稻草NH4OH-KOH蒸煮反应历程和动力学研究

在合适的蒸煮工艺条件下，研究了稻草NH4OH-KOH法制浆的反应历程和反应动力学。反应历程研究表明，脱木质素过程分为开始升温至100℃的大量脱木质素、100-155℃下保温45min补充脱木质素和155℃下保温45min以后的残余脱木质素3个阶段；脱硅过程分为开始升温至100℃的大量脱硅、100-155℃下整个保温的少量脱硅两个阶段，硅的脱除易于木质素的脱除。动力学研究表明，脱木质素反应对残余木质素呈表观一级，对[OH^-]呈0.3级，反应活化能为35.60kJ/mol；脱硅反应对残余硅呈表观一级，对[OH^-]呈0.6组，反应活化能为30.91kJ/mol。     

麦草碱性亚硫酸盐制浆生物炼制的研究(I) ——深度脱木质素及木质素磺化特性

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响。结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱木质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0%,亚硫酸化度85.0%,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8%,黏度为33.3 mPa.s的优良纸浆,此时黑液中磺化木质素磺酸基含量达2.16 mmol/g(以固形物计)。从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景。     

Study on Wheat Straw Alkaline Sulfite Pulping Biorefinery(Ⅰ)——Characteristics of Extended Delignification and Lignin Sulfonation

提出了非木材木质纤维生物质碱性亚硫酸盐制浆(ASP)生物炼制的理念,研究了总用碱量、亚硫酸化度、温度和时间对麦草碱性亚硫酸盐法蒸煮深度脱木质素特性和木质素磺化的影响.结果表明:麦草ASP法具有高的深度脱木质素选择性;深度脱本质素延伸与木质素磺化度提高具有一致性;总用碱量、亚硫酸化度、最高温度和保温时间对深度脱木质素选择性和木质素磺化度都有重要的影响;在总碱用量18.0％,亚硫酸化度85.0％,液比值3.5,最高温度168℃,保温150 min的条件下,可制得卡伯值8.8,得率56.8％,黏度为33.3 mPa·s的优良纸浆,此时黑液中磺化本质素磺酸基含量达2.16 mmol/g(以固形物计).从深度脱木质素选择性、木质素磺化和纸浆基本特性考虑,麦草ASP法具有制浆生物炼制的前景.     

杉木纤维素的热稳定性及热分解动力学参数

杉木纤维素的热稳定性和热分解动力学参数是模拟杉木高温热处理的重要参数,研究采用化学方法分离得到木材各主要化学成分的含量,采用热重分析仪在不同升温速率下测试了纤维素的热稳定性,并采用FWO法、Friedman法和ASTM E1641法计算得到纤维素的活化能和指前因子。研究结果表明,杉木纤维素、半纤维素、Klason木质素和苯醇抽提物的含量分别为48.5%、19.9%、33.5%和2.6%。纤维素的热分解峰值在1、5、10、15、20℃/min升温速率下对应的热分解温度分别为293.8、320.4、332.4、340.3℃和346.0℃。杉木纤维素热分解活化能和指前因子随转化率的变化有波动,不同计算方法得到的活化能和指前因子数值具有一定差异,在转化率为0.3至0.6期间时,FWO法、Friedman法和ASTM E1641法计算得到的活化能平均值为167.3、160.9 kJ/mol和164.4 kJ/mol,计算得到的指前因子自然对数平均值为33.2、32.4 min~(-1)和34.5 min~(-1)。     

玉米秸秆水热焦热解及动力学特性研究

以玉米秸秆为原料制备水热焦,分析了不同反应强度下水热焦碳质量分数的变化规律,并采用Friedman法、Flynn-Wall-Ozawa(FWO)法和Kissenger-Akahira-Sunose(KAS)法,研究了玉米秸秆原料及水热焦(250℃、480 min)的热解过程,计算了其反应活化能。结果表明:在210~290℃,30~480 min反应区间内,玉米秸秆水热焦碳质量分数随水热反应强度增加而增加;水热焦的固体焦产率和热解最大反应速率随水热反应强度增加均呈降低趋势,最大反应速率对应的热解温度区间由280~380℃变为400~450℃,当反应强度超过7.11(250℃、480 min)时,最大反应速率变化相对平稳;玉米秸秆原料及水热焦的热解均可分为脱水、主热解、炭化3个阶段;FWO和KAS模型计算得到的活化能值较为接近,在高转化率阶段(转化率大于20%),水热焦(250℃、480 min)活化能远高于玉米秸秆活化能,当转化率为75%时,通过FWO和KAS法计算得到的水热焦活化能分别为260.87和261.84 kJ/mol,而玉米秸秆的活化能仅为145.55和142.74 kJ/mol。     

麦草有机酸生物炼制的研究(I)——常压下复合有机酸与麦草的反应特性

研究了麦草在甲酸-乙酸-水复合有机酸(FAWOA)体系中于常压反应条件下,反应温度和时间对麦草各组分溶出规律的影响。结果表明:麦草在与复合有机酸反应过程中,脱木质素历程可以分为3个阶段:大量脱木质素阶段,补充脱木质素阶段和残余脱木质素阶段,各阶段木质素溶出分别为37.1%、27.2%和2.50%;戊聚糖的反应历程也分为3个阶段:戊聚糖大量反应阶段、补充反应阶段和少量反应阶段,各阶段戊聚糖溶出分别为50.0%、24.9%和3.20%;综纤维素、苯-乙醇抽出物和灰分的溶出呈现与脱木质素、戊聚糖溶出相似的趋势;黑液中有机物含量的增加趋势与木质素和戊聚糖溶出趋势相似,而无机物含量变化很小,基本维持在2.0 g/L左右。     

木材热解及金属盐催化热解动力学特性研究

通过不同升温速率下杉木的热重实验,对比分析钾盐催化杉木热裂解动力学特性.借助于DTG重叠峰的分离以及分布活化能模型计算不同转化率条件下的反应活化能,得到钾盐对生物质中半纤维素的低温段分解、纤维素的整个热裂解过程存在催化效果,使失重曲线(200~270℃)肩状峰衰退乃至消失,并促进脱水和交联反应,导致焦炭产率的提高和残碳的有序化,体现为焦炭产量从16.3%提高到25.3%(质量分数),而且80%转化率后残碳分解活化能的急剧提高.基于三组分平行反应机理,采用非线性回归法拟合计算杉木热解动力学参数,得到纤维素的热裂解基本上属于一阶反应,而且钾盐对纤维素和半纤维素的热裂解具有较大程度促进,活化能分别从148.12和235.43kJ/mol下降到108.84和171.41kJ/mol,但对木质素的催化影响并不显著.     

核桃壳与煤共热解的热重分析及动力学研究

利用热重分析在不同升温速率(5～50 K/min)和氮气气氛下对核桃壳、褐煤以及核桃壳-褐煤(质量比1∶1)混合物的热解失重行为进行了研究,求取了热解动力学参数。实验结果表明,随着升温速率的提高,3种原料的失重率下降,热失重速率升高;核桃壳与褐煤共热解时存在协同作用;三者的平衡热解温度分别为568.9、709.9和571.0K。应用Coats-Redfern方法进行热解动力学过程分析表明,3种原料均可由一级反应过程描述。核桃壳快速热解和残余物缓慢热解阶段的平均活化能分别为50.6、17.3 kJ/mol,褐煤的平均活化能为21.1 kJ/mol,核桃壳-褐煤混合物快速热解和残余物缓慢热解阶段的平均活化能分别为34.2和14.5 kJ/mol。     

和稀盐酸联合催化下的水解动力学研究

以微晶纤维素为原料,在1 g/L的FeCl3存在下和2%的盐酸溶液体系中进行水解,根据水解属于串联反应的特点,研究了微晶纤维素在H+和Fe3+共同作用下的水解动力学规律。研究采用目标物产率与模型函数值残差(S)为最小确定模型函数,对实验数据进行了处理。结果表明:H+和Fe3+共同作用能显著降低纤维素水解和葡萄糖降解的活化能。其中,纤维素水解成为葡萄糖的活化能为81.70 kJ/mol,葡萄糖降解成为小分子的活化能为43.85 kJ/mol,在温度为130、140和150℃时,纤维素水解速率常数分别为0.041 4、0.073 2和0.115 3 h-1,相应温度下葡萄糖降解速率常数分别为0.205 3、0.242 4和0.356 5 h-1。     

Thermogravimetric Analysis and Kinetics of Walnut Shell and Coal Co-pyrolysis

利用热重分析在不同升温速率(5 ～50 K/min)和氮气气氛下对核桃壳、褐煤以及核桃壳-褐煤(质量比1∶1)混合物的热解失重行为进行了研究,求取了热解动力学参数.实验结果表明,随着升温速率的提高,3种原料的失重率下降,热失重速率升高;核桃壳与褐煤共熟解时存在协同作用;三者的平衡熟解温度分别为568.9、709.9和571.0K.应用Coats-Redfern方法进行热解动力学过程分析表明,3种原料均可由一级反应过程描述.核桃壳快速热解和残余物缓慢热解阶段的平均活化能分别为50.6、17.3 kJ/mol,褐煤的平均活化能为21.1 kJ/mol,核桃壳-褐煤混合物快速热解和残余物缓慢热解阶段的平均活化能分别为34.2和14.5 kJ/mol.     

Development of high-performance UF-bonded reed and wheat straw medium-density fiberboard

Urea formaldehyde resin-bonded reed and wheat straw fiberboards were produced from the fibers made under different steam cooking conditions in refining processes at densities of 500 and 700kg/m³. The effect of steam cooking conditions on the board properties was examined. The steam pressure and cooking time for reed and wheat straws were 0.4MPa/10min and 0.4MPa/5min, respectively, and 0.6MPa/3min and 0.6MPa/10min for both straws. The effect of steam cooking treatment before the fiber refining process on the wettability and weight losses of the straws was also investigated. The results indicated that the mechanical properties and linear expansion of the straw medium-density fiberboard (MDF) were improved with increasing steam cooking pressure and time during the refining process, whereas the thickness swelling (TS) did not vary much. The wettability of the straws was improved by cooking treatment. The steam cooking conditions had little effect on the wettability of the straw surfaces. For reed and wheat straws, the weight losses increased with increasing steam pressure and cooking time. In addition, it was found that the properties of MDF were significantly higher than those of particleboard, especially the internal bond (IB), where the IB values of MDF were more than 10 times higher than those of particleboard. All the properties of the straw MDF, except the TS of wheat board, can meet the requirement of JIS fiberboard standard. The high performances of MDF could be due to the improved wettability and the removal of extractives during the refining process.     

Acetic acid pulping of wheat straw under atmospheric pressure

Atmospheric acetic acid pulping of wheat straw was carried out. Pulping conditions and their effects on pulp properties were investigated in detail, and a comparison between acetic acid (AcOH) pulp and soda-anthraquinone (AQ) pulps of wheat straw was made of the chemical composition, strength, and fiber morphology of the pulps. Wheat straw was successfully pulped and fractionated into pulp (cellulose), acetic acid lignin, and sugars (monosaccharides from hemicellulose), making it easy to utilize them. It was found that among the pulping conditions the dosage of H₂SO₄ as catalyst was the most notable, and the extent and rate of delignification could be controlled by varying the amount of the catalyst. The results also showed that acetic acid pulp was quite different from soda-AQ pulp. About 70% of the ash or 90% of the silica in wheat straw were kept in AcOH pulp. The ash might function as filler and be beneficial to the printability of paper. It was known that many epidermal cells existed in AcOH pulp in bundles or in single cells. These ash-rich nonfiber cells seemed to hinder the bonding between fibers. AcOH pulp had lower strength than soda-AQ pulp, which might result mainly from the chemical damage of fibers caused by acid, not from the depolymerization of cellulose.Part of this paper was presented at the 65th Pulp and Paper Research Conference of Japan TAPPI, Tokyo, June 1998     

Differential behavior between acacia and Japanese larch woods in the formation and decomposition of hexenuronic acid during alkaline cooking

The effects of anthraquinone (AQ) and polysulfide (PS) on the hexenuronic acid (HexA) content of pulp during kraft cooking were studied using Acacia mearnsii (acacia) and Larix leptolepis (Japanese larch) sapwood. In contrast to the results of cooking Japanese larch at an H-factor of 1200, the HexA contents of acacia pulp with a kappa number of 20 at an H-factor of 291 did not differ greatly between the kraft, kraft-AQ, and PS-AQ cooking methods, although the hydroxide ion concentration in the acacia cooking liquor decreased on the addition of AQ or sulfur. To explain this difference, we studied the behavior of the formation and degradation of HexA during alkaline cooking of glucuronoxylan from cotton linter, which was cooked with 1.0 and 2.0 mol/l NaOH. The relationship between HexA content and H-factor during alkaline cooking of glucuronoxylan was clarified. The amount of HexA and its rate of decomposition were higher in the 2.0 mol/l solution than in the 1.0 mol/l solution. At a low H-factor similar to that for hardwood cooking, HexA content increased to a maximum level and then started to decrease at high hydroxide ion concentrations such as 2.0 mol/l, whereas it slowly decreased at low hydroxide concentrations such as 1.0 mol/l. At an H-factor of around 450, the HexA formation/degradation curve for 1.0 mol/l of hydroxide crossed the decomposition curve for 2.0 mol/l of hydroxide. Therefore, it was shown that at a low H-factor, a decrease in hydroxide ion concentration during acacia wood cooking had little effect on the HexA content of pulp.     

杨木水热预处理过程中水解反应动力学研究

探讨了预处理温度和预处理时间对杨木水热预处理液中各组分含量的影响,同时采用改良的Saeman双相动力学模型建立了预处理液中木糖和葡萄糖的反应动力学方程,通过非线性拟合确定了不同条件下木糖和葡萄糖生成及分解的反应速率常数,由阿伦尼乌斯公式线性拟合得出木质纤维原料水解反应活化能.杨木预处理过程中木聚糖易降解部分活化能(Ef...     

麦秸秆外表面膜及异氰酸酯对麦秸与LDPE界面结合的影响

采用物理及力学性能以及界面结合形态分析相结合的方法,研究了麦秸秆外表面膜及异氰酸酯(PAPI)对麦秸与低密度聚乙烯(LDPE)两相界面结合的影响.研究结果表明:1.3% PAPI可显著提高麦秸/回收LDPE复合材料干态及 2h 沸水后内结合强度、静曲强度及弹性模量,对24h 吸水厚度膨胀率的降低改善不大;麦秸秆外表面膜具有改善麦秸与LDPE两相界面结合作用;PAPI可将麦秸与回收LDPE、麦秸秆外表面与新LDPE两相界面由相分离转变为相连续.PAPI具有有效改善麦秸与LDPE两相界面结合强度的作用.     

二次正交旋转试验对麦秸塑料复合材料冲击强度影响

选用农作物秸秆-麦秸粉和热塑性塑料-高密度聚乙烯（HDPE）为原料，添加马来酸酐接枝聚乙烯（MAPE）为改性剂，利用单双螺杆挤出机组，采用熔融挤出方式制备麦秸塑料复合材料。在其它条件固定的情况下，研究双螺杆挤出机温度、转速和麦秸粉含量等因素对麦秸塑料复合材料冲击强度的影响，设计二次正交旋转回归组合试验方案对双螺杆挤出工艺进行优化。麦秸塑料复合材料的冲击强度与双螺杆挤出机的温度和转速以及原料中麦秸粉添加比例存在一定的相关性，通过试验建立了麦秸塑料复合材料冲击强度（y）对双螺杆挤出机温度（x1）、转速（x2）、麦秸粉比例（x3）三个试验因素之间的正交回归模型方程：y=17．98106—0．82505x1^2-0．94349x2^2-1．00182x3^2；；从模型推知，当温度为160℃、双螺杆转速为30rpm和麦秸粉用量为60％时，冲击强度达到最大值17．98kJ／m2，实验验证结果与模型值相符。研究结果对提高麦秸塑料复合材料冲击强度和优化工艺参数具有重要的指导意义和应用价值。     

生物质醇解重质油燃烧动力学研究

在热重分析仪上研究马尾松、桉木和麦秸秆的醇解重质油的燃烧过程及其动力学特性。结果发现,这3种重质油燃烧过程均可分为3个阶段:1)室温到300℃,为小分子有机物挥发阶段;2)300～480℃,为挥发分析出与燃烧阶段;3)480℃以上,为固定碳燃烧与燃尽阶段。动力学计算结果表明,这3个阶段都符合一级反应过程。同时,麦秸秆醇解重质油快速燃烧阶段(300～480℃)活化能最低,对应的失重速率最大,为0.188%/min,且着火温度最低,为405℃,因而其最易于燃烧。     

Thermal degradation of bending strength of plywood and oriented strand board: a kinetics approach

The construction industry has relied heavily on wood and wood-based composites, such as oriented strand board (OSB) and plywood for timber frame construction. Therefore, it is highly imperative to categorize the response of wood-based composites when exposed to elevated temperatures for a sustained period of time. The essence of fire-resistant structural design is to ensure that structural integrity be maintained during and after the fire, prevent collapse and maintain means of egress. Another aspect is to assess post-fire structural integrity and residual strength of existing structure. The objective of this project was (a) to study the effect of exposure time on bending strength (MOR) of OSB and plywood at elevated temperatures, (b) to interpret any relationships between different temperature and time of exposure using a kinetics model for thermal degradation of strength, and (c) to develop a master curve representing temporal behavior of OSB and plywood at a reference temperature. As much as 1,152 samples were tested in static bending as a function of exposure time and several temperatures. Strength (MOR) of both OSB and plywood decreased as a function of temperature and exposure time. These results were fit to a simple kinetics model, based on the assumption of degradation kinetics following an Arrhenius activation energy model. The apparent activation energies for thermal degradation of strength were 54.1 kJ/mol for OSB and 62.8 kJ/mol for plywood. Furthermore, using the kinetics analysis along with time–temperature superposition, a master curve was generated at a reference temperature of 150°C which predicts degradation of strength with time on exposure at that reference temperature. The master curves show that although plywood has a higher initial strength, OSB performs better in terms of strength degradation after exposure to elevated temperature.     

越南甜竹纤维形态特征的研究

对甜竹原料、甜竹浆的纤维形态进行了研究。结果表明:甜竹原料纤维平均长度为2.37 mm、平均宽度17.91μm、长宽比值132.40;纤维平均壁厚为8.13μm、平均腔径为2.57μm、壁腔比值6.33。研究了在蒸煮过程中纤维形态的变化。结果表明,在蒸煮过程中甜竹纤维长度不断变小,从2.37 mm(原料)到1.79 mm(全浆),减少24%;蒸煮过程中纤维长宽比值也不断缩小,从132.40(原料)到98.89(全浆)。与青皮竹浆、桉木浆(阔叶木)、马尾松浆(针叶木)和麦草浆(草类)的纤维形态相比,甜竹浆纤维长度大于麦草浆纤维,小于马尾松浆纤维,与青皮竹浆和桉木浆纤维长度基本相近,因此甜竹浆纤维属于长纤维范围,是一种优良的造纸原料。