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1.
The content and structure of lignin have been considered as important factors that affect both pretreatment and enzymatic hydrolysis of lignocellulosic biomass. In this work, wheat stems (WS) were pretreated using mild alkali including green liquor (GL) and sodium carbonate (SC). The results indicate that GL pretreatment exhibits better delignification selectivity and higher enzymatic digestibility than SC pretreatment. Analysis of 1H–13C HSQC NMR and FTIR on cellulolytic enzyme lignin (CEL) preparations isolated from untreated and pretreated WS also proves that a certain amount of lignin degrades which leads to a decrease of β-O-4′ linkages. Under mild alkaline conditions, more guaiacyl units in lignin are removed than syringyl units, which results in a higher condensation degree and S/G ratio of CELs isolated from GL- and SC-pretreated stems. Compared with p-coumarate structures, ferulates in lignin are more stable under mild alkaline conditions.  相似文献   

2.
Long‐term lime pretreatment has proven to increase digestibility of many herbaceous lignocellulose sources; but until this work, its effects had not been evaluated on wood, whose lignin content is higher, and therefore, more recalcitrant to enzymatic hydrolysis. In this study, the mild conditions of long‐term lime pretreatment (1‐atm pressure, temperatures ranging from 25 to 75°C, and reaction times between 1 and 12 weeks, with and without air) were systematically applied to poplar wood available in two batches with different lignin contents. These batches were designated as low‐lignin biomass (LLB) with lignin content of 21.4% and high‐lignin biomass (HLB) with lignin content of 29.1%. Full factorial designs resulted in 79 samples of pretreated poplar that were analyzed for lignin and carbohydrates pretreatment yields, and enzymatic digestibility (15 FPU/g glucan in raw biomass cellulose loading). After aerated lime pretreatment at 65°C for 4 weeks, and subsequent enzymatic hydrolysis, an overall yield of 0.76 g glucan + xylan recovered per gram glucan + xylan in raw biomass was obtained. This is equivalent to an increased poplar wood digestibility of 7.5‐fold compared with untreated biomass. Different batches of the feedstock resulted in different lignin and carbohydrates pretreatment yields; however, overall yields of carbohydrates (combining pretreatment and enzymatic hydrolysis) were similar. © 2010 American Institute of Chemical Engineers AIChE J, 2011  相似文献   

3.
Structural characteristics of lignocellulosic biomass such as surface area, pore volume, crystallinity, hemicellulose, and lignin content significantly affect the yield of fermentable sugars for bioethanol production. In the present work, the effect of dilute acid pretreatment was studied on structural characteristics of wheat straw, using different combinations of process variables (temperature, time, and acid concentration). Pretreated wheat straw (PWS) exhibited higher available surface area and pore volume along with low hemicellulose and lignin content. Crystallinity index (CrI) of biomass at different pretreatment conditions showed an increased trend followed by sharp decrease at high temperature (190°C) conditions. Maximum increase in surface area (7.1 m2/g compared to 4.0 m2/g for untreated wheat straw) was obtained at pretreatment conditions of 180°C temperature, 0.5% (v/v) acid, and 7 min time. SEM imaging of biomass revealed that pore breaking, compression of pores, and partial pore blocking in the case of high temperature (190°C) pretreatment conditions may be the reason behind decreased surface area of biomass. FT-IR analysis showed almost complete hemicellulose removal and acid-soluble lignin removal after dilute acid pretreatment but insufficient removal of acid insoluble lignin.

[Supplementary material is available for this article. Go to the publisher's online edition of Chemical Engineering Communications for the following free supplemental resource: figure showing XRD pattern of biomass with respect to different pretreatment conditions.]  相似文献   

4.
A prototype hardwood Populus deltoids has been fractionated in kg quantities into its primary constitutive polymers, namely, cellulose, hemicelluloses, and lignin, under optimal recovery conditions for each fraction. Our approach is targeted at processing sawdust or finally divided wood (dp ≤ 0.5 mm) and involves a thermomechano-solvolytic treatment of medium consistency suspensions in two process development units operated sequentially. Firstly, the hemicellulose fraction is removed from the initial wood by a aqueous-steam pretreatment (auto-hydrolysis) at conditions where nearly 90% of the hemicelluloses are solubilized. Secondly, the treated wood (lignocellulose) is separated into cellulose and lignin rich fractions by subjecting it to an organosolvolytic treatment using ethylene glycol as solvent. An experimental unit which can be operated in semi-continuous or continuous modes is described and was employed for this step. The recovery of each fraction via appropriate mass balances is presented. Also, a comparative characterization of the lignins isolated via (a) the direct solvolysis route and (b) the sequential aqueous-steam pretreatment followed by solvolysis approach is made using solvent fractionation, molar mass distribution, and 13C NMR spectroscopy methods.  相似文献   

5.
Resorcinol‐formaldehyde adhesives can reinforce stress fractures that appear from wood surface preparation. Researchers have found that applying the resorcinol‐formaldehyde prepolymer, hydroxymethylated resorcinol, to the surface of wood improves the bond strength of epoxy and polyurethane adhesives to wood. Hydroxymethylated resorcinol is thought to plasticize lignin components and stabilize stress fractures through reactions with lignin subunits and hemicelluloses in wood. In this study, a dilute solution of hydroxymethylated resorcinol (HMR) is cured in the presence of a crude milled‐wood lignin (cMWL) from Acer saccharum and subsequently dissolved in dimethylsulfoxide‐d6 to delineate reactivity with lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan using solution‐state NMR spectroscopy. 1H–13C single‐bond correlation NMR experiments revealed that the HMR only formed 4,4′‐diarylmethane structures with itself in the presence of the cMWL; the 2‐methylols that formed remained free and did not crosslink with resorcinol. Cured HMR resin formed both 4,4′‐ and 2,4‐diarylmethane structures, confirming that the presence of lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan hinders crosslinking at the C‐2 position. No evidence of reactivity between HMR and lignin subunits was found. New peaks consistent with ester linkages were observed in 13C‐NMR spectra of the cMWL sample treated with HMR that may be attributable to HMR moieties condensing with glucuronic acid substituents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45398.  相似文献   

6.
The posttreatment of various organosolvs pretreated wheat straw with cyanamide-activated hydrogen peroxide was studied. About 44–80% of the total residual lignin and 38–85% of the total residual hemicelluloses were released or degraded during the posttreatment with 1.8% H2O2–0.18% cyanamide at 50°C under pH 10.0 for 4 h from different aqueous organic acids or alcohols pretreated straw. The seven degraded residual lignin preparations were subjected to a comprehensive physicochemical and structural characterization by UV, FTIR, and 1H and 13NMR spectroscopy, and GPC. The nitrobenzene oxidation method was also applied to the in situ lignins. It was found that the seven residual lignin preparations contained large amounts of noncondensed syringyl and guaiacyl units, together with fewer noncondensed p-hydroxyphenyl units, esterified p-coumaric acid, and mainly etherified ferulic acid. All of the lignin fractions are free of associated polysaccharides and had molecular-average weights ranging between 2980 and 3820 g mol−1. Analysis of these low molecular weight degradation products revealed an oxidation of residual lignin had occurred. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

7.
In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.  相似文献   

8.
Abstract

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO4), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO4. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO4 does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm?1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process.  相似文献   

9.
A parametric investigation of NH4OH catalyzed solvent delignification of poplar was conducted to define pretreatment conditions which would yield an optimal separation of the biomass components and an enzymatic susceptible solid carbohydrate phase. Delignification parameters of interest included concentration of NH4OH, time and temperature of the reaction, and type of solvent. The addition of 0.82 M NH4OH to the delignification liquor increased lignin removal and decreased carbohydrate degradation, but increasing NH4OH concentration had no additional effect. At lower reaction temperatures, the extent of delignification increased with reaction time; at higher temperatures, a “relignification” of the pretreated wood was observed. The delignification and hemicellulose solubilization were modelled and rate constants reported. No major difference between three potential pulping solvents—ethanol, butanol, phenol—was observed. The enzymatic susceptibility of pretreated wood samples was approximately 6-fold greater than that of the untreated poplar. UV absorbance was used to qualitatively characterize the soiubilized lignins.  相似文献   

10.
The injection of biomass in a pressurised entrained flow reactor is challenging. Biomass preparation by torrefaction before gasification could be a suitable option to improve it. Transformation of the material induced by this treatment lead to interesting features: increased brittleness, improved fluidisation properties of the powder, hydrophobicity, higher energy content. The major biomass constituents, cellulose, hemicelluloses and lignin are variously affected by torrefaction, depending on their respective reactivity. The objective of this work is to investigate the transformation of the biomass constitutive polymers induced by this thermal treatment. For that purpose, both solid-state NMR and EPR investigations have been performed on wood samples (beech) torrefied at different temperatures ranging from 200 °C to 300 °C. The results of these investigations have been compared with data obtained on untreated wood. These characterizations have brought to light different transformations of the polymers: de-acetylation of hemicelluloses, demethoxylation of lignin, changes in the cellulose structure. Furthermore, the temperature at which depolymerisation of the different components begins to occur has been identified.  相似文献   

11.
In order to investigate the possibility of waste mushroom medium as a biomass resource for biorefinery, characteristics of hydrolysate and pretreated biomass obtained from oxalic acid pretreatment were examined. The hydrolysate contained high glucose and low concentrations of inhibitors. The glucose concentration in the hydrolysate particularly increased when temperature gradient was used during pretreatment, compared with that of isocratic condition. The highest increase rate of glucose was 63.16% when pretreatment was performed at 140 °C for 25 min with 0.032 oxalic acid (g/g), and increased temperature to 170 °C. At the same time, ethanol production of Scheffersomyces stipitis using hydrolysate was 15.72 g/L after 48 h, which correspond to an ethanol volumetric productivity of 0.33 g L?1 h?1. Most of the lignin and some of the cellulose remained in the pretreated biomass. The total lignin content of the pretreated biomass, represent between 31.81 and 45.05%, compared to 28.8% of the raw material. The calorific value of the pretreated biomass ranged from 4940 to 5111 kcal/kg which represent increase of 3–6% compared to the raw material, due to higher contents of lignin in the pretreated biomass.  相似文献   

12.
BACKGROUND: Lignocellulose should undergo pretreatment to enhance its enzymatic digestibility before being saccharified. Peracetic acid (PAA) is a strong oxidant that can remove lignin under mild conditions. The sulfuric acid in the PAA solution also can cause degradation of hemicelluloses. The objective of the present work is to investigate the effect of several factors on peracetic acid pretreatment of sugarcane bagasse. RESULTS: It was found that PAA charge, liquid/solid (l/s) ratio, temperature, time, interactions between PAA charge and l/s ratio, temperature and time, all had a very significant effect on the enzymatic conversion ratio of cellulose. The relative optimum condition was obtained as follows: PAA charge 50%, l/s ratio 6:1, temperature 80 °C and time 2 h. More than 80% of the cellulose in bagasse treated under the above conditions was converted to glucose by cellulase of 20 FPU g?1 cellulose. Compared with H2SO4 and NaOH pretreatments under the same mild conditions, PAA pretreatment was the most effective for enhancement of enzymatic digestibility. CONCLUSION: PAA pretreatment could greatly enhance the enzymatic digestibility of sugarcane bagasse by removing hemicelluloses and lignin, but removal of lignin was more helpful. This study can serve as a step to further optimization of PAA pretreatment and understanding the mechanism of enhancement of enzymatic digestibility. Copyright © 2007 Society of Chemical Industry  相似文献   

13.
《分离科学与技术》2012,47(8):1272-1279
Dewaxed Calamagrostis angustifolia Kom was pretreated with hot water at 60 and 90°C for 3 h, and then the residue obtained was successively treated with 70% ethanol, and 70% ethanol containing 0.2%, 1.0%, 2.0%, 4.0%, and 8.0% NaOH at 80°C for 3 h. The dissolved components were subjected to further separation to get eight lignin fractions, which were characterized by gel permeation chromatography, Fourier transform infrared, and sugar analysis. All the lignin fractions had small weight-average molecular weights between 810 and 2580 g/mol. Two typical lignins, L3 (prepared with 70% ethanol) and L5 (prepared with 70% ethanol containing 1.0% NaOH), were further analyzed using 1H, 13C NMR and HSQC spectroscopy. Signals from guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) units observed in aromatic/olefinic region of HSQC spectra indicated that the lignin from Calamagrostis angustifolia Kom could be classified as “GSH” lignin. In aliphatic-oxygenated region, β-O-4′ together with small amounts of β-5′, β-β′, and p-hydroxycinnamyl alcohol end group were the main interunit linkages observed. Aqueous ethanol, which could avoid the cleavage of ether bonds in lignin at neutral condition, was more effective than water on lignin extraction.  相似文献   

14.
Miscanthus sinensis L. was fractionated by different reagents (ethanol, soda and soda–ethanol) in order to obtain cellulose, hemicelluloses and lignin. Characterization of original M. sinensis fibres (66.6% holocellulose, 36.1% α-cellulose, and 15.5% lignin) was done and compared with other biomass species chemical composition (alternative raw materials, agriculture residues, coniferous and leafy plants). Obtained solid fractions were chemically characterized and compared with solid fractions from other biomass products (palm oil empty fruit bunches (EFB) and rice straw) generated by similar fractionation processes (soda and organosolv). Soda process produced the solid fraction with the highest content in α-cellulose and lowest content in lignin revealing a strong fractionation effect. On the contrary, soda–ethanol process was found to present low fractionation capability. Obtained cellulose samples were characterized by FTIR to complete the chemical structure analysis. Lignin samples isolated from the liquid fractions were submitted to FTIR, 1H NMR, GPC, DSC and TGA in order to suggest suitable applications for the products based on their properties.  相似文献   

15.
Enzymatic hydrolysis and fermentation methods were evaluated on alkaline peroxide pretreated shea tree sawdust conversion to ethanol. Optimum pretreatment conditions of 120 °C reaction temperature, 30 min reaction time, and 20 mL L?1 of water hydrogen peroxide concentration (1%(v/v)H2O2) solubilized 679 g kg?1 of hemicellulose and 172 g kg?1 of lignin. 617 g kg?1 cellulose was retained in the solid fraction. The maximum yield of reducing sugar with optimized enzyme loadings by two enzyme preparations (cellulase and β-glucosidase) was 165 g kg?1 of dry biomass. The ethanol yield was 7.35 g L?1 after 72 h incubation period under the following conditions: 2% cellulose loading, enzyme concentration was 25 FPU (g cellulose)?1 loading, yeast inoculums was 10% (v/v), 32 oC, and pH 4.8. The pretreatments gave information about the hindrances caused by lignin presence in lignocellulosic materials and that hemicelluloses are better hydrolyzed than lignin, thereby enhancing enzymatic digestibility of the sawdust material.  相似文献   

16.
This work explores the factors that control the dispersion of exfoliated montmorillonite (MMT) in poly(vinyl alcohol) (PVOH) during solution blending and solvent evaporation. Nanocomposite films were prepared by solution blending of aqueous PVOH solutions with dilute suspensions of fully exfoliated MMT platelets (as confirmed by AFM). Dynamic light scattering (DLS) indicates that addition of MMT suspensions to PVOH solutions results in undesired particle aggregation and thus poor MMT dispersion in cast films (as evidenced by transmission electron microscopic images and gas permeation measurements). We believe that PVOH bridging induces MMT platelet aggregation. To counteract bridging aggregation, we explore the novel idea of pretreating the MMT surface with a small amount of compatible polymer prior to solution blending with PVOH. We hypothesize that “pretreating” the MMT platelet surfaces with adsorbed polymer in dilute suspensions will protect the platelets from bridging aggregation during solution blending and solvent evaporation. MMT/PVOH composite films have been prepared using low‐molecular‐weight PVOH as the pretreatment polymer; and low‐, medium‐, and high‐molecular‐weight PVOH as the matrix polymer. A PEO‐PPO‐PEO triblock copolymer (F108 from the Pluronics® family) was also evaluated as the pretreatment polymer. DLS shows that pretreated MMT platelets are less susceptible to aggregation during blending with PVOH solutions. Results compare the crystalline structure, thermal properties, dynamic mechanical properties, gas permeability, and dissolution behavior of MMT/PVOH films incorporating untreated versus pretreated MMT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41867.  相似文献   

17.
The pretreatment of lignocellulosic residues has been extensively studied as a method to disrupt the cellulose–hemicelluloses–lignin complex in biomass to access the sugars in their respective components. In this work, we carried out a study using sulfuric acid pretreatment of sugarcane bagasse by varying the following operational parameters: solid loading (10–30% of bagasse relative to the volume of the sulfuric acid solution), sulfuric acid concentration (0.5–2.5% relative to the dry mass of bagasse), reaction time (5–25?min), and temperature (135–195°C). The obtained solids from each pretreatment condition were submitted to enzymatic hydrolysis under the same process conditions: 0.232?g of Celluclast 1.5?L and 0.052?g of Novozym 188 per g of pretreated sugarcane bagasse, 72?h of hydrolysis, and 200?rpm of agitation at 50°C. Using central composite rotational design configuration in the experiments and analysis of variance, the results indicate that the conditions that produced larger quantities of glucose by enzymatic hydrolysis (0.35?g glucose/g pulp) with minimum amounts of degradation products were as follows: 20% solids loading, 15?min of reaction time, 1.5% sulfuric acid, and a minimum temperature of reaction of 170°C.  相似文献   

18.
将离子液体氯化1-丁基-3-甲基咪唑([BMIM]C1)、水、固体酸催化剂组成的混合溶剂应用于微晶纤维素的预处理过程中,并尝试把经过预处理的微晶纤维素应用于随后的溶剂液化的研究中,对经过混合溶剂处理后的微晶纤维素进行表征分析。通过测定纤维素的聚合度、官能团基变化、热重分析、结晶结构和表面结构等对微晶纤维素结构进行比较分析。通过对苯酚溶剂液化的基本表征、残渣物的结晶结构以及生成物相对分子质量的变化了解了混合溶剂对微晶纤维素的处理效果。结果表明,通过混合离子液体[BMIM]C1和水并且添加固体酸催化剂形成新的混合溶剂体系对微晶纤维素进行预处理,发现溶剂在保留纤维素主要葡萄糖单元的同时能够有效地降低聚合度。聚合度从未处理时的190降到样品[B]C1(10)的165和样品[B]C1(10)+NR50的151。混合溶剂对非结晶或低结晶物质具有一定的溶解能力,并且对高结晶性纤维素部分的氢键结构起到破坏作用和造成整体结晶结构的歪曲。在随后的液化过程中,处理后的纤维素液化效率有所提高,在反应2min时,固体酸加混合溶剂处理的微晶纤维素液化残渣率为19%,而未处理的液化残渣率29%。表明使用了混合溶剂添加固体酸的溶剂体系对加速液化的效果更佳,预处理对最终液化生成物的性质影响不大。  相似文献   

19.
The processing of rapeseed oil seeds for biodiesel production generates huge amounts of lignocellulosic cake residue mainly composed by cellulose, hemicelluloses and lignin. In this work, the valorisation of these components, especifically the majoritary fraction, hemicelluloses, was studied. Hemicelluloses were extracted, purified and characterized by different techniques (FTIR, 1H NMR, 13C NMR, and GPC). Autohydrolysis and acid hydrolysis processes were applied to obtain sugar monomers and oligomers. Glucose and xylose were the main simple sugars in the obtained hydrolysates, representing 22.7% and 40.2% of total sugars content in the autohydrolysis hydrolysates and 27.7% and 36.6% in the acid hydrolysates respectively. Arabinose, galactose and mannose were present in relatively minor quantities.  相似文献   

20.
Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry  相似文献   

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