Catalytic organosolv fractionation of willow wood and wheat straw as pretreatment for enzymatic cellulose hydrolysis

BACKGROUND: Ethanol‐based organosolv fractionation of lignocellulosic biomass is an effective pretreatment technology for enzymatic cellulose hydrolysis to produce sugars and lignin within a biorefinery. This study focuses on the catalytic effect of H₂SO₄, HCl, and MgCl₂ on organosolv pretreatment of willow wood and wheat straw. RESULTS: The use of catalysts improved fractionation of both feedstocks. The maximum enzymatic cellulose digestibility obtained was 87% for willow wood (using 0.01 mol L^?1 H₂SO₄ as catalyst) and 99% for wheat straw (0.02 mol L^?1 HCl). Non‐catalytic organosolv fractionation at identical conditions resulted in 74% (willow wood) and 44% (wheat straw) glucose yield by enzymatic hydrolysis. Application of catalysts in organosolv pretreatment was particularly effective for wheat straw. The influence of the acid catalysts was found to be primarily due to their effect on the pH of the organosolv liquor. Acid catalysts particularly promoted xylan hydrolysis. MgCl₂ was less effective than the acid catalysts, but it seemed to more selectively improve delignification of willow wood. CONCLUSION: Application of catalysts in organosolv pretreatment of willow wood and wheat straw was found to substantially improve fractionation and enzymatic digestibility. The use of catalysts can contribute to achieving maximum utilization of lignocellulosic biomass in organosolv‐based biorefineries. Copyright © 2011 Society of Chemical Industry     

Chemical characterization and liberation of pentose sugars from brewer's spent grain

The chemical composition of brewer's spent grain (BSG), generated from a process using 100% malted barley, was investigated. BSG is mainly composed of (g kg^?1) hemicellulose (284), lignin (278), cellulose (168) and protein (152.5), but it also contains extractives and ashes in smaller proportions. Minerals in BSG include calcium, sodium, potassium, magnesium, aluminum, iron, barium, strontium, manganese, copper, zinc, phosphorus, sulfur, chromium and silicon. In order to find alternative uses for BSG, this by‐product was subjected to acid hydrolysis process to recover the hemicellulosic sugars, which have a large number of industrial applications. The process was carried out under different conditions of liquid‐to‐solid ratio and acid concentration to evaluate the influence of these two variables on BSG hemicellulose hydrolysis. Under all the hydrolysis conditions evaluated, arabinose was recovered with higher efficiency than xylose. Under the best evaluated reaction conditions (liquid‐to‐solid ratio of 10 g g^?1 and 120 mg H₂SO₄ g^?1 dry matter) 76.2% of the hemicellulose was hydrolyzed and the xylose and arabinose sugars were recovered with 67 and 97.8% efficiency, respectively. Copyright © 2005 Society of Chemical Industry     

Enzymatic hydrolysis of autohydrolyzed barley husks

BACKGROUND: Barley husks were subjected to non‐isothermal autohydrolysis of different severities, yielding a liquid phase rich in hemicellulose‐derived compounds and a solid phase, composed mainly of cellulose and lignin. This solid phase was subjected to enzymatic hydrolysis in order to assess the effects of severity on the susceptibility of substrates to enzymatic hydrolysis. The effects of the liquid to solid ratio (LSR, in the range 6 to 18 g g^?1) and cellulase to substrate ratio (CSR, in the range 3.3 to 8.2 FPU g^?1) on the enzymatic hydrolysis were assessed. RESULTS: Up to 25.8 g oligomers per 100 g raw material were present in liquors from the hydrothermal processing. Enzymatic hydrolysis of solid phases obtained under selected conditions (log Ro = 4.14, LSR = 6 g g^?1 and CSR = 5.8 FPU g^?1) yielded glucose concentrations up to 67 g L^?1 (corresponding to cellulose to glucose conversions close to 100%). CONCLUSION: It was shown that autohydrolysis is an effective method for improving the enzymatic susceptibility of barley husks. High cellulose conversions resulting in high glucose yields were achieved by enzymatic hydrolysis at low LSR and CSR. The liquid fraction obtained upon autohydrolysis contained large amounts of hemicellulose‐derived compounds. Copyright © 2010 Society of Chemical Industry     

Graft polymerization of acrylonitrile onto wheat straw

Acrylonitrile was graft polymerized onto ground, water-washed wheat straw using Fe²⁺-H₂O₂ as initiator. Reaction conditions were selected to minimize homopolymer formation and maximize the amount of polyacrylonitrile (PAN) grafted to straw. Polymerizations typically yielded straw-g-PAN containing 30–35% PAN. A two-step fractionation scheme was developed for determining the relative amounts of PAN grafted to cellulose, hemicellulose, and lignin. This scheme involved (1) delignification of straw-g-PAN with sodium chlorite followed by removal of lignin-grafted PAN by extraction with dimethylformamide (DMF), and (2) hydrolysis of the hemicellulose component with 1 N trifluoroacetic acid followed by DMF extraction of hemicellulose-grafted PAN. Product remaining after these two treatments was assumed to be cellulose-g-PAN. When relative amounts of PAN grafted to cellulose, hemicellulose, and lignin were compared with relative percentages of these components present in wheat straw, the percentage of total PAN grafted to lignin was less than its relative percentage in straw, whereas that grafted to hemicellulose was considerably more. Although the use of Ce⁴⁺ as initiator gave little or no polymer with whole, water-washed straw, grafted polymerization occurred when delignified straw was used as substrate. Relative amounts of PAN grafted to cellulose and hemicellulose were not greatly different from those observed with Fe²⁺-H₂O₂ initiation onto whole straw.     

Enhanced enzymatic hydrolysis of rice straw pretreated by alkali assisted with photocatalysis technology

BACKGROUND: The fermentable sugars in lignocellulose are derived from cellulose and hemicellulose, which are not readily accessible to enzymatic hydrolysis because of their biological resistance, so that pretreatment of lignocellulose is needed for this process. In this work, a novel lignocellulose pretreatment method using alkali solution assisted by photocatalysis was investigated. RESULTS: The reaction conditions of nano‐TiO₂ dosage and photocatalysis time were optimized at 2 g L^?1 and 1 h, respectively. After pretreatment under these conditions, cellulose in rice straw was increased from 37.5% to 71.5%, and lignin decreased from 18.5% to 9.0%. The results of X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) and scanning electron microscopy (SEM) analysis showed that the physical properties and microstructure of the straw were changed by this pretreatment, which favored the following enzymatic hydrolysis. The enzymatic hydrolysis rate of the straw pretreated using this technology was verified to be 73.96%, which was 2.56 times higher than that obtained with the alkali procedure. CONCLUSION: The proposed photocatalysis pretreatment technology was more efficient at degrading the lignin and hemicellulose in rice straw than alkali pretreatment, making it more readily available for the following enzymatic hydrolysis process. Copyright © 2009 Society of Chemical Industry     

Utilization of lignocellulosic waste for ethanol production : Enzymatic digestibility and fermentation of pretreated shea tree sawdust

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.     

Kinetic modeling of hemicellulose hydrolysis in the presence of homogeneous and heterogeneous catalysts

Kinetic models were developed for the hydrolysis of O‐acetyl‐galactoglucomannan (GGM), a hemicellulose appearing in coniferous trees. Homogeneous and heterogeneous acid catalysts hydrolyze GGM at about 90°C to the monomeric sugars galactose, glucose, and mannose. In the presence of homogeneous catalysts, such as HCl, H₂SO₄, oxalic acid, and trifluoroacetic acid, the hydrolysis process shows a regular kinetic behavior, while a prominent autocatalytic effect was observed in the presence of heterogeneous cation‐exchange catalysts, Amberlyst 15 and Smopex 101. The kinetic models proposed were based on the reactivities of the nonhydrolyzed sugar units and the increase of the rate constant (for heterogeneous catalysts) as the reaction progresses and the degree of polymerization decreases. General kinetic models were derived and special cases of them were considered in detail, by deriving analytical solutions for product distributions. The kinetic parameters, describing the autocatalytic effect were determined by nonlinear regression analysis. The kinetic model described very well the overall kinetics, as well as the product distribution in the hydrolysis of water soluble GGM by homogeneous and heterogeneous catalysts. The modelling principles developed in the work can be in principle applied to hydrolysis of similar hemicelluloses as well as starch and cellulose. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1066–1077, 2014     

大豆秸秆酶水解及L-乳酸发酵

用纤维素酶对氨预处理后的大豆秸秆进行酶水解,利用纤维素酶的作用使纤维素、半纤维素水解为可溶性糖,继而研究了用干酪乳杆菌及清酒乳杆菌进行L-乳酸发酵,通过微生物发酵将生成的可溶性糖转化为用于生产具有可生物降解性的聚乳酸塑料的原料乳酸,实现可再生资源的充分利用.结果表明,实验条件下,5%的大豆秸秆经酶水解后,还原糖浓度为242.25 mg•g^-1,纤维素糖化率为51.22%.清酒乳杆菌、干酪乳杆菌及该两种混合菌种发酵酶解液所得L-乳酸的转化率分别为 48.27%、56.42%和71.05%.     

Delignification of intact biomass and cellulosic coproduct of acid‐catalyzed hydrolysis

The kinetics of acid‐catalyzed hemicellulose removal and also alkaline delignification of oat hull biomass were investigated. All three operational parameters namely, catalyst concentration (0.10–0.55 N H₂SO₄), temperature (110–130°C), and residence time (up to 150 min) affected the efficiency of hemicellulose removal, with 100% of hemicellulose removed by appropriate selection of process parameters. Analysis of delignification kinetics (in the temperature range of 30–100°C) indicated that it can be expressed very well by a two‐phase model for the crude biomass and also for the hemicellulose‐prehydrolyzed material. The application of acid‐catalyzed prehydrolysis improved the capacity of lignin dissolution especially at lower temperatures (30 and 65°C) and accelerated the dissolution of lignin. This acceleration of delignification by prehydrolysis was possible at all levels of temperature in the bulk phase; however, results were more significant at the lower temperatures in the terminal phase. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1783–1791, 2015     

Production of xylose,furfural, fermentable sugars and ethanol from agricultural residues

With the developing shortage of petroleum, reliance on biomass as a source of chemicals and fuels will increase. In the present work, bagasse and rice husk were subjected to dilute acid (H₂SO₄) hydrolysis using pressurised water to obtain furfural and fermentable sugars. Various process conditions such as particle size, solid-liquid ratio, acid concentration, reaction time and temperature have been studied to optimise yields of furfural, xylose and other fermentable sugars. The use of particle sizes smaller than 495 μm did not further increase the yield of reducing sugars. A solid-liquid ratio of 1:15 was found to be the most suitable for production of reducing sugars. Hydrolysis using 0.4% H₂SO₄ at 453 K resulted in selective yields (g per 100 g of dried agricultural residues) of xylose from bagasse (22.5%) and rice husk (21.5%). A maximum yield of furfural was obtained using 0.4% H₂SO₄ at 473 K from bagasse (11.5%) and rice husk (10.9%). It was also found that hydrolysis using 1% H₂SO₄ at 493 K resulted in maximum yields of total reducing sugar from bagasse (53.5%) and rice husk (50%). The reducing sugars obtained were fermented to ethanol after removal of furfural. The effect of furfural on the fermentation of sugars to ethanol was also studied. Based on these studies, an integrated two-step process for the production of furfural and fermentable sugars could be envisaged. In the first step, using 0.4% H₂SO₄ at 473 K, furfural could be obtained, while in the second step, the use of 1% H₂SO₄ at 493 K should result in the production of fermentable sugars.     

Kinetic studies of wheat straw hydrolysis using sulphuric acid

The kinetics of cellulose and hemicellulose hydrolysis of wheat straw was studied using both isothermal and non-isothermal techniques in a batch reactor. Reactions were carried out between 100 and 210°C and product sugars were analyzed using a Bio-Rad HPX-87P liquid chromatographic column. A simple first order series reaction model was used for both cellulose and hemicellulose hydrolysis reactions and kinetic parameters were obtained for the Arrhenius rate equations for three different sulphuric acid concentrations (0.5, 1.O and 1.5%). Activation energies remained constant with acid concentration but the pre-exponential factors showed an increase with acid concentration. To minimize the amount of experimental data required and to achieve a unique solution to the kinetic parameters, the technique of combining isothermal and non-isothermal reaction data was studied.     

［Bmim］Cl离子液体中微波辐射加热促进稻草秸秆酸水解制备还原糖

以［Bmim］Cl离子液体为介质,研究了微波辐射加热对硫酸催化稻草秸秆水解的促进作用,并对水解产物中的还原糖进行了测定。着重考察了［Bmim］Cl离子液体用量、硫酸浓度、反应温度和反应时间等因素对还原糖收率的影响,并采用正交试验法对微波辐射下稻草酸水解条件进行了优化。结果表明,在［Bmim］Cl离子液体介质中,用微波辐射加热促进稻草酸水解制备还原糖的最佳条件是：［Bmim］Cl用量10.0ml,硫酸浓度10.0%,微波加热温度85℃,反应时间60 min。在此条件下还原糖的收率可达到23. 22%,而常规酸水解得到的还原糖收率仅为18.74%。通过显微镜和红外光谱对水解残余物与稻草原料进行分析后发现：水解后的稻草残渣变细、变薄,并且与稻草原料的结构基本一致,保留了较好的纤维素特征。     

秸秆中木质素对其超低酸水解过程的影响

以湖北稻草秸秆为研究对象,研究了超低酸水解木质纤维素的适宜条件,测定了适宜条件下的超低酸法水解15种不同种类秸秆的纤维素及半纤维素的转化率、还原糖得率及结晶度的变化。实验结果表明:秸秆投料量3 g、硫酸投料量45 mL(硫酸质量分数0.05%)、搅拌转速500 r/min、反应温度210 ℃、反应时间10 min为适宜的水解条件。对15种不同种类秸秆的水解结果统计得到,随着秸秆中木质素含量的增大,纤维素和半纤维素的转化率都逐渐降低,还原糖得率逐渐降低;通过SEM和X衍射分析水解前后的木质纤维素结构,得到了木质素影响水解过程的方式:1)木质素含量越大,纤维素的结晶度越大,纤维素的非晶化越困难,从而影响了纤维素的水解;2)原木质素不溶于反应体系且在酸性条件下相对稳定,富木质素层的木质素阻碍反应物与产物扩散,使富木质素层内的纤维素、半纤维素水解速率降低;3)木质素含量越高,木质纤维素的富木质素层越厚、强度越大,水解时难以从颗粒表面脱落,进一步降低水解速率。     

Effect of calcium carbonate in waste office paper on enzymatic hydrolysis efficiency and enhancement procedures

Hydrolysis of waste office paper (WOP) into fermentable sugars is an important option of WOP utilization. In this work, the effect of major chemicals in WOP on its hydrolysis using industrial cellulase Accellerase 1000 (Genencor, Rochester, NY, USA) was investigated, and calcium carbonate (CaCO₃) was found to be the key parameter affecting the enzymatic hydrolysis efficiency of WOP. The pretreatment methods, acid washing and acid presoaking, were tested for the removal of CaCO₃ from WOP. It was found that the presoaking of sulfuric acid (H₂SO₄) in WOP was an effective way. The pretreating parameters of WOP were studied on maximizing the hydrolysis efficiency. The conversion yield of cellulose to glucose and cellobiose using the pretreated WOP reached 73.3% after 96 hours hydrolysis at the optimal conditions. The results provided the WOP utilization with a practical enzymatic hydrolysis method with industrial application potential.     

Fermentation of enzymatic hydrolysates from olive stones by Pachysolen tannophilus

BACKGROUND: Olive stones were pretreated with liquid hot water (LHW or autohydrolysis) at maximum temperatures between 175 and 225 °C (severity factors, logR₀, between 2.73 and 4.39) to be subjected (both liquid and solid components) afterwards to enzymatic hydrolysis with cellulases from Trichoderma viride. Ethanol fermentation of hydrolysates was performed with the non‐traditional yeast Pachysolen tannophilus ATCC 32691. RESULTS: After the enzymatic step, yields of hemicellulose solubilization reached 100%, while the cellulose was only partially hydrolysed (23%, logR₀ = 4.39). The maximum yields in total reducing sugars and acetic acid, at the upper end of the severity range, was close to 0.25 and 0.04 g g^?1 dry stone, respectively. During the fermentation stage, the increase in R₀ reduced the maximum specific growth rate, biomass productivity, and overall biomass yield. The overall yields of ethanol and xylitol ranged, respectively, from 0.18 to 0.25 g g^?1 and from 0.01 to 0.13 g g^?1. CONCLUSIONS: The results demonstrate the possibility of producing ethanol from olive stones, making use of the cellulose and hemicellulose fraction of the waste. It was confirmed that the overall yield in xylitol strongly depended on severity factor, while the overall yield in ethanol remained practically constant for all the pretreatment conditions tested. Copyright © 2008 Society of Chemical Industry     

Characterisation of Oligosaccharides Released by Steam Explosion of Sulphur Dioxide ImpregnatedPinus Radiata

The nature of the solubilized oligosaccharides released from the softwood Plnus radiata by the steam explosion process in the presence or absence of sulphur dioxide are described in this paper. Steam explosion in the absence of sulphur dioxide (215δ, 3 min) resulted in partial solubilization of only the hemicelluloses (14.5 g of neutral sugars/100 g o.d. wood) to their respective oligomers, which ranged in degree of polymerization from 1 to at least 12. The effect of adding 2.5% sulphur dioxide to the substrate was to facilitate the removal and hydrolysis of both hemicellulose and cellulose components (29.5 g of neutral sugars/100 g o.d. wood) by acid catalysis. Steam explosion of the substrate at an elevated temperature of 248° in the presence of 2.5% sulphur dioxide, caused almost complete cellulose and hemicellulose solubilization, and subsequent degradation reflected in poor carbohydrate survival (24.7 g of neutral sugars/100 g o.d. wood). The addition of sulphur dioxide to the process results in enhanced hydrolysis of the solubilized material to mainly mono- and disaccharides. However, the acid reversion products such as isomaltose and gentiobiose are formed, although their effect on total fermentable sugar yield is very small. Under normal steam explosion conditions the acidic aldooligouronic acid hydrolysis products represent only about 6% of total soluble carbohydrate. Interestingly, some demethylation of 4–0-methyl-D-glucuronic acid residues were observed as a consequence of sulphur dioxide catalysis.     

酸和碱预处理对麻竹酶水解糖化的影响

研究了121℃下硫酸和氢氧化钠预处理对麻竹酶水解还原糖收率的影响,测定了不同预处理液质量分数和预处理时间对还原糖收率的影响,以及预处理后的预处理液中还原糖含量。结果表明,氢氧化钠预处理能显著提高还原糖收率,在氢氧化钠质量分数为2%,预处理时间60min时还原糖收率可达0.367g/gDS。硫酸预处理对还原糖收率的提高幅度不大。但硫酸预处理后的预处理液中还原糖含量较高,在硫酸预处理液质量分数为2%,预处理时间为90min时还原糖收率可达0.152g/gDS。两种预处理方法在121℃下的还原糖收率均高于100℃下的还原糖收率。     

Low-Temperature Dilute Acid Hydrolysis of Oil Palm Frond

Oil palm frond (OPF) fiber, a lignocellulosic waste from the palm oil industry, contains high cellulose and hemicellulose content, thus it is a potential feedstock for simple sugars production. This paper describes the two-stage hydrolysis process focusing on the use of low-temperature dilute acid hydrolysis to convert the hemicellulose in OPF fiber to simple sugars (xylose, arabinose, and glucose). The objective of the present study was to evaluate the effect of operating conditions of dilute sulfuric acid hydrolysis undertaken in a 1 L self-built batch reactor on xylose production from OPF fiber. The reaction conditions were temperatures (100–140°C), acid concentrations (2–6%), and reaction times (30–240 min). The mass ratio of solid/liquid was kept at 1:30. Analysis of the three main sugars glucose, xylose, and arabinose were determined using high-pressure liquid chromatography. The optimum reaction temperature, reaction time, and acid concentration were found to be 120°C, 120 min, and 2% acid, respectively. Based on the potential amount of xylose (10.8 mg/mL), 94% conversion (10.15 mg/mL) was obtained under the optimum conditions with small amount of furfural (0.016 mg/mL). To enhance the effectiveness of dilute acid hydrolysis, the hydrolysis of OPF fiber was also performed using ultrasonic-pretreated OPF fiber. The effects of ultrasonic parameters power (40–80%) and ultrasonication times (20–60 min) were determined on sugar yields under optimum hydrolysis conditions (2% acid sulfuric, 120°C and 120 min). However, the use of ultrasonication was found to have detrimental effect on the yield of simple sugars due to the 10-fold increase in the formation of furfural.     

醋酸水解玉米芯中木聚糖的动力学

利用醋酸作为催化剂水解玉米芯中半纤维素来制备还原糖,测定了温度在160-200℃、固液质量比为1∶15、搅拌速度为500 r/min下,不同水解时间水解液中还原糖的收率以及副产物糠醛的收率.利用半纤维素高温液态水的Garrote模型拟合还原糖生成过程.实验表明,该模型能够较好地描述还原糖生成过程以及副产物糠醛的产生过程...     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.