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Hemicelluloses consume alkali during kraft pulping and dissolve in the black liquor as a low energy fuel. Acidic pre-hydrolysis of softwood chips removes hemicelluloses but preserves cellulose content prior to pulping. This study compared mild pre-hydrolysis (140 °C) kraft pulping with conventional kraft pulping of commercial softwood chips at two H-factors for wood chips with thickness ranging from less than 2 mm to over 6 mm. The chip thickness less than 2 mm increased hemicelluloses oligomer yield and showed little influence on pulp fiber yield. However, the kraft pulp fiber length decreased 5.6%. Kappa number and fiber reject increased dramatically when chip thickness was greater than 6 mm. The detailed compositional analysis of kraft pulp and fiber quality analysis indicate that pre-hydrolysis followed by kraft pulping enhanced delignification with limited reduction of fiber length and width, and increased kinks. Strategic considerations for the integration of pre-hydrolysis into kraft pulping for future biorefineries were outlined.

Previously it was shown that wood chip compression or enzyme impregnation prior to refining reduces energy consumption and improves pulp quality. This work characterizes the effect of different magnitudes and rates of compression on the extent of enzymatic hydrolysis. A laboratory compressor and a controlled uniaxial load set-up were used to apply different compression ratios and compression times to mixed-softwood wood chips. The chips were subsequently subjected to enzymatic hydrolysis with a high-yield exoglucanase preparation to demonstrate changes in cellulose hydrolysis. Enzymatic hydrolysis yield increased with compression ratio but was unaffected by compression time. Increasing compression ratio increased removal of soluble molecules such as sugars and acid-soluble lignin. Microscopy imaging showed increased cell wall buckling and fracturing with increased compression. The morphological changes led to improved enzyme diffusion and resulted in higher available surface area. The improved cellulose hydrolysis is due to changes in wood morphology as well as the removal of extractives.

The adsorption of locust bean gum (LBG) onto Northern Bleached Softwood Kraft (NBSK) pulp improved paper tensile and burst strength and lowered refining energy by strengthening inter-fibre bonding. Adsorption kinetics and isotherms were investigated to develop a fundamental understanding of the adsorption mechanism. The adsorption rate followed pseudo-second-order kinetics and the activation energy was 99.34 kJ·mol−1, suggesting chemisorption. The adsorption rate constant increased rapidly with temperature from 25 to 45 °C (k = 1.93 to 24.03 g·mg−1·min−1), but the amount adsorbed at equilibrium decreased (qe = 1.91 to 0.48 mg·g−1 o.d. fibre). LBG adsorption to NBSK at 25 °C was consistent with the Langmuir adsorption model for LBG n = 5.00, and the equilibrium constant Kf = 2.57 mg·g−1·(mg·L−1)−1/n at 25 °C. Favorable adsorption conditions for negatively charged LBG were identified: 25 °C for 10 min, low dosage level ( 150 r.p.m.), acidic or neutral conditions (pH 2–7) without salt addition. Graphic abstract

Hemicelluloses are amorphous polymers of sugar molecules that make up a major fraction of lignocellulosic biomasses. They have applications in the bioenergy, textile, mining, cosmetic, and pharmaceutical industries. Industrial use of hemicellulose often requires that the polymer be hydrolyzed into constituent oligomers and monomers. Traditional models of hemicellulose degradation are kinetic, and usually only appropriate for limited operating regimes and specific species. The study of hemicellulose hydrolysis has yielded substantial data in the literature, enabling a diverse data set to be collected for general and widely applicable machine learning models. In this paper, a dataset containing 1955 experimental data points on batch hemicellulose hydrolysis of hardwood was collected from 71 published papers dated from 1985 to 2019. Three machine learning models (ridge regression, support vector regression and artificial neural networks) are assessed on their ability to predict xylose yield and compared to a kinetic model. Although the performance of ridge regression was unsatisfactory, both support vector regression and artificial neural networks outperformed the simple kinetic model. The artificial neural network outperformed support vector regression, reducing the mean absolute error in predicting soluble xylose yield of test data to 6.18%. The results suggest that machine learning models trained on historical data may be used to supplement experimental data, reducing the number of experiments needed.

The fate of hydrogen during glycerol aqueous phase reforming (APR) and the effect of in situ phenol hydrogenation (IGAPH) with Raney Ni on the glycerol APR mechanism were studied. Glycerol APR proc...

The diversity of hemicellulose oligomers enables many potential applications, but controlling yield and oligomer molar mass is challenging. Oligomer production by hydrolysis of softwoods was invest...

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Xylan obtained from birch (betula pendula) by a novel semi-industrial scale aqueous based method was used for studying the hydrolysis and consecutive hydrolysis-hydrogenation processes in continuous reactors. Dowex 50WX2-100 was chosen as the hydrolysis catalyst based on the results of catalyst screening performed previously in batch reactor. It was also observed to perform well in continuous reactor converting xylan to xylose in high yield under the studied reaction conditions. The influence of several reaction parameters were investigated for optimization. Similar experimental conditions used in the hydrolysis were then applied for studying one flow through hydrolysis and hydrogenation of the semi-industrial xylan. A consecutive catalyst bed consisting of ruthenium on carbon was introduced into the continuous reactor downstream from the hydrolysis bed to hydrogenate monosaccharides to xylitol. Hydrogen was co-fed into the reactor with the xylan solution. Reaction parameters, including temperature, residence time and hydrogen pressure, were varied to maximize the xylitol yield. The developed continuous process was demonstrated to be highly selective and efficient for the valorization of the semi-industrial xylan by yielding over 90% xylitol under optimal experimental conditions. It was noticed, that co-feeding hydrogenation decreased the degradation of monosaccharides during hydrolysis, thus improving the selectivity towards the target product and enabling remarkable process intensification. Moreover, mathematical modelling was performed for the hydrolysis and one flow through hydrolysis and hydrogenation processes. The models take into account the consecutive reaction pathways and the influence of the experimental conditions. Good fits of the model to the experimental data were obtained. The conversion of this novel, well characterized wood-based xylan to produce xylose or xylitol in continuous reactors has not been studied previously. The current work contributes significantly to understanding the processing of real feedstock in one flow through employing consecutive reactions and provides necessary data for process intensification.

In-situ glycerol aqueous phase reforming and phenol hydrogenation (IGAPH) was conducted with Raney Ni® at 180–240 °C for phenol to glycerol ratios from 0 to 4.88. Thermodynamic analysis of the complex IGAPH reaction system revealed the need to balance endothermic glycerol aqueous phase reforming (APR) and exothermic phenol hydrogenation reactions. It was found that maximum glycerol carbon selectivity for APR and maximum hydrogen selectivity for phenol hydrogenation occurred at 220 °C. Addition of phenol to glycerol APR increased glycerol conversion and glycerol carbon selectivity for APR. These observations can be attributed to an equilibrium shift to the forward APR reaction due to hydrogen consumption and suppression of competing parallel reactions by phenol hydrogenation. An initial rate model of the system suggests that IGAPH proceeds via the Langmuir-Hinshelwood mechanism and is rate-limited by phenol hydrogenation. Perspectives for future process development in terms of reaction heat and catalyst stability are provided.

Author(s): Jung, Seokwon; Trajano, Heather L; Yoo, Chang Geun; Foston, Marcus B; Hu, Fan; Tolbert, Allison K; Wyman, Charles E; Ragauskas, Arthur J

Enzyme recycling by adsorption from supernatant to fresh substrate is a promising strategy to reduce enzyme expenses and the production cost of lignocellulosic ethanol. The study was performed using oxygen-delignified wheat straw, and the effect of lignin content, enzyme loading, and hydrolysis time on recycling was determined. The percent of recycled cellulases, 0–35% of initial cellulase loading, increased with increasing enzyme loading and hydrolysis time but decreased with increasing lignin content. Cellulose conversions of 10–71% were achieved during the second hydrolysis round using only recycled cellulases indicating the existence of a highly active subset of enzymes. To achieve constant production of sugars during enzyme recycling, fresh cellulases were loaded before the second hydrolysis round to match the cellulase loading used in the first round. Subsequently, similar glucose, xylose, and protein concentrations were obtained at the end of the first and second rounds for all conditions. Recyclin...

Open foam structures are very beneficial as heterogeneous catalysts for three-phase processes, because they have high efficiency and low pressure drop. A mathematical model for open foam catalyst structures was developed. It was based on the concept of axial dispersion as flow pattern, on liquid-solid mass transfer effects and intrinsic kinetics on the active sites of the catalyst. Rate equations were presented for the hydrogenation of individual sugars and binary sugar mixtures on Ru/C catalysts and they were implemented in the mass transfer and flow models of the open foam catalyst. The flow pattern in the foam structure was confirmed with step change experiments with an inert tracer. The multiphase model was applied on the hydrogenation of arabinose and galactose in a laboratory-scale open foam catalyst bed. The model was able to reproduce the main features of the experimental observations, both for individual sugars and binary sugar mixtures.

To improve the efficiency of enzymatic hemicellulose removal from bamboo pre-hydrolysis kraft pulp, mechanical refining was conducted prior to enzyme treatment. Refining significantly improved the subsequent hemicellulose removal efficiency by xylanase treatment. Results showed that when PFI refining was followed by 3 h xylanase treatment, the xylan content of the bamboo pre-hydrolysis kraft pulp (after first stage oxygen delignification) could be decreased to 2.72% (w/w). After bleaching of enzyme treated pulp, the alpha-cellulose content was 93.4% (w/w) while the xylan content was only 2.38%. The effect of refining on fibre properties was investigated in terms of freeness, water retention value, fibre length and fibrillation characteristics. The brightness, reactivity and viscosity were also determined to characterize the quality of final pulp. Results demonstrated the feasibility of combining refining and xylanase treatment to produce high quality bamboo dissolving pulp.

This study presents high temperature water-only continuous flowthrough pretreatment coupled with nuclear magnetic resonance (NMR) as a promising analytical tool to examine the plant cell wall, to understand its recalcitrance (i.e., cell wall resistance to deconstruction), and to probe the chemistry occurring during batch pretreatment of biomass. (13)C-enriched corn stover stems were pretreated at 170°C for 60min with a hot-water flow rate of 20mL/min to control fractionation of the cell wall. This approach helped elucidate the nature of plant cell wall chemical recalcitrance and biomass pretreatment chemistry by tracking cell wall fragmentation as a function of time. Fractions of the reactor effluent were collected in a time-resolved fashion and characterized by various NMR techniques to determine the degree and sequence of fragments released, as well as, the chemical composition, molecular structure, and relative molecular weight of those released fragments.

Previous studies defined easy and difficult to hydrolyze fractions of hemicellulose that may result from bonds among cellulose, hemicellulose, and lignin. To understand how such bonds affect hydrolysis, Populus trichocarpa × Populus deltoides, holocellulose isolated from P. trichocarpa × P. deltoides and birchwood xylan were subjected to hydrothermal flow-through pretreatment. Samples were characterized by glycome profiling, HPLC, and UPLC-MS. Glycome profiling revealed steady fragmentation and removal of glycans from solids during hydrolysis. The extent of polysaccharide fragmentation, hydrolysis rate, and total xylose yield were lowest for P. trichocarpa × P. deltoides and greatest for birchwood xylan. Comparison of results from P. trichocarpa × P. deltoides and holocellulose suggested that lignin-carbohydrate complexes reduce hydrolysis rates and limit release of large xylooligomers. Smaller differences between results with holocellulose and birchwood xylan suggest xylan-cellulose hydrogen bonds limited hydrolysis, but to a lesser extent. These findings imply cell wall structure strongly influences hydrolysis.

Biorefineries of second generation (2G) are receiving more attention nowadays as an option for the development of bioeconomy all over the world. One of the main pretreatments utilized in this type of facilities for the conversion of lignocellulosic biomass is the use of hydrothermal processing using only water/steam as catalyst under different forms of heating (steam, electric heating jackets, or microwave radiation) at different temperatures. Currently, biorefineries are focused on obtaining feedstocks to produce biofuels, but the current position of these on the market shows that the new biorefineries must be integrated systems and so there is a need to focus on the valorization of the whole coproducts. One of them is hemicellulose, from which for instance oligomers could be derived and used in different areas as pharmaceutical products, food ingredients, fuels, chemicals, and bioplastics. In Mexico, avocado represents an important source for agro-industrial residues. These residues are in a process of valorization under the biorefinery concept, to obtain different types of bioproducts. This chapter describes the concepts usually utilized for the definition and understanding of biorefinery, especially the utilization of hydrothermal pretreatments. It focuses also on linking the concept of bioeconomy with biorefineries, and it introduces the utilization of avocado residues as an example of a Mexican residue with potential importance in the global market.

Hydrolysis to remove hemicellulose and/or generate saccharides is an integral unit operation for the production of chemicals, fuels, and materials from lignocellulosic biomass. Softwoods and bamboo are both widely available but comparatively understudied feedstocks. This paper first reviews the unique hemicellulose chemistry of these feedstocks and the fundamental mechanism of polysaccharide hydrolysis. The influence of temperature, time, acid concentration, particle size, and reactor configuration on water-only hydrolysis, or autohydrolysis, and dilute acid hydrolysis are summarized. The composition, molecular weight, and yields of saccharides and degradation products generated during hydrolysis are presented. Finally, the types, strengths, and weaknesses of current hemicellulose hydrolysis kinetic models are reviewed. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd

Both fluidized sand baths and steam chambers have been used to heat laboratory reactors, in particular for studies of biomass pretreatment. In this study, several aspects of the heating performance of these devices were compared: time to heat reactors to reaction temperature, the stability of reactor temperature, and the convection coefficient. The convection coefficient was determined using correlations and multiple analyses of empirical data. On the basis of the results presented in this study, the steam chamber can heat reactors to temperature in a tenth of the time sand baths can, can maintain a more stable temperature during pretreatment, and has a convection coefficient one to two magnitudes greater than that of the sand bath. Therefore if heat transfer is critical, a steam chamber is advantageous.

Considerable effort has been devoted to the development of biofuels from renewable lignocellulosic biomass. To resolve the challenges associated with the structural barrier of lignocellulosic biomass, hydrothermal pretreatment is applied to alter the structure and improve the accessibility of carbohydrate sugars to microorganisms or chemicals in the subsequent conversion processes. Hydrothermal pretreatment takes advantage of high moisture content of biomass and efficiently converts polysaccharides into monomeric sugars and their corresponding degradation products. To achieve this goal, multiple technologies have been explored using liquid water as the media, with or without addition of chemicals (acids or alkalis). However, there are difficulties in developing an optimized and universal treatment approach due to the heterogeneity of biomass. In this chapter, four major biomass types, wood, bamboo, agricultural residues, and agave, are discussed and compared with respect to feedstock composition and response to the various hydrothermal pretreatments. Moreover, the reaction pathways of individual biomass components (hemicellulose, cellulose, lignin, extractive, and ash) under different treatment conditions (acidic and alkaline) are also comparatively reviewed. Finally, the effects of pH, biomass solid loading, and reactor selection on pretreatment are presented.

Background During pretreatment, hemicellulose is removed from biomass via proton-catalyzed hydrolysis to produce soluble poly- and mono-saccharides. Many kinetic models have been proposed but the dependence of rate on proton concentration is not well-defined; autohydrolysis and dilute-acid hydrolysis models apply very different treatments despite having similar chemistries. In this work, evolution of proton concentration is examined during both autohydrolysis and dilute-acid hydrolysis of hemicellulose from green bamboo. An approximate mathematical model, or “toy model”, to describe proton concentration based upon conservation of mass and charge during deacetylation and ash neutralization coupled with a number of competing equilibria, was derived. The model was qualitatively compared to experiments where pH was measured as a function of time, temperature, and initial acid level. Proton evolution was also examined at room temperature to decouple the effect of ash neutralization from deacetylation. Results The toy model predicts the existence of a steady-state proton concentration dictated by equilibrium constants, initial acetyl groups, and initial added acid. At room temperature, it was found that pH remains essentially constant both at low initial pH and autohydrolysis conditions. Acid is likely in excess of the neutralization potential of the ash, in the former case, and the kinetics of neutralization become exceedingly small in the latter case due to the low proton concentration. Finally, when the hydrolysis reaction proceeded at elevated temperatures, one case of non-monotonic behavior in which the pH initially increased, and then decreased at longer times, was found. This is likely due to the difference in rates between neutralization and deacetylation. Conclusions The model and experimental work demonstrate that the evolution of proton concentration during hydrolysis follows complex behavior that depends upon the acetyl group and ash content of biomass, initial acid levels and temperature. In the limit of excess added acid, pH varies very weakly with time. Below this limit, complex schemes are found primarily related to the selectivity of deacetylation in comparison to neutralization. These findings indicate that a more rigorous approach to models of hemicellulose hydrolysis is needed. Improved models will lead to more efficient acid utilization and facilitate process scale-up.

The economical production of fuels and commodity chemicals from lignocellulose requires the utilization of both the cellulose and hemicellulose fractions. Xylanase enzymes allow greater utilization of hemicellulose while also increasing cellulose hydrolysis. Recent metabolic engineering efforts have resulted in a strain of Thermoanaerobacterium saccharolyticum that can convert C 5 and C 6 sugars, as well as insoluble xylan, into ethanol at high yield. To better understand the process of xylan solubilization in this organism, a series of targeted deletions were constructed in the homoethanologenic T. saccharolyticum strain M0355 to characterize xylan hydrolysis and xylose utilization in this organism. While the deletion of β-xylosidase xylD slowed the growth of T. saccharolyticum on birchwood xylan and led to an accumulation of short-chain xylo-oligomers, no other single deletion, including the deletion of the previously characterized endoxylanase XynA, had a phenotype distinct from that of the wild type. This result indicates a multiplicity of xylanase enzymes which facilitate xylan degradation in T. saccharolyticum . Growth on xylan was prevented only when a previously uncharacterized endoxylanase encoded by xynC was also deleted in conjunction with xynA . Sequence analysis of xynC indicates that this enzyme, a low-molecular-weight endoxylanase with homology to glycoside hydrolase family 11 enzymes, is secreted yet untethered to the cell wall. Together, these observations expand our understanding of the enzymatic basis of xylan hydrolysis by T. saccharolyticum .

Background Effective enzymatic hydrolysis of lignocellulosic biomass benefits from lignin removal, relocation, and/or modification during hydrothermal pretreatment. Phase transition, depolymerization/repolymerization, and solubility effects may all influence these lignin changes. To better understand how lignin is altered, Populus trichocarpa x P. deltoides wood samples and cellulolytic enzyme lignin (CEL) isolated from P. trichocarpa x P. deltoides were subjected to batch and flowthrough pretreatments. The residual solids and liquid hydrolysate were characterized by gel permeation chromatography, heteronuclear single quantum coherence NMR, compositional analysis, and gas chromatography–mass spectrometry. Results Changes in the structure of the solids recovered after the pretreatment of CEL and the production of aromatic monomers point strongly to depolymerization and condensation being primary mechanisms for lignin extraction and redeposition. The differences in lignin removal and phenolic compound production from native P. trichocarpa x P. deltoides and CEL suggested that lignin-carbohydrate interactions increased lignin extraction and the extractability of syringyl groups relative to guaiacyl groups. Conclusions These insights into delignification during hydrothermal pretreatment point to desirable pretreatment strategies and plant modifications. Because depolymerization followed by repolymerization appears to be the dominant mode of lignin modification, limiting the residence time of depolymerized lignin moieties in the bulk liquid phase should reduce lignin content in pretreated biomass. In addition, the increase in lignin removal in the presence of polysaccharides suggests that increasing lignin-carbohydrate cross-links in biomass would increase delignification during pretreatment.

A wide variety of conversion processes can be used to generate fuels and chemicals from biomass, with many including a hydrolysis and/or dehydration reaction at low pH as an initial stage. In the case of acid hydrolysis of biomass prior to enzymatic hydrolysis and fermentation, this step is called pretreatment. Due to the diversity of conversion processes, it is difficult to define a single set of objectives; the general goals however are to generate reactive intermediates in high yields for subsequent conversion to final products and minimize generation of compounds that interfere with downstream operations. For example, if lignocellulosic biomass is to be converted to ethanol through dilute acid pretreatment, enzymatic hydrolysis, and fermentation, the objectives of pretreatment are to produce high yields of hemicellulose sugars, improve the enzymatic digestibility of the remaining solids to realize high yields of glucose, and avoid generating biological inhibitors such as furfural and acetic acid. On the other hand, if lignocellulosic biomass is to be converted into jet fuel alkanes through cellulose hydrolysis to levulinic acid followed by catalytic processing of levulinic acid to alkanes, the objectives are to generate levulinic acid in high yields and avoid solid catalyst poisons such as mineral acids. Two of the primary advantages of low-pH reactions are the ready availability of catalysts such as H2SO4 and SO2 and high product yields. However, the capital costs of reactors and associated equipment used for low-pH reactions are high due to the need for expensive, corrosion-resistant materials. In addition, the solid and liquid streams resulting from low-pH pretreatment often require washing or neutralization. Both of

The cost of enzymes makes enzymatic hydrolysis one of the most expensive steps in the production of lignocellulosic ethanol. Diverse studies have used commercial enzyme cocktails assuming that change in total protein concentration during hydrolysis was solely due to adsorption of endo- and exoglucanases onto the substrate. Given the sensitivity of enzymes and proteins to media conditions this assumption was tested by evaluating and modeling the protein concentration of commercial cocktails at hydrolysis conditions. In the absence of solid substrate, the total protein concentration of a mixture of Celluclast 1.5 L and Novozyme 188 decreased by as much as 45% at 50 °C after 4 days. The individual cocktails as well as a mixture of both were stable at 20 °C. At 50 °C, the protein concentration of Celluclast 1.5 was relatively constant but Novozyme 188 decreased by as much as 77%. It was hypothesized that Novozyme 188 proteins suffer a structural change at 50 °C which leads to protein aggregation and precipitation. Lyophilized β-glucosidase (P-β-glucosidase) at 50 °C exhibited an aggregation rate which was successfully modeled using first order kinetics (R (2) = 0.97). By incorporating the possible presence of chaperone proteins in Novozyme 188, the protein aggregation observed for this cocktail was successfully modeled (R (2) = 0.96). To accurately model the increasing protein stability observed at high cocktail loadings, the model was modified to include the presence of additives in the cocktail (R (2) = 0.98). By combining the measurement of total protein concentration with the proposed Novozyme 188 protein aggregation model, the endo- and exoglucanases concentration in the solid and liquid phases during hydrolysis can be more accurately determined. This methodology can be applied to various systems leading to optimization of enzyme loading by minimizing the excess of endo- and exoglucanases. In addition, the monitoring of endo- and exoglucanases concentrations can be used to build mass balances of enzyme recycling processes and to techno-economically evaluate the viability of enzyme recycling.