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Camellia Oleifera Shell (COS) is a kind of renewable lignocellulose resource and contains abundant hemicelluloses. In this work, the hemicelluloses in COS were extracted by alkali treatment and precipitated by ethanol with different concentration. Thermal pyrolysis kinetics of COS hemicelluloses were investigated using a thermogravimetric analyzer at the heating rates of 5, 10, and 20 °C/min based on Coats-Redfern, Flynn-Wall-Ozawa (FWO), and Kissinger-Akahira-Sunose (KAS) model. The results showed that the best fitting thermal pyrolysis mechanism of COS hemicelluloses was one-dimensional diffusion reaction analyzed by Coats-Redfern model. The activation energies of COS hemicelluloses ranged from 175.07 to 247.87 kJ·mol -1 and from 174.74 to 252.50 kJ·mol -1 calculated by FWO and KAS, respectively. The thermal stabilities of COS hemicelluloses were enhanced with the precipitated ethanol concentration increasing, and reflected by thermodynamic parameters ΔH, ΔG and ΔS. This study may provide basic theoretical supports for the thermochemical conversion of COS hemicelluloses., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Formic acid/water binary solvent extraction with formic acid fraction lower than 77.5% (w/w) of azeotrope was used to extract hemicellulose-derived saccharides from poplar wood at various levels of severity. The highest xylose yield of 77.8% and arabinose yield of 93.5% were obtained at 120 °C and 1 h. To reduce cellulose hydrolysis and facilitate downstream xylose crystallization, mild conditions at 90 °C and 4 h was chosen as optimum severity, which led to the highest xylose fraction of 81.7% in all saccharides extracted, with a remarkable xylose yield of 73.1%. Mass balance analysis showed that 5.84% of xylan was degraded, but only 0.25% of xylan ended up as furfural at optimum severity. The proposed extraction process has high feasibility for industrial application since the low formic acid fraction in solvent allows simple recovery and concentration of used solvent., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The effective separations of cellulose and hemicelluloses from cellulosic fibers are the prerequisite for creating high-value to the abundant and green cellulose materials. In this study, the process concept of cellulase pretreatment, followed by a cold caustic extraction (CCE) was investigated for a softwood sulfite pulp. The results showed that the cellulase pretreatment led to favorable fiber morphological changes, including the increases of the specific surface area (SSA), pore volume and diameter, and the water retention value (WVR). These changes can induce more pronounced fiber swelling in the subsequent CCE process so that the hemicelluloses removal is enhanced. After the cellulase pretreatment (cellulase dosage of 1 mg/g) and CCE process, the cellulose purity was as high as 97.49%, while the hemicelluloses removal selectivity reached 76.42%., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In this study, the microwave was employed during the alkaline treatment process, in order to separate the hemicelluloses and cellulose from a delignified hardwood kraft pulp. In relation to hemicelluloses yield, the integrated microwave and alkaline treatment resulted in 9.25% and 12.05% at 50°C and 80°C, respectively. Correspondingly, the resultant pulp fibers presented the increased cellulose content, which was desirable for manufacturing dissolving pulp. Additionally, the effect from mechanical refining pretreatment followed microwave and alkaline treatment, on the separation of hemicelluloses and cellulose, was also investigated., (Copyright © 2017. Published by Elsevier Ltd.)

The viability of single-step microwave-induced pressurized hot water conditions for co-production of xylan-based biopolymers and bioethanol from aspenwood sawdust and sugarcane trash was investigated. Extraction of hemicelluloses was conducted using microwave-assisted pressurized hot water system. The effects of temperature and time on extraction yield and enzymatic digestibility of resulting solids were determined. Temperatures between 170-200°C for aspenwood and 165-195°C for sugarcane trash; retention times between 8-22min for both feedstocks, were selected for optimization purpose. Maximum xylan extraction yields of 66 and 50%, and highest cellulose digestibilities of 78 and 74%, were attained for aspenwood and sugarcane trash respectively. Monomeric xylose yields for both feedstocks were below 7%, showing that the xylan extracts were predominantly in non-monomeric form. Thus, single-step microwave-assisted hot water method is viable biorefinery approach to extract xylan from lignocelluloses while rendering the solid residues sufficiently digestible for ethanol production., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This work is aimed at investigating the influence of changes in the content of hemicelluloses of the autohydrolyzed poplar sapwood on the subsequent alkali impregnation for chemi-mechanical pulping (CMP). An alkali impregnation process was conducted using the autohydrolyzed poplar sapwood with different content of hemicelluloses as raw materials. The results showed that both the amount of NaOH consumption and swelling degree of poplar sapwood increased with the removal of hemicelluloses, thus enhancing the alkali impregnation effectiveness. The hemicelluloses removal can also shorten the alkali impregnation time for the autohydrolyzed poplar sapwood to achieve the similar impregnation effectiveness of unautohydrolyzed poplar sapwood. All of these can be attributed to the fact that the hemicelluloses removal would result in the exposure of more free hydroxyl groups on the cellulose and an increase in the porosity of the fiber cell walls., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Prehydrolysis of lignocellulose produces abundant hemicellulose-derived saccharides (HDS). To obtain pure HDS for application in food or pharmaceutical industries, the prehydrolysis liquor (PHL) must be refined to remove non-saccharide compounds (NSC) derived from lignin depolymerization and carbohydrate degradation. In this work, activated carbon (AC) adsorption was employed to purify HDS from NSC with emphasis on adsorption selectivity. The adsorption isotherms showed the priority of NSC to be absorbed over HDS at low AC level. However, increase of AC over 90% of NSC removal made adsorption non-selective due to competitive adsorption between NSC and HDS. Size exclusion chromatography showed that the adsorption of oligomeric HDS was dominant while monomeric HDS was inappreciable. The limited selectivity suggested that AC adsorption is infeasibility for HDS purification, but applicable as a pretreatment method., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A combined process of lime treatment and mixed bed ion exchange was proposed to separate hemicellulose-derived saccharides (HDS) from prehydrolysis liquor (PHL) of lignocellulose as value added products. The optimization of lime treatment achieved up to 44.2% removal of non-saccharide organic compounds (NSOC), mainly colloidal substances, with negligible HDS degradation at 0.5% lime level and subsequent neutralization by phosphoric acid. The residual NSOC and calcium ions in lime-treated PHL were eliminated by mixed bed ion exchange. The breakthrough curves of HDS and NSOC showed selective retention toward NSOC, leading to 75% HDS recovery with 95% purity at 17 bed volumes of exchange capacity. In addition, macroporous resin showed higher exchange capacity than gel resin as indicated by the triple processing volume. The remarkable selectivity of the combined process suggested the feasibility for HDS separation from PHL., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A modified process consisting of an initial mechanical refining (R) followed by a low-alkali (5.5% NaOH) cold caustic extraction (CCE) and finally an endoglucanase (EG) treatment (R-5.5%CCE-EG) was investigated for upgrading paper-grade pulp to dissolving pulp. Results showed that compared to the conventional process (9%CCE-EG), the modified process can decrease the alkali concentration (from 9% to 5.5%) to achieve a similar hemicelluloses removal while simultaneously enhancing the Fock reactivity (from 62.2% to 81.0%). The improved results were due to the fact that the mechanical refining resulted in favorable fiber morphological changes, including increased pore volume/size, water retention value and specific surface area. Consequently, the hemicelluloses removal was enhanced even under the subsequent low-alkali CCE condition. A synergic effect of refining, low alkali concentration and enzymatic activation was responsible for the higher reactivity of resulting dissolving pulp., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Prehydrolysis of wood biomass prior to kraft cooking provides a stream containing hemicellulose-derived saccharides (HDSs) but also undesired non-saccharide compounds (NSCs) that were resulted from lignin depolymerization and carbohydrate degradation. In this study, a combined process consisting of lime treatment, resin adsorption, and gel filtration was developed to separate HDSs from NSCs. The macro-lignin impurities that accounted for 32.2% of NSCs were removed by lime treatment at 1.2% dosage with negligible HDSs loss. The majority of NSCs, lignin-derived phenolics, were eliminated by mixed bed ion exchange resin, elevating NSCs removal to 94.0%. The remaining NSCs, furfural and hydroxymethylfurfural, were excluded from HDSs by gel filtration. Chemical composition analysis showed that xylooligosaccharides (XOS) with the degree of depolymerization from 2 to 6 accounted for 28% of the total purified HDSs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Hemicelluloses removal is a prerequisite for the production of high-quality cellulose (also known as dissolving pulp), and further recovery and utilization of hemicelluloses, which can be considered as a typical Integrated Forest Biorefinery concept. In this paper, a process of combined mechanical refining and cold caustic extraction (CCE), which was applied to a softwood sulfite sample, was investigated. The results showed that the hemicelluloses removal efficiency and selectivity were higher for the combined treatment than that for the CCE alone. The combined treatment can thus decrease the alkali concentration (from 8% to 4%) to achieve a similar hemicelluloses removal. The improved results were due to the fact that the mechanical refining resulted in increases in pore volume and diameter, water retention value (WRV) and specific surface area (SSA), all of which can make positive contributions to the hemicelluloses removal in the subsequent CCE process., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Hemicelluloses removal is highly desirable in many biomass processes, including the pretreatment steps of the bioconversion for ethanol production, production of high-quality dissolving pulps. In this study, a sequential treatment consisting of pulp fractionation, followed by caustic treatment to remove hemicelluloses from a softwood sulfite pulp, was investigated. The long-fiber fraction obtained after pulp fractionation, had a lower hemicelluloses content and smaller specific surface area, but larger pore diameter than the short-fiber fraction. The fiber fractions were subsequently treated in a cold caustic extraction (CCE) or hot caustic extraction (HCE). Results showed that hemicelluloses removal in the long-fiber fraction was more pronounced than the short-fiber fraction in both CCE and HCE processes. Other parameters, such as hemicelluloses removal selectivity, yield were studied. The underlying explanations were given., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Direct catalytic transformation of xylan-type hemicelluloses to furfural in the aqueous system and the biphasic system were comparatively investigated under mild conditions. Screening of several promising chlorides for conversion of beech xylan in the aqueous system revealed the Lewis acid SnCl4 was the most effective catalyst. Comparing to the single aqueous system, the bio-based 2-methyltetrahydrofuran (2-MTHF)/H2O biphasic system was more conducive to the synthesis of furfural, in which the highest furfural yield of 78.1% was achieved by using SnCl4 as catalysts under the optimized reaction conditions (150°C, 120 min). Additionally, the influences of xylan-type hemicelluloses with different chemical and structural features from beech, corncob and bagasse on the furfural production were studied. It was found that furfural yield to some extent was determined by the xylose content in hemicelluloses and also had relationships with the molecular weight of hemicelluloses and the degree of crystallization., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The conversion of xylose, water-insoluble hemicelluloses (WIH) and water-soluble fraction (WSF) of corncob to furfural was performed using montmorillonite with tin ions (Sn-MMT) containing double acid sites as a solid acid catalyst. The co-existence of Lewis acids and Brønsted acids in Sn-MMT was shown to improve the furfural yield and selectivity. 76.79% furfural yield and 82.45% furfural selectivity were obtained from xylose using Sn-MMT as a catalyst in a biphasic system with 2-s-butylphenol (SBP) as the organic extracting layer and dimethyl sulfoxide (DMSO) as the co-solvent in contact with an aqueous phase saturated with NaCl (SBP/NaCl-DMSO) at 180°C for 30min. Furthermore, Sn-MMT also demonstrated the excellent catalytic performance in the conversion of pentose-rich materials of corncob and 39.56% and 54.15% furfural yields can be directly obtained from WIH and WSF in the SBP/NaCl-DMSO system, respectively., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study aimed to produce furfural from waste aqueous hemicellulose solution of a hardwood kraft-based dissolving pulp production processing in a green method. The maximum furfural yield of 82.4% and the xylose conversion of 96.8% were achieved at 463K, 1.0g ZSM-5, 1.05g NaCl and organic solvent-to-aqueous phase ratio of 30:15 (V/V) for 3h. The furfural yield was just 51.5% when the same concentration of pure xylose solution was used. Under the optimized condition, furfural yield was still up to 67.1% even after the fifth reused of catalyst. Catalyst recycling study showed that ZSM-5 has a certain stability and can be efficiently reused., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This work investigated the feasibility of recovering and concentrating sugars and acetic acid (HAc) from prehydrolysis liquor (PHL) of the kraft-based dissolving pulp process prior to fermentation of hemicellulosic sugars, by the combination of activated carbon adsorption, nanofiltration (NF) and reverse osmosis (RO) processes. To reduce the fouling PHL was subjected to adsorption on activated carbon, then the treated PHL (TPHL) passed through a nanofiltration (NF DK) membrane to retain the sugars, and the permeate of acetic acid rich solution was passed through a reverse osmosis membrane (RO SG). It was found that for NF process sugars were concentrated from 48 to 227g/L at a volume reduction factor (VRF) of 5 while 80 to 90% of acetic acid was permeated. For the reverse osmosis process, 68% of acetic acid retention was achieved at pH 4.3 and 500 psi pressure and the HAc concentration increased from 10 to 50g/L., (Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.)

In order to establish the correlation between hemicelluloses removal and bioconversion efficiency of cellulose, fractionation process with increasing NaOH concentration selectively released the hemicellulosic polymers with increasing molecular weight and decreasing degree of substitution. Not only the initial hydrolysis rates also the concentrations of glucose and ethanol were significantly enhanced from 5.93 and 8.39 g/L to the range of 8.67-9.60 g/L and 11.53-13.71 g/L after alkaline treatment, respectively. However, the maximum conversions of cellulose to glucose (61.9%) and ethanol (64.6%) were achieved as 33.0% hemicelluloses was still remained. Excluding the negligible effect on the crystal transformation of cellulose, the improvement of bioconversion efficiency was resulted from the synergetical effects of surface exposure, multi-layers collapse and the hydrophilic property of the cellulosic substrate. It is critical task to balance these factors by the partial removal of hemicellulosic component, not complete., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The effect of five different wood particle size fractions between 0.5 and 12.5 mm on hot-water extraction of acetylated water-soluble hemicelluloses from spruce wood with a batch extraction setup at 170 °C was investigated. Extraction kinetics, with regard to particle size, was also studied. The purpose was to intensify the hemicellulose extraction for high molar mass hemicelluloses at high yield and purity. About 30% of the wood was dissolved and basically all the hemicelluloses could be extracted. The average molar masses of the extracted hemicelluloses decreased rapidly during the first 10 min of the extraction, but were not much affected by the difference in wood particle sizes. Smaller particles resulted in higher extraction rates. The reaction order was established to be of pseudo-first order for particles above 2mm and 1.5st order for particles smaller than 2mm. The effective diffusion coefficient was determined to be 9.11×10(-10) m(2)/s., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The potential of near infrared spectroscopy in conjunction with partial least squares regression to predict chemical composition of various wood species including softwoods and hardwoods was examined. Hot-water-soluble extractive, pentosan and cellulose content of various wood species were predicted with high coefficient of determination between the predicted and measured values, the ratio of performance to deviation, range error ratio, and low root mean square error of cross validation for cross-validation and root mean square error of prediction for test set validation. Hot-water-soluble extractive and cellulose content models were only suitable for quality control analysis, but pentosan content model had an excellent fit with the data and could be used in any application. All the results indicate that Fourier transform near infrared spectroscopy could be applied to predict the chemical composition of various wood species., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Two methods for separation of polymeric galactoglucomannans (GGMs) from a hot-water extract of spruce wood, i.e., membrane filtration and precipitation in ethanol-water, were compared. Filtration through a series of membranes with different pore sizes separated GGMs of different molar masses, from polymers to oligomers. Only polysaccharides were precipitated in ethanol-water. With the optimal water content of 5-15%, the precipitated amount was about 6% on wood basis. The average molar mass of the precipitated polysaccharides was 10-12kDa with a molar mass range of 4-20kDa. GGMs comprised about 80% of the precipitated hemicelluloses. Other precipitated polysaccharides were mainly arabinoglucuronoxylans and pectins (rhamnogalacturonans). Analysis of a lignin-free, ethanol-precipitated GGM preparation by (13)C NMR spectroscopy verified that it was structurally almost identical with a GGM-rich ethanol precipitate obtained from spruce wood by extraction at much milder conditions, 90°C for 60min., (Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.)

To test a biorefinery concept, the non-wood biomass of Eulaliopsis binata was treated with dilute acid prior to dissolving pulp production at 160 °C for 30 min. The pretreatment liquor (PL) contained 42.04 g/L sugars, of which 81.46% was xylose and only 2.91% was glucose. Furfural and hydroxymethylfurfural in PL were 0.37% and 0.06%, respectively. Chemical or enzymatic hydrolysis of carbohydrates could be omitted when producing bioethanol with PL because 87.32% of the total sugars were in the form of monosaccharides. Membrane filtration with a molecular-weight cut-off of 100 Da was employed to concentrate the sugars and a concentration of 170.49 g/L was achieved. A method of zero release of the PL is proposed, which consists of ethanol production from the concentrated PL and recycling the permeate stream into the pretreatment process., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Ground spruce wood was extracted with water at 170 °C at four different pH levels (3.8, 4.0, 4.2 and 4.4) achieved by using phthalate buffers. Static batch extractions were carried out in an accelerated solvent extractor (ASE-300). The extracted non-cellulosic carbohydrates, predominantly galactoglucomannans (GGMs), were characterised mainly by sugar unit analysis and molar mass determination. Compared to extraction with plain water, extractions with phthalate buffer solutions gave similar yields of non-cellulosic carbohydrates, but gave up to 70% less monosaccharides, and consequently higher molar masses of extracted GGMs. Moreover, at these pH levels, the hydrolysis of acetyl groups were decreased by 40% compared to extraction with plain water, thus maintaining the water solubility of GGMs. It is concluded that hot water extraction of hemicelluloses in high-molar-mass form (average Mw about 10 kDa) from wood in good yields (8% of wood) demands appropriate control of pH, to a level of about 4., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

Hemicelluloses in industrially produced pre-hydrolysis liquor (PHL) were precipitated with ethanol. These PHL-derived hemicelluloses (PHL-EH) and a commercial, pure birch wood xylan sample (powder form) (BWX) were bleached using chlorine dioxide (D(0) and D(1)) and hydrogen peroxide (Ep) in the D(0)EpD(1) sequence, and the chemical compositions, molecular weights and charge densities of the treated samples were assessed. When applied to high-yield pulp (HYP) at 50 mg/g, 26 and 20 mg/g of the bleached PHL-EH and BWX, respectively, were adsorbed without significantly affecting paper properties. These results suggest that semi-bleached hemicelluloses could be used to increase the basis weight of paper products. Furthermore, an integrated process was proposed that converts the kraft-based dissolving pulp production process into a biorefinery unit with dissolving pulp, bleached hemicelluloses and lignin as main products., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

In this study the influence of the insoluble solids in nano-filtrated sugar maple hemicellulosic hydrolysate on the metabolic behavior of Pichia stiptis was investigated. The particle properties of hemicellulosic hydrolysate were analyzed. Phosphoric acid and ammonium (PA) were applied to remove the particles. The metabolic behavior and growth property of P. stipitis in particle--removed hydrolysate was measured. Results demonstrated that the average particle size and zeta potential of the untreated hydrolysate were 2266.9±78.2 nm and -6.09±0.49 mV. Xylose consumption and ethanol production rate were significantly decreased when particle content is greater than 1.63 g/L. Because the majority of particles (34 g/L) were removed from hydrolysates by phosphoric acid and ammonium treatment, the fermentability of the hydrolysate was significantly improved. These results indicated particles play an important role in hydrolysate inhibition effect., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

In this paper, we proposed a new modification for an ethanol-based pulping process, which would consist of the pre-hydrolysis (pre-extraction) of wood chips for removing hemicelluloses; the ethanol extraction of pre-hydrolyzed wood chips for removing lignin; and the post purification of cellulose, leading to the production of pure cellulose. We also experimentally evaluated the separation of hemicelluloses from the pre-hydrolysis liquor (PHL) obtained from a pulp mill. To remove lignin from the PHL, it was acidified to a pH of 2, which resulted in 47% lignin precipitation. The lignin separation from the acidified PHL was further improved via adding polyethylene oxide and poly aluminum chloride or adding ethyl acetate. To recover the hemicelluloses from the acidified PHL, ethanol was added to the acidified PHL with a volumetric ratio of 4 to 1. The isolated lignin and hemicelluloses were characterized by a Fourier transform infrared spectroscopy (FTIR) and a gas permeation chromatography (GPC)., (Copyright © 2010 Elsevier Ltd. All rights reserved.)