纤维素木聚糖和木质素含量对生物质热解特性及产物的影响

采用热重法研究了纤维素、木聚糖和木质素含量对生物质热解特性的影响,分析了三组分相互混合热解时的交互作用规律,及其对热解动力学参数的影响;同时,在生物质真空热解液化系统上考察了三组分含量对热解液化产物分布及生物油组成的影响。结果表明,纤维素热解较为剧烈,生物油中芳香族、糖类、醛类和醇类含量较高;木聚糖的热稳定性较差,生物油中芳香族、酮类和酸类物质较多;木质素热解较为平缓且固体残留物较多,生物油成分主要为芳香族化合物。纤维素对活化能和指前因子的影响较大,木聚糖和木质素对反应级数的影响较大;纤维素的热解有利于减少固体残留物,而木质素的热解产物有利于促进糖类的分解;木聚糖对纤维素的热解具有明显的抑制作用;木聚糖能促进木质素的低温热解,两者混合热解对生物油组成影响较小。因此,高纤维素含量的生物质可以获得更高的生物油产率,且适量的木质素有利于促进纤维素的分解,为进一步提高生物油产率和品质提供了理论依据。     

玉米秸秆与油页岩混烧的热重试验

为了充分燃烧利用农业生物质与油页岩,采用热重-差示扫描量热(TG-DSC,thermogravimetric-differential scanning calorimetry)技术对玉米秸秆与油页岩混合燃料进行了热重试验,对其各燃烧特性与燃烧机理进行了分析并计算了燃烧动力学参数。结果表明,混烧试样的微分热重(DTG,differential thermogravimetric)曲线出现4个峰值,主要分别是半纤维素热解、纤维素热解、木质素和油页岩热解,以及油页岩焦炭燃烧和油页岩无机盐热解。在DTG曲线第1至第3峰之间出现DSC曲线放热峰,在DTG曲线第3峰至第4峰之间出现DSC曲线吸热峰,需要强化混合燃料的前期燃烧;玉米秸秆与油页岩的质量比例为4∶1时的混合燃料S2,其混烧的可燃特性、着火特性及综合燃烧特性指数均最大,燃尽时间最短,燃尽特性指数较大;在前3个温度区段,混合试样的活化能及频率因子均随温度区段的升高而降低,体现了活化能与频率因子变化的一致性;低温阶段与高温阶段反应级数分别约为1.5及0.7。研究结果可为生物质和油页岩的混烧利用提供参考。     

乌拉草纤维热解及其产物挥发性有机物特性分析

为探究乌拉草纤维的热解性能及其在热解过程中挥发性有机物释放情况,基于傅里叶红外光谱仪及同步热分析质谱联用系统对乌拉草纤维及汉麻纤维的主要化学成分进行分析,探究其热分解过程,采用Coats-Redfern法进行热动力学计算,并对其热分解过程中挥发性有机物释放进行检测。研究结果发现,乌拉草纤维与汉麻纤维主要成分相似,以纤维素、半纤维素、木质素为主。其热分解过程可依次分为水分挥发失重、半纤维素热解、纤维素及木质素热解3个主要阶段,并可用半纤维素热解、纤维素热解、木质素热解3个独立的一级反应描述,纤维素与木质素热解阶段反应活化能较高,热解过程与汉麻纤维热分解过程相似。在乌拉草纤维热解过程中,除H2O、CO2气体释放以外,同时释放少量甲醛等挥发性有机物。研究结果为乌拉草纤维实际应用中阻燃及环保问题的考虑提供参考。     

酸-碱两段组合预处理对杨木发酵的影响

为提升杨木的酶解发酵效率，该研究探究了酸-碱两段组合预处理对半纤维素、木质素的降解、纤维素保留以及后续发酵的影响；通过扫描电镜（scanning electron microscopy，SEM）、X射线衍射（X-ray diffraction，XRD）和傅里叶变换红外光谱（fourier transform infrared spectroscopy，FT-IR）对杨木进行表征分析，探究预处理对杨木表面形貌、组成成分和热稳定性的影响。对杨木进行两段HAc-NaOH组合预处理，第一段是采用1% HAc作为酸性催化剂在不同预处理温度（160～200 ℃）下进行预处理，第二段预处理则是以第一段预处理后样品为底物进行不同NaOH质量分数（0.3%～1.2%）的碱预处理。结果表明酸-碱两段预处理的效果优于仅一段酸预处理，在200 ℃ HAc组合0.8% NaOH的两段预处理下获得的乙醇浓度为18.72 g/L，结合SEM、XRD和FT-IR分析发现预处理中半纤维素和木质素的脱除显著提升预处理杨木中纤维素含量，木质纤维致密结构被破坏，提高了酶对纤维素的可及性，也有助于提高后续乙醇发酵浓度。最后通过对葡聚糖、木聚糖、酸不溶性木素含量、木聚糖、酸不溶性木素去除率以及结构特性对乙醇得率的相关性进行分析，表明预处理样品中具有较低半纤维素/木质素含量和较高纤维素结晶度的预处理样品具有更强的发酵潜力。     

农业生物质燃烧特性及燃烧动力学

为了充分燃烧利用农业生物质,采用 TG-DTG-DSC ( thermogravimetric-differential thermogravimetric-differential scanning calorimetry)联用技术对玉米杆、玉米芯、稻草、龙眼枝、荔枝条及其混合燃料进行了热重试验,考察了其可燃特性、着火特性、燃尽特性及综合燃烧特性,计算了燃烧动力学参数.结果表明,玉米杆及玉米芯燃烧前期DTG曲线分别出现2、3个峰值,而稻草、龙眼枝及荔枝条燃烧前期DTG曲线均只出现一个峰值;玉米杆及稻草燃烧中后期出现DSC曲线的吸热峰;玉米杆的可燃特性指数及着火特性指数均最大,且着火温度最低,荔枝条的燃尽特性指数最大,玉米芯的综合燃烧特性最好;低温阶段反应级数约为1.0~1.2,高温阶段反应级数约为0.5~0.8,低温阶段活化能大于高温阶段的活化能;生物质燃烧前期属于均相着火,后期属于多相着火.秸秆类生物质纯烧的后期稳定性较差,在木质类生物质中适当加入秸秆类生物质有利于混合燃料的前期燃烧,研究结果可为农业生物质的燃烧利用提供指导.     

干/湿法烘焙预处理对稻壳燃烧反应特性的影响

烘焙是提高生物质燃料性质的重要技术手段,探究干/湿法烘焙对稻壳热解燃烧反应特性的影响具有重要意义。该研究利用固定床与高压反应釜对稻壳进行了不同温度下的干法烘焙和湿法烘焙（水热碳化）预处理,并利用热重分析仪对稻壳、稻壳烘焙炭和稻壳水热炭开展了非等温燃烧反应特性分析,并且利用Coats?Redfern法与三种常见的气-固反应机理模型对样品的燃烧反应特性进行了动力学分析。最后,该研究对干法与湿法烘焙两种预处理方式对稻壳的热解燃烧反应特性的影响进行了比较。结果表明两种预处理方式对稻壳的热解与燃烧反应参数存在影响：均导致热解反应性降低,干烘焙提高稻壳燃烧反应性,且反应性随着干烘焙温度的提高而升高。但湿烘焙使稻壳燃烧反应性略有降低。在相同的预处理温度条件下,稻壳烘焙炭较稻壳水热炭具有更高的热解起始失重温度、更低的热解最大失重速率及其对应温度和热解反应性。对于稻壳、稻壳烘焙炭及稻壳水热炭的热解燃烧反应性,模型O1较其他两个模型的线性回归指数更高。干/湿法烘焙使稻壳热解活化能升高,而湿烘焙使燃烧活化能降低。此外,两个阶段样品的指前因子（A）均随活化能的增大而增大,二者间存在明显的线性关系（R2均大于0.95）,表明反应过程具有动力学补偿效应。     

碱浓度和温度对玉米秸秆木聚糖提取率和品质的影响

由于提取率和产品品质等方面的原因,作为玉米秸秆主要成分之一的木聚糖还未能得到充分有效的利用。为改善玉米秸秆木聚糖的提取率和品质,对影响木聚糖提取的碱浓度和温度2个关键因素进行了研究。使用组分分析和凝胶渗透色谱等手段对木聚糖得率、纯度和结构进行了研究,同时分离得到纤维素和醇溶木质素。结果表明,Na OH浓度对木聚糖得率和结构的影响比温度显著,较优提取条件为:Na OH浓度为10%(w/v),提取温度90℃,此条件下木聚糖的溶出率和回收率分别为86.37%和76.92%,木聚糖纯度为63.90%。凝胶渗透色谱结果显示,碱浓度的增加使木聚糖的分子量降低,而随温度的升高则呈先升后降的趋势。此外,提取剩余物中纤维素的含量随碱浓度和温度强度的增加而增加。研究证明组合适当的碱浓度和提取温度可以在保证品质的前提下得到较高的木聚糖提取率。     

水热生物炭燃烧特性与动力学分析

采用热重法对锯末、玉米秸秆水热生物炭燃烧特性及动力学进行了研究,考察了不同升温速率(10、20、40℃/min)对燃烧特性的影响,分析了它们的燃烧特性及动力学参数。结果表明:1)水热炭化前后生物质燃烧质量损失集中在挥发分和固定碳燃烧阶段,升温速率快,着火温度、燃尽温度高,整体向高温区转移,综合燃烧特性指数越大;2)40℃/min时,锯末水热生物炭综合燃烧特性指数远大于玉米秸秆,在其余升温速率下区别不明显;3)以20℃/min相同升温速率时,锯末、玉米秸秆水热生物综合炭燃烧特性相对于未炭化生物质下降27%、13%;4)采用一级反应动力学模型和积分法对水热生物炭燃烧动力学进行了研究,一级反应动力学能很好的描述2种生物炭的燃烧动力学,相关系数(R2)均高于0.9,挥发分阶段活化能大于固定碳阶段的活化能。研究结果可为水热生物炭的燃烧应用能提供理论指导。     

基于木质素部分脱除及其含量对生物质热解特性的影响

该研究采用固定床热解炉,研究不同木质素含量花生壳、核桃壳样品的裂解行为,利用元素分析、工业分析、气相色谱-质谱联用以及气相色谱法对原料和热解产物进行分析,探究木质素与综纤维素在原始交联结构下的交互作用及其对热解产物分布特性影响。研究结果发现,300℃热解条件下,随着木质素含量的增加,样品中固体产率增加,液体产率和气体产率下降。500、700℃热解条件下,固体产率相比300℃有大幅度的下降,且随样品中木质素含量的增加,固体产率无明显变化,液体产率稍微增加,气体产率下降。500℃时,H2产率很低,随样品中木质素含量的增加,CO2含量减少,CH4含量增加,CO含量有稍微的上升。而700℃时,综纤维素的脱氢、缩合、成环会生成大量的H2。同时,木质素能够促进综纤维素分解生成大量左旋葡聚糖,并抑制其分解;而综纤维素抑制木质素单体愈创木基的脱甲氧基反应,促进苯丙烷基的脱烷基反应,形成更多的酚类化合物。该研究对于生物质组分间交互和产物形成特性研究具有积极意义。     

黑沙蒿根系抗拉特性及其与化学成分的关联性

[目的] 探讨根系抗拉特性与主要化学成分含量的关联性，以期充实根系固土力学特性研究以及提供矿区生态恢复和植物保护的理论支持。[方法] 以神东矿区广泛分布的多年生灌木黑沙蒿（Artemisia ordosica）为研究对象，利用TY8000伺服式强力机，研究1~4 mm径级直根段、含侧根分支处根段抗拉材料的力学特性并测定各径级的纤维素、半纤维素和木质素，研究根系材料力学及其与化学成分的关联性。[结果] ①随着根系直径增加，黑沙蒿直根段、含侧根分支处根段抗拉力增加，而抗拉强度和杨氏模量减小，且抗拉力、抗拉强度和杨氏模量都与根系直径呈幂函数关系。②直根段、含侧根分支处根段化学成分含量差异显著（p<0.05），平均化学成分含量为：半纤维素（31.69%，32.18%） > 木质素（28.42%，25.30%） > 纤维素（15.50%，15.35%）。③随着根系直径增加，直根段纤维素含量减小，半纤维素和木质素含量增加，而含侧根分支处根段纤维素含量减小，半纤维素和木质素含量无变化。④直根段抗拉强度、杨氏模量与纤维素极显著正相关（p<0.01），与半纤维素、木质素极显著负相关（p<0.01）。含侧根分支处根段抗拉强度、杨氏模量与纤维素极显著正相关（p<0.01），与半纤维素、木质素无相关性。[结论] 黑沙蒿根系抗拉特性与化学成分表现出一定的相关性，且纤维素是影响灌木根系材料力学特性的主要化学组分。     

Production and characterization of films from cotton stalk xylan

Composite film production based on cotton stalk xylan was studied, and the mechanical and physical properties of the films formed were investigated. Xylan and lignin were separated from cellulose by alkali extraction and, then, lignin was removed using ethanol washing. Self-supporting continuous films could not be produced using pure cotton stalk xylan. However, film formation was achieved using 8-14% (w/w) xylan without complete removal of lignin during xylan isolation. Keeping about 1% lignin in xylan (w/w) was determined to be sufficient for film formation. Films were produced by casting the film-forming solutions, followed by solvent evaporation in a temperature (20 degrees C) and relative humidity (40%) controlled environment. The elastic modulus and hypothetical coating strength of the films obtained by using 8% xylan were significantly different from the ones containing 10-14% xylan. The water vapor transfer rates (WVTR) decreased with increasing xylan concentration, which made the films thicker. The glycerol addition as an additional plasticizer resulting in more stretchable films having higher WVTR and lower water solubility values. As a result, film production was successfully achieved from xylan, which was extracted from an agricultural waste (cotton stalk), and the film-forming effect of lignin on pure xylan has been demonstrated.     

Fermentation of a bacterial cellulose/xylan composite by mixed ruminal microflora: implications for the role of polysaccharide matrix interactions in plant cell wall biodegradability

Growth of the cellulose-synthesizing bacterium Acetobacter xylinum ATCC 53524 in media supplemented with 5% (w/v) glucose and 0.2% (w/v) of a water-soluble, nearly linear xylan from tobacco stalks resulted in the synthesis of a highly crystalline composite having a xylose/glucose ratio ranging from 0.06 to 0.24. The digestion of one composite (88% cellulose/12% xylan) by mixed ruminal microflora displayed kinetics of gas production similar to those of an unassociated mixture of the two components added in a xylan/cellulose ratio similar to that of the composite. The data suggest that intimate association of xylan and cellulose, as is typically found in secondary plant cell walls, does not inhibit the rate of digestion of the component polysaccharides.     

Chemical composition and enzymatic degradability of xylem and nonxylem walls isolated from alfalfa internodes

During plant maturation, degradability of alfalfa (Medicago sativa L.) stems declines due to accumulation of highly lignified xylary tissue. Xylem and nonxylem tissues dissected from lower alfalfa internodes were analyzed for cell wall constituents and degradability. Cell walls comprised 740 mg g(-1) of xylem and 533 mg g(-1) of nonxylem tissues. Xylem tissues contributed about 60% of the cell wall mass in internodes. Xylem walls contained 28% lignin, 4% pectin, 29% hemicellulose, and 39% cellulose as compared to 15% lignin, 25% pectin, 30% hemicellulose, and 30% cellulose in nonxylem walls. Fungal enzymes hydrolyzed 22 and 73% of the structural carbohydrates in xylem and nonxylem walls, respectively. In both cell wall fractions, the release of xylose was 56-90% lower than that of other sugars, indicating that lignin preferentially restricted xylan degradation in secondary walls and xyloglucan degradation in primary walls. Elucidation of lignin-xylose interactions may reveal strategies for improving fiber degradability of alfalfa.     

Influence of non-cellulose structural carbohydrate composition on plant material decomposition in soil

The C mineralisation pattern during the early stage of decomposition of plant materials is largely determined by their content of different carbohydrates. This study investigated whether detailed plant analysis could provide a better prediction of C mineralisation during decomposition than proximate analysis [neutral detergent solution (NDF)/acid detergent solution (ADF)]. The detailed analysis included sugars, fructans, starch, pectin, cellulose, lignin and organic N. To determine whether differences in decomposition rate were related to differences in hemicellulose composition, the analysis particularly emphasised the concentrations of arabinose and xylose in hemicelluloses. Carbon dioxide evolution was monitored hourly in soil amended with ten different plant materials. Principal component and regression analysis showed that C mineralisation during day 1 was closely related to free sugars, fructans and soluble organic N components (R ² = 0.83). The sum of non-cellulose structural carbohydrates (intermediate NDF/ADF fraction) was not related to C mineralisation between days 1 and 9. In contrast, a model including starch and protein in addition to the non-cellulose structural carbohydrates, with the hemicelluloses replaced by arabinose and xylose, showed a strong relationship with evolved CO₂ (R ² = 0.87). Carbon mineralisation between days 9 and 34 was better explained by xylan, cellulose and lignin (R ² = 0.72) than by lignocellulose in the ADF fraction. Our results indicated that proximate analyses were not sufficient to explain differences in decomposition. To predict C mineralisation from the range of plant materials studied, we propose a minimum set of analyses comprising total N, free sugars, starch, arabinose, xylan, cellulose and lignin.     

乙二醇-氯化铁预处理对棉秆酶水解效率的影响

为提高棉秆的纤维素酶水解效率,该研究以乙二醇为预处理溶剂,氯化铁为催化剂对棉秆进行预处理,实现了棉秆木质素和半纤维素的有效去除,提高了酶水解效率。以木质素和半纤维素的去除率为指标,运用正交试验方法优化乙二醇-氯化铁预处理条件。结果表明,棉秆在90%乙二醇水溶液,0.1 mol/L氯化铁,固液比1∶15,160 ℃条件下处理20 min,木质素和半纤维素去除率分别为85.7%和88.9%。相较原料,预处理后棉秆酶解率提高了7.6倍,葡萄糖产率达到100%（基质浓度5%,酶载量8.3 FPU/g,水解72 h条件下）。通过结构表征发现乙二醇-氯化铁预处理使棉秆的比表面积增大,致密结构被破坏,有效提高了棉秆的纤维素酶可及性。     

根系主要成分含量对根系固土效能的影响

选取中国北方两种常见树种油松(Pinus tabulaeformis)和元宝枫(Acer truncatum),对这两种树0.2~6mm直径的根系直径、根系抗拉强度、整根的根土复合体强度、根系3种主要成分含量(纤维素含量、半纤维素含量与木质素含量)进行测定。结果表明,随着根系直径的增加,植物根系半纤维素含量增高,纤维素含量与木质素含量降低,从而植物的抗拉强度降低。植物根系抗拉强度与纤维素含量、木质素含量成正相关关系,与半纤维素含量成负相关关系。因此,在排除根系结构影响的前提下,植物根系纤维素含量与木质素含量是导致不同植物种固土效果差异的直接原因。     

Formation of nitric oxide during tobacco oxidation

The sources of NO during biomass oxidation, and in particular tobacco oxidation, have been disputed. Literature results range from decomposition of nitrate to the oxidation of atmospheric nitrogen. To rectify these discrepancies, this study focuses on the sources of nitric oxide (NO) during the oxidation of tobacco samples. When Burley tobacco was heated in a partially oxidized atmosphere, NO was produced at two distinct temperature ranges, namely 275-375 degrees C (the low-temperature range) and 425-525 degrees C (the high-temperature range). The formation of NO at the low-temperature range with Burley tobacco was found to be unaffected by oxygen, while the formation of NO at the high-temperature range required an oxygen atmosphere. With Bright and Oriental tobacco, NO was produced only within the higher-temperature range. To understand the formation processes and the sources of NO formation within these two temperature ranges, several endogenous nitrogenous tobacco compounds were examined. These were mixed with non-nitrogenous biomass model materials, namely cellulose, pectin, xylan, or lignin, which also occur naturally in tobacco, and the mixtures were heated in a flow tube reactor under a partially oxidative atmosphere. A commercial gas analyzer was used to monitor the formation of NO during heating. Nitrate ion was determined to be the source of NO formation in the range of 275-375 degrees C. This ion was decomposed in a carbonaceous surrounding to produce NO. For NO formation at the higher temperature range, amino acids and proteins were shown to be the sources. The interaction between nitrogenous organic compounds (amino acids and proteins) and pectin first produced a nitrogen-containing char at a temperature below 350 degrees C. Oxidation of this char at the higher temperatures produced NO.