小麦秸秆水热预处理半纤维素降解动力学研究

水热预处理是木质纤维素原料高效能源转化的主要工艺流程之一,但是以小麦秸秆为原料的水热预处理的反应路径与反应机理仍有研究不足之处,制约该预处理过程的优化及实际生产应用。本文以小麦秸秆为研究对象,实验研究了木质纤维素水热预处理过程反应动力学。研究发现,在水热预处理过程中,小麦秸秆的主要降解过程是半纤维素降解产生低聚木糖、木糖以及糠醛的过程,半纤维素在水热过程中几乎完全降解。随着预处理温度的升高,水解液中低聚木糖和木糖的浓度降低,而糠醛的浓度增加;随着保温时间的延长,低聚木糖与木糖的浓度先增加后减小,糠醛的浓度会趋于稳定。根据实验结果提出反应路径并拟合获得动力学速率常数和反应活化能,所获的动力学模型可以很好地解释反应物浓度的变化,与实验数据吻合良好。该模型可以为小麦秸秆水解预处理系统的设计提供参考。     

盐酸水解玉米秸秆木聚糖的动力学研究

对稀盐酸水解秸秆半纤维素生成木糖水解液过程进行动力学研究。分别测定了不同温度下,不同水解时间水解液中木糖质量浓度以及其降解产物糠醛的质量浓度。利用Saeman模型拟合木糖生成过程。实验表明,该模型能够较好地描述木糖生成过程以及其降解产物糠醛的产生过程。通过曲线拟和确定了不同水解温度下木糖的生成速率以及分解速率常数,同时利用Arrhenius方程确定木糖生成活化能Ea为116 kJ/mol。综合比较不同温度下水解液中的木糖以及糠醛质量浓度,确定使用质量分数为2%的稀盐酸于120℃下水解60 min为最佳水解条件。其水解液中木糖质量浓度可达20.99 g/L,糠醛质量浓度可维持在1.46 g/L以下。     

玉米秸秆稀酸水解与水解液发酵的实验研究

研究了玉米秸秆的稀酸水解性能,考察了底物浓度、反应温度、反应时间、硫酸浓度和秸秆粒径对水解得率和木糖得率的影响.在硫酸浓度为1.0%、水解温度126℃、水解时间1 h、底物浓度为50～80g/L情况下,玉米秸秆的水解得率为21.7%～24.6%,木糖得率为68.0%-77.1%.所得水解液主要成分为木糖和葡萄糖,经处理后可直接用于微生物的发酵培养.     

玉米秸秆稀酸蒸汽爆破协同作用机制研究

以玉米秸秆原料,进行蒸汽爆破处理,比较了水蒸气蒸爆、稀酸和稀酸蒸爆3种预处理方法,通过对3种预处理过程中米秸秆纤维组分变化、纤维素和半纤维素降解产物和玉米秸秆结构分析以及酶解试验,探讨稀酸蒸汽爆破的协同作用机制.结果表明,稀酸蒸爆协同作用包括稀酸的软化和蒸汽爆破的活化两种机制:一是通过稀酸脱除大部分的半纤维素破坏了半纤...     

采用稀盐酸和硝酸水解玉米芯产木糖及其优化

采用稀HCl和HNO₃在酸质量分数为1.0%、2.5%和4.0%,反应时间10、30、50、90和120 min,温度90和150 ℃条件下,对玉米芯水解产木糖进行研究。通过动力学模型数据预测木糖浓度,并采用响应曲面优化各个温度下的水解条件。优化得到的最适宜水解条件为温度150 ℃,预处理时间10 min,酸质量分数为1.0%;对应HNO.₃.得到的木糖浓度为56.77 g/L,产率96.31%;HCl木糖浓度为45.38 g/L,产率76.99%。动力学结果成功预测了反应条件下的木糖浓度。通过对比得出HNO.₃.对玉米芯的水解效果要优于HCl。     

草酸水解甜高粱秸秆渣的Saeman动力学模型

利用草酸作为催化剂水解甜高粱秸秆渣制备木糖,测定了不同温度下的木糖收率和副产物糠醛产量;依据半纤维素水解的Saeman模型,计算得到了木聚糖水解和木糖降解的动力学数据,其活化能分别为5.89×104,1.38×104J/mol。分析结果表明:木聚糖水解反应速度快,但是生成的木糖容易发生降解;模型最优化反应条件为125℃和77min,实验得到的木糖收率为52.11%。草酸作为一种有机酸,能够用于催化半纤维素水解制备木糖,副产物糠醛的产率较低。     

高温液态水中甜高粱渣半纤维素水解及其机理

为了回收甜高粱渣中的半纤维素衍生糖并了解其水解机理,在自行设计的Flowthrough反应器中对甜高粱渣进行了高温液态水水解,分别考察了不同反应温度和反应液流量下水解液中产物的生成情况。研究表明,相对葡萄糖和阿拉伯糖而言,木糖的生成受反应温度和反应液流量影响更大。温度高于195 ℃时糖降解加剧,总木糖浓度不断降低;低流量（5 ml?min-1）条件下生成的木糖不能被及时排出而进一步降解。通过产物分析可知,甜高粱渣半纤维素中含有典型的O-乙酰基-4-O-甲基葡萄糖醛酸基阿拉伯糖基木聚糖结构,木糖、葡萄糖、阿拉伯糖、各种低聚糖、乙酸和葡萄糖醛酸等是半纤维素水解的直接产物,糠醛和5-羟甲基糠醛等是糖类的降解产物, 甲酸等小分子酸是它们的进一步降解产物。     

4-硝基苯胂酸合成反应的热力学计算机模拟

采用密度泛函理论中的B3LYP方法,通过计算机模拟,研究了4-硝基苯胂酸合成反应中各物质的结构。在此基础上对反应热力学进行了模拟计算,通过计算,优化了反应物与产物的几何构型与电子分布,并得到了4-硝基苯胂酸合成反应的主副反应焓变、Gibbs自由能变以及反应平衡常数。模拟计算结果表明,主反应的焓变 为-15.0 kJ·mol^-1,为放热反应,副反应的焓变为10.0 kJ·mol^-1,为吸热反应,主反应的标准Gibbs自由能变为39.7 kJ·mol^-1,而副反应的Gibbs自由能为45.2 kJ·mol^-1,该反应为不可逆反应。4-硝基苯胂酸合成反应的热力学性质的计算为反应工艺条件的控制和热力学研究提供了理论指导。     

阻燃HIPS塑料热解动力学模型

采用热重法进行了含阻燃添加剂的高抗冲聚苯乙烯塑料（flame retarded high impact polystyrene,Br-Sb-HIPS）在不同升温速率下的热解实验,建立了包含3个连续反应的阻燃HIPS热解动力学模型。通过Flynn-Wall-Ozawa法得到阻燃HIPS热解过程的活化能为103～307 kJ·mol^-1,利用多元非线性无约束最优化方法求得模型参数。研究表明,Br-Sb-HIPS 3个反应的活化能和指前因子分别为191.632、213.263、238.331 kJ·mol^-1和11.641、12.772、11.666 min^-1。动力学模型能够很好地预测阻燃HIPS热解过程。     

低冰镍转炉渣中钴的氧压酸浸行为及其动力学

研究了转炉渣中钴氧压硫酸体系选择性浸出过程的行为及其动力学。通过改变搅拌速度、反应温度、硫酸浓度、氧分压、物料粒度以及反应时间等浸出条件,考察钴浸出率的变化及影响,获得转炉渣中钴的浸出动力学规律。结果表明,钴的浸出率随着温度、酸度、氧分压的增加而增加;硫酸质量浓度大于0.4 mol·L^-1会导致铁大量溶出;浸出过程符合未反应芯收缩核模型,前期受化学反应控制,然后转变为混合控制,后期受固体产物层扩散控制。化学反应控制和固体产物层扩散控制过程的活化能分别为43.19 kJ·mol^-1 和10.49 kJ·mol^-1。化学反应控制过程对硫酸浓度、氧分压及粒度的反应级数分别为0.79、0.85和 -0.95。     

Kinetic studies of xylan hydrolysis of corn stover in a dilute acid cycle spray flow-through reactor

Xylan of corn stover was pretreated with 1%, 2% and 3% (w/w) sulfuric acid at relatively low temperatures (90°C, 95°C and 100°C) in a dilute acid cycle spray flow-through reactor (DCF). The hydrolysis of xylan to its monomeric xylose was modeled by a series of first-order reactions. Both biphasic and Saeman hydrolysis models were applied to fit the experimental data. The results confirmed that the kinetic data of xylan hydrolysis fitted a first-order irreversible reaction model and the experimental data. The reaction rates of xylose monomer formation and degradation were sensitive to catalyst concentration and temperature. Higher catalyst concentration and lower reaction temperature result in high xylose yield. The activation energy for xylose formation and degradation were determined to be 112.9 and 101.0 kJ·mol^-1, respectively. Over 90% theoretical xylose obtained from corn stover can be used to produce ethanol, xylitol and fumaric acid by fermentation.     

高温液态水中2,6-二氟苯腈水解反应动力学

为了开发2,6-二氟苯甲酰胺的绿色制备工艺以及探讨高温液态水中腈类物质的水解规律,研究了高温液态水中2,6-二氟苯睛无催化水解反应动力学.系统地研究了不同初始浓度、不同温度下2,6-二氟苯腈、2,6-二氟苯甲酰胺的水解反应动力学以及2,6-二氟苯甲酸的脱羧反应动力学.采用一级串联反应动力学方程拟合2,6-二氟苯腈的水解...     

有机酸对甜高粱渣亚临界水解产物的影响

半纤维素的高效转化是提高甜高粱渣原料全组分利用的关键技术之一。采用亚临界水热预处理方法,并将强度因子R₀引入研究过程,考察了不同温度（160~200℃）和反应时间（10~60 min）对甜高粱渣水解反应的影响。在这基础上,进一步考察了多种有机酸（乳酸、醋酸及乳酸+醋酸）对亚临界水解效果的影响。实验表明,当强度因子lgR₀=3.96（180℃,40 min）时,采用不外加酸的亚临界水热预处理工艺得到的最大木糖浓度为4.79 g·L^-1;有机酸的加入可强化水解反应,提高木糖浓度;与单一乳酸或醋酸处理方法相比,加入同浓度的乳酸+醋酸既可以促进半纤维素水解,又可以抑制副产物生成;在温度180℃,时间40 min,乳酸+醋酸（乳酸：醋酸=6：4）的浓度1%（质量）的条件下,木糖浓度为7.92 g·L^-1。     

纤维素在离子液体中均相酰化反应动力学

以离子液体1-烯丙基-3-甲基咪唑氯盐（AmimCl）为反应媒介,以微晶纤维素为原料,研究了离子液体中纤维素与酸酐均相酰化反应的动力学,通过实验考察了纤维素初始羟基浓度（0.21～0.85 mol·L^-1）及反应温度（353～373 K）对酰化反应速率的影响。结果表明,随着离子液体中纤维素羟基浓度的增大和反应温度的升高,纤维素酰化反应的速率都呈增大趋势。通过实验得到了纤维素均相酰化反应的动力学方程,纤维素乙酐酰化及乙酐、丁酐混合酸酐酰化反应的反应级数均为1,表观活化能分别为19.03 kJ·mol^-1和20.04 kJ·相似文献   

Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers

Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5‐dimethylphenylboronic acid, 4‐tert‐butylphenylboronic acid, trans‐β‐styreneboronic acid or naphthalene‐2‐boronic acid) dissolved in an organic diluent (Shellsol^® 2046 or Exxal^® 10) containing the quaternary amine Aliquat^® 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene‐2‐boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid‐soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation. Copyright © 2004 Society of Chemical Industry     

Sugarcane bagasse hydrolysis with phosphoric and sulfuric acids and hydrolysate detoxification for xylitol production

The effectiveness of phosphoric acid to release xylose from sugarcane bagasse hemicellulose was assessed through a 2³ full factorial design. The maximum xylose concentration in the hydrolysate (17.1 g dm^?3) was attained when the bagasse was treated at 160 °C for 60 min, using 70 mg of phosphoric acid per gram of dry‐bagasse. Hydrolysis carried out with sulfuric acid, under optimum conditions previously determined, provided a hydrolysate with a similar xylose concentration (17.2 g dm^?3). After vacuum concentration, these hydrolysates were detoxified and used for xylitol production with the yeast Candida guilliermondii. Two different detoxification strategies, which consisted of adjusting the pH of the hydrolysates to 5.5 with either calcium oxide or ammonium hydroxide, both followed by active charcoal adsorption, were tested. The best xylitol productions (18.1 and 19.2 g dm^?3) were observed when calcium oxide was used to adjust the pH of both the phosphoric and the sulfuric acid hydrolysates, respectively. Copyright © 2004 Society of Chemical Industry     

Degradation Kinetics of Xylose and Glucose in Hydrolysate Containing Dilute Sulfuric Acid

In preparation of fuel alcohol from biomass as feedstock, hydrolysis with dilute acid as catalyst is one way to produce fermentable saccharide, xylose and glucose. However, the acid is also the catalyst in degradation of xylose and glucose and the yield of sacchride is dependent on the kinetic behaviors of saccharide. The degradation kinetics of xylose and glucose in the hydrolysate was investigated under the conventional process conditions of hydrogen ion concentration from 0.05 to 0.2 mol/L and temperature from 150 to 200℃. With a numerical calculation method, the kinetic parameters were estimated, and the activation energy of xylose and glucose in the degradation reaction was obtained. The kinetic equations correlating the effect of hydrogen ion concentration on the rate constants of degradation reaction were established. Comparison between the calculated results from the equations and experimental ones proved that the established kinetic model could satisfactorily predict the degradation behavior of xylose and glucose in the acidic hydrolysate.     

Modeling and optimization of dilute nitric acid hydrolysis on corn stover

BACKGROUND: Because of its high cost, nitric acid has not been widely employed as the catalyst for hydrolysis of lignocellulosic biomass to obtain fermentable sugars. However, recently more and more research results have reported that nitric acid was more effective than other acids for the hydrolysis of lignocellulose. Therefore, it is necessary to find an optimum condition for nitric acid pretreatment and a means of reducing the cost. RESULTS: In this work, low concentrations of nitric acid and short reaction times were considered to optimize the pretreatment process. The kinetic parameters of models to predict the concentrations of xylose, glucose, arabinose, acetic acid and furfural in the hydrolysates were obtained. Applying the kinetic models, the optimum conditions were: 150 °C, 0.6% HNO₃ and 1 min, which yielded a solution containing up to 22.01 g L^?1 xylose, 1.91 g L^?1 glucose, 2.90 g L^?1 arabinose, 2.42 g L^?1 acetic acid and 0.21 g L^?1 furfural, which were consistent with the predicted values. The influence of temperature was also studied using the Arrhenius equation. CONCLUSIONS: A combination of experimental data and model analysis suggested that 96% xylose yield can be achieved by using low concentration nitric acid for a short reaction time, which could greatly reduce the pretreatment cost. Therefore, dilute nitric acid could be considered a good choice for the hydrolysis of corn stover. Copyright © 2010 Society of Chemical Industry