications with respect to enzymatic deconstruction efforts. Results Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultra structure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons' stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. Conclusions Overall, the results indicate a strong influence of lignin content on cellulose ultra structural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of cellulose micro fibril dimensions and crystallite size becomes more apparent. Further, this enlargement of cellulose micro fibril dimensions is attributed to specific processes, including the co-crystallization of crystalline cellulose driven by irreversible inter chain hydrogen bonding (similar to hornification) and/or cellulose annealing that converts amorphous cellulose to paracrystalline and crystalline cellulose. Essentially, lignin acts as a barrier to prevent cellulose crystallinity increase and cellulose fibril coalescence during DAP. [ABSTRACT FROM AUTHOR]

Biofuels are particularly attractive and play an increasingly important role in sustainable energy. However, biofuels originating from lignocellulosic biomass (LCB) are extremely challenging because of their low carbon content, low stability, and high oxygen content. This work evaluates the supercritical methanol (scMeOH) co-liquefaction of rice straw and linear low-density polyethylene (LLDPE) at temperature range of 240–340 °C for 0–2 h, to obtain hydrocarbons (HCs)-rich oil and carbon-rich solid product. Results show that reaction temperature dominated the yield and properties of products, but not the holding time. Among parameters tested, 30.07 wt% oil yield with 75.79% HCs content and 33.05 wt% oil yield with 70.91% HCs content were obtained at 300 °C for 1 h and 1.5 h, respectively. Simultaneously, the remaining solid products were still as high as 53.85 wt% with a carbon content of 79.59% and 48.28 wt% with carbon content of 81.34% under 300 °C for 1 h and 1.5 h, respectively. Ultimate analysis, FT-IR, TGA, and SEM show that solid products could be used as sustainable carbon resources, and solid fuel rather than soil amendment because of risk of micro plastic or adsorbent due to smooth surface without pores. [Display omitted] • Rice straw and LLDPE were co-liquefied in supercritical methanol. • Reaction temperature dominated products distribution and properties. • Oil with 75.79% hydrocarbons content was produced free of catalyst. • Potential application of solid product containing micro plastic was clarified. • High grade solid fuel with HHV of 47.23 MJ/kg was obtained. [ABSTRACT FROM AUTHOR]

Novel bionanocomposite films have been prepared by depositing xylan onto cellulose nanowhiskers through a pH adjustment. Analysis of strength properties, water vapour transmission, transparency, surface morphology and thermal decomposition showed the enhancement of film performance. This provides a new green route to the utilization of biomass for sustainable biomaterials production. [ABSTRACT FROM AUTHOR]

A quick examination of today's biorefining leaders in government, academia and industry brings to mind a group of experts in the prime of their life. Nonetheless, the field has attracted numerous students globally which will become the generation that converts the vision to an established industry. To reflect their interests, I asked several graduate/undergraduate students involved in the field to provide 'Twitter-like' definitions of the 'A, B, C' of biorefining, which have been summarized below: [ABSTRACT FROM AUTHOR]

Three biomass feedstocks (Loblolly pine, Sweetgum, and Miscanthus) were subjected to a novel, two-step ozone pretreatment to enhance the enzymatic digestibility of cellulose. The results show that ozone pretreatment alone did not significantly reduce recalcitrance of the three feedstocks. However, the ozone pretreatment was capable of generating oxidative biomass fragments that can be utilized in a subsequently conventional pretreatment without the need for exogenous acid to be added. For example, employing a dose of ozone followed by an ethanol organosolv pretreatment led to significant delignification and preserved most of the carbohydrates in the three biomass feedstocks. Likewise, ozone treatment followed by autohydrolysis gave higher solubilization of hemicelluloses and distinctive results in terms of enzymatic glucose release and fermentation yields for both Sweetgum (14.00 g ethanol/100.00 g biomass) and Miscanthus (11.10 g ethanol/100.00 g biomass) feedstocks. Although ozone treatment followed by organosolv pretreatment gave low enzymatic glucose release yield for Loblolly pine, a two-step ozone pretreatment has been shown in this study to be a very promising strategy for Sweetgum and Miscanthus feedstocks. [ABSTRACT FROM PUBLISHER]

To improve the bondability between clay filler and lignocellulosic fiber, Kaolin clay particles were modified using a starch−fatty acid complex method. The coating efficiency of starch on clay particle surfaces was investigated by measuring the dissolved starch in the supernatant. The experimental results indicated that more than 98% of the applied starch was precipitated onto the surface of the filler, and the resulting starch−fatty acid−clay composites had relatively good resistance against moderate shear force. The morphology, particle size, and ζ potential of the starch modified filler were also determined with scanning electron microscopy, Malvern particle size analyzer, and Malvern Zetasizer, respectively. An aqueous slurry of linerboard pulp containing 5−15 wt % modified fillers was used for handsheet preparation, and the effects of the addition of modified filler on the paper properties were studied. At a dosage of 10% of the modified filler (based on filler), the retention of the filler was higher than 75%. The strength properties of paper with starch modified fillers were improved by approximately 15% when compared against those of paper with unmodified fillers. [ABSTRACT FROM AUTHOR]

The lignin content of biomass can impact the ease and cost of biomass processing. Lignin reduction through breeding and genetic modification therefore has potential to reduce costs in biomass-processing industries (e.g. pulp and paper, forage, and lignocellulosic ethanol). We investigated compositional changes in two low-lignin alfalfa (Medicago sativa) lines with antisense down-regulation of p-coumarate 3-hydroxylase (C3H) or hydroxycinnamoyl-CoA:shikimate hydroxycin-namoyltransferase (HCT). We investigated whether the difference in reactivity during lignification of 4-coumaryl alcohol (H) monomers versus the naturally dominant sinapyl alcohol and coniferyl alcohol lignin monomers alters the lignin structure. Sequential base extraction readily reduced the H monomer content of the transgenic lines, leaving a residual lignin greatly enriched in H subunits; the extraction profile high- lighted the difference between the control and transgenic lines. Gel permeation chromatography of isolated ball-milled lignin indicated significant changes in the weight average molecular weight distribution of the control versus transgenic lines (CTR1a, 6000; C3H4a, 5500; C3H9a, 4000; and HCT30a, 4000). [ABSTRACT FROM AUTHOR]