煤液化残渣与生物质混合燃烧过程中硫污染物动态排放特性研究

生物质在全球总能源消耗中占有相当大的比例，世界各国对生物质能利用新技术的研究日益重视。用生物质燃料替代传统的化石燃料，不仅可以缓解日益严重的能源问题，也可以减少环境污染和降低CO2的排放心。但生物质的热值比较低，单独利用效率较低，因此一些欧美发达国家采取了将部分生物质与煤混和燃烧发电或气化的新技术。     

秸秆燃烧排放PM2.5特征及影响因素研究

生物质燃烧向大气中排放大量颗粒污染物, 在中国, 收获季节大量秸秆被直接露天燃烧处理, 对区域环境质量和人体健康造成严重影响. 对我国最主要的两种粮食作物玉米和小麦秸秆的露天燃烧进行模拟, 分析颗粒物排放水平, 特征及影响因素. 玉米和小麦秸秆燃烧PM_2.5排放因子分别为1082.8和835.7~897.3 mg/kg. 有机物是颗粒物最主要组分, 总量占PM_2.5质量的42%~66%. Cl^-和K⁺分别占PM_2.5总质量的4%~15%和2%~14%, K⁺/EC值为0.5~3.8. 各物种在颗粒物中所占比例与之前研究结果一致. 秸秆含水量和燃烧温度影响PM_2.5排放水平和组成特征. 随秸秆含水量增加, PM_2.5和OC的排放因子增加; 秸秆含水量增加, 燃烧温度逐渐降低, 由生物质燃料释放进入烟气中的K⁺和Cl^-比例逐渐减小导致二者在颗粒物中的比例降低. 我国每年由玉米和小麦秸秆露天燃烧排放的PM_2.5和OC分别为92.7 Gg和47.5 Gg, 在总量中占重要比例.     

生物质秸秆热重分析及几种动力学模型结果比较

利用热重分析在不同升温速率和氮气气氛下对两种生物质（玉米秸秆和稻秆）的热失重行为进行了研究。根据热重实验数据，采用四种利用热分析获取动力学参数的方法（Coats-Redfern法，Doyle法，最大速率法和分布活化能模型(DAEM)），计算生物质秸秆热分解反应活化能E、反应级数n及频率因子A，并进行比较。结果表明，采用不同的处理方法，得出的热分解动力学参数不同。利用Coats-Redfern法，玉米秸秆和稻秆在热解主要阶段（失重约5 w%～80 w%时）可由一段一级反应过程描述，升温速率10 K/min时活化能值分别为68.8 kJ/mol和70.0 kJ/mol。Doyle法和DAEM模型得到的结果较为接近，可以得到生物质热解过程中的活化能随失重率的变化曲线。生物质秸秆热解包含分子键能断裂的一系列复杂、连续反应过程。     

生物质焦制备条件对其燃烧反应特性的影响

在热重分析仪上,研究了生物质焦的制备条件对其燃烧反应特性的影响。生物质焦由闪速裂解技术制得,裂解温度为 748 K、773 K和823 K;原料含水质量分数为0、7.0%和11.3%。研究发现,生物质焦中挥发性物质的质量分数和H/C质量比随裂解温度的增加而降低,其燃烧反应性随裂解温度的增加而降低;与高裂解温度条件下制得的生物质焦相比,低裂解温度条件下制得的生物质焦具有较高的反应活化能和对燃烧温度更敏感。原料含水量对生物质焦的燃烧反应特性影响很小;但对高裂解温度条件下制得的生物质焦中的挥发性组分含量有较大的影响。简化的生物质焦本征燃烧反应幂函数动力学模型可以很好地描述其燃烧行为。     

玉米秸热解动力学研究

生物质能具有低硫和二氧化碳零排放的特点，其在能源结构中的地位越来越重要。作为一种高效生物质能转化途径，热化学转化可获得气、液和固态多种能源产物。其中，热解是热化学转化中最为基本的过程，是气化、液化及燃烧过程的初始和伴生反应，对热解的分析有助于热化学转化过程控制及高效转化工艺的开发。热解动力学是表征热解过程中反应过程参数对原料转化率影响的重要手段，通过动力学分析可深入了解反应过程和机理，预测反应速率及难易程度，为生物质热化学转化工艺的研究开发提供重要的基础数据。国外对纤维素热解动力学已进行了一些研究，但生物质作为纤维素、半纤维素、木质素等的复杂聚合物，其热解行为与单纯纤维素差别较大。因此本文的热解研究集中在玉米秸这种常见的软质秸秆类生物质原料。     

生物质燃烧碳烟的物化特性及生成机理研究

以棉花秸秆和木屑为研究对象,设定不同的燃烧工况,在管式炉中进行燃烧并采集碳烟物质,采用TEM、EDS、GC-MS等检测方法对生物质燃烧过程中生成碳烟的物化特性进行研究,并根据检测结果对碳烟生成机理进行分析和推测。检测及分析结果表明,碳烟颗粒典型形貌有胶囊状、球状、链状、网状等。燃烧工况影响燃烧过程使碳烟颗粒表现出不同的微观形貌。碳烟生长过程中伴随着颗粒的碰撞和凝并,形成形貌复杂的链状或网状颗粒聚团。生物质燃烧中碳烟主要由纤维素热裂解生成,成分包括糠醛类、酚类、醛类、呋喃、烷烃、烯烃等含碳化合物。推测碳烟生成机理为,在生物质燃烧过程中,纤维素发生化学键的断裂与重排,生成CO、CO₂和残炭分子碎片等,而残余碳基再通过重整、脱水、碳化、断键等反应生成各种醛类、酮类等产物,醛类、酮类化合物之间通过缩聚、环化反应生成苯环结构,再进一步转化为苯酚、甲苯等化合物。     

钾对秸秆混煤燃烧特性影响的研究

选用经酸洗法脱灰的煤和秸秆制得实验样品。采用TG/DTG/DTA技术研究了不同秸秆含量下碱金属钾对秸秆与煤混合燃烧特性的影响。研究结果表明,KOH促进脱灰煤和脱灰混合样品的着火燃烧,使其最大燃烧速率温度及燃尽温度降低,但提高了脱灰秸秆的着火温度。秸秆混煤燃烧反应符合一级反应模型,KOH的添加对混煤燃烧具有催化作用,使混合燃烧反应活化能降低10kJ/mol。     

北京市大气颗粒物中生物质燃烧排放贡献的季节特征

研究了1997年11月~1998年10月期间一年四季北京郊区十三陵(一号站)和市区天坛(五号站)采集的110个大气颗粒物样品中有机碳(OC)与水溶性钾(K⁺)的质量浓度变化. 利用指示物K⁺定性识别了春耕(清明)、麦收、秋收、秋季落叶等4个生物质燃烧过程. 对OC与K⁺数据进行了回归分析, 用以表征生物质燃烧的特征, 并在此基础上评估了生物质燃烧对北京市大气颗粒物OC的贡献. 春耕(清明)、麦收、秋季落叶期间回归斜率在两站点之间比较一致, 表现了生物质燃烧排放的区域性特点. 回归截距的差异反映了两个站点的不同属性. 1998年秋收时段北京市发生重污染事件, 二次有机碳大量形成, 生物质燃烧是主要排放源之一. 生物质燃烧排放具有季节性与周期性, 是北京市大气颗粒物有机碳的一个重要来源, 在生物质燃烧典型样品中, 其贡献高达三至六成.     

生物质燃烧源PM2.5在水汽条件下长大特性的研究

研究了生物质燃烧源产生的细颗粒在水汽条件下的长大特性,通过生长管实验研究了不同的热水温度、颗粒初始浓度、颗粒在生长管中的停留时间及表面活性剂下生物质燃烧源细颗粒在水汽过饱和条件中的长大特性。与燃煤细颗粒在水汽条件下的长大结果进行对比,生物质燃烧源细颗粒的长大效果要比燃煤细颗粒长大效果要好,热水温度的升高、停留时间的延长有利于细颗粒的长大,小粒径段颗粒的长大则几乎不受颗粒初始浓度的影响,添加一定量的表面活性剂可以使得生物质燃烧源细颗粒全部长大至1μm以上。     

农作物秸秆解聚研究

农作物秸秆是重要的生物质资源。本文从我国建立资源节约和环境友好社会目标的角度,论述了农作物秸秆高效利用的重要性和研究农作物秸秆解聚对开发农作物秸秆高效利用的新工艺的重要意义。介绍了农作物秸秆解聚的典型工艺及解聚产物组成分析和利用研究的进展,预测了农作物秸秆解聚研究的发展方向。     

秸秆发酵燃料乙醇关键问题及其进展

利用木质纤维素原料生产燃料乙醇是国际公认的难题。本文从秸秆原料组分不均一性出发,分析了秸秆难以高值化原因;进一步分析了秸秆酶解发酵燃料乙醇的关键问题,介绍了有关秸秆原料预处理、纤维素酶生产、秸秆酶解发酵乙醇和产业化示范工程等的进展。秸秆酶解发酵燃料乙醇产业化示范工程具有自主知识产权,为实现我国秸秆转化燃料乙醇的规模化、产业化、低成本生产奠定了基础。     

石油焦与稻草焦共气化研究

在热天平中采用等温热重法对石油焦、稻草焦、石油焦/稻草混合物以及石油焦/稻草焦混合物进行了CO₂共气化研究,实验温度900~1 050 ℃,添加稻草焦的质量比为0~0.5,考察稻草焦对石油焦的催化气化作用。结果表明,在一定气化温度下,石油焦和稻草焦混合物的共气化碳转化率高于各自气化碳转化率的简单加和,具有一定的协同效应,混合物的气化反应速率随着稻草焦添加比例的增加而升高。石油焦、稻草、稻草焦及其各个混合物的反应活性由大到小的顺序为:稻草半焦>脱灰稻草半焦>石油焦/稻草混合物>石油焦/稻草焦混合物>石油焦/脱灰稻草混合物>石油焦/脱灰稻草半焦混合物>石油焦。     

秸秆发酵燃料乙醇关键问题及其进展

利用木质纤维素原料生产燃料乙醇是国际公认的难题.本文从秸秆原料组分不均一性出发,分析了秸秆难以高值化原因;进一步分析了秸秆酶解发酵燃料乙醇的关键问题,介绍了有关秸秆原料预处理、纤维素酶生产、秸秆酶解发酵乙醇和产业化示范工程等的进展.秸秆酶解发酵燃料乙醇产业化示范工程具有自主知识产权,为实现我国秸秆转化燃料乙醇的规模化、产业化、低成本生产奠定了基础.     

Comparison of Different Pretreatment Strategies for Enzymatic Hydrolysis of Wheat and Barley Straw

In biomass-to-ethanol processes a physico-chemical pretreatment of the lignocellulosic biomass is a critical requirement for enhancing the accessibility of the cellulose substrate to enzymatic attack. This report evaluates the efficacy on barley and wheat straw of three different pretreatment procedures: acid or water impregnation followed by steam explosion versus hot water extraction. The pretreatments were compared after enzyme treatment using a cellulase enzyme system, Celluclast 1.5 L from Trichoderma reesei, and a beta-glucosidase, Novozyme 188 from Aspergillus niger. Barley straw generally produced higher glucose concentrations after enzymatic hydrolysis than wheat straw. Acid or water impregnation followed by steam explosion of barley straw was the best pretreatment in terms of resulting glucose concentration in the liquid hydrolysate after enzymatic hydrolysis. When the glucose concentrations obtained after enzymatic hydrolyses were related to the potential glucose present in the pretreated residues, the highest yield, approximately 48% (g g-1), was obtained with hot water extraction pretreatment of barley straw; this pretreatment also produced highest yields for wheat straw, producing a glucose yield of approximately 39% (g g-1). Addition of extra enzyme (Celluclast 1.5 L+Novozyme 188) during enzymatic hydrolysis resulted in the highest total glucose concentrations from barley straw, 32-39 g L-1, but the relative increases in glucose yields were higher on wheat straw than on barley straw. Maldi-TOF MS analyses of supernatants of pretreated barley and wheat straw samples subjected to acid and water impregnation, respectively, and steam explosion, revealed that the water impregnated + steam-exploded samples gave a wider range of pentose oligomers than the corresponding acid-impregnated samples.     

稻草与煤固定床共热解特性的研究

选取稻草为生物质原料,将其与两种不同煤阶的煤(内蒙褐煤和神府烟煤)分别以0∶100、20∶80、40∶60、60∶40、80∶20、100∶0的干基质量比均匀混合.借助固定床反应器,研究了稻草与两种煤的共热解特性,探讨了共热解过程中可能存在的协同作用.结果表明,稻草添加有利于共热解气体产物的生成,且对神府煤作用更明显;稻草含量越高,热解气体产量的实验值与加权平均计算值的偏差也越大,说明稻草与煤共热解过程发生了协同作用.而共热解所得焦产量的实验值与加权平均计算值基本一致.热解焦傅里叶红外光谱分析结果表明,稻草添加对热解焦的官能团未造成显著影响.     

Wear behavior of straw fiber-reinforced polyvinyl chloride composites under simulated acid rain conditions

In order to investigate the effect of simulated acid rain (SAR) corrosion on the wear-resistance properties of straw fiber/polyvinyl chloride (SPVC) composites, four types of straw fibers (wheat straw (WS), rice straw (RS), corn straw (CS), and sorghum straw (SS) fibers) were utilized and incorporated into poly(vinyl chloride) (PVC). The results show that the SS fibers have high levels of cellulose, lignin and crystallinity, and it also exhibited high adhesion strength with PVC matrix, which endow the SS/PVC with high wear-resistance compared with other three SPVC composites. After SAR corrosion, SPVC composites exhibited severe degradation of the physical, mechanical, and thermal properties, and the fibers were easily pulled out from the matrix to form abrasive particles. The high-speed fiber debris in high-temperature and high-loading environments can be deemed a kind of “incompressible lumps” that will form a certain abrasive wear.     

农作物秸秆红外指纹图谱双指标序列分析

采用傅立叶红外光谱技术研究了不同地区、不同种类农作物秸秆的红外指纹图谱,对其谱带归属进行了判别分析;并利用共有峰率和变异峰率双指标序列法对农作物秸秆样品进行分析鉴别。结果表明:同种农作物秸秆化学成分相似,不同农作物秸秆化学成分差异较大,其中花生秆与其他农作物秸秆化学成分差异最大。     

Crystallisation of polypropylene matrix in composites filled with wooden parts of rapeseed straw

Nucleation ability of native and modified rapeseed straw during the polypropylene crystallization from the melt was investigated by the DSC method. Composites were made from isotactic polypropylene and lignocellulosic material using extrusion and injection moulding techniques. They were obtained using polypropylenes differing with respect to melt flow rates and different varieties of rapeseed straw. Chemical modification was carried out in two stages: through mercerisation and treatment with acetic acid anhydride. In the course of investigations, it was found that both native and modified rapeseed straw acted as an active nucleant of polypropylene crystallisation characterised by low values of MFR indices. It was found that for polypropylenes with high MFR values, the values of crystallization temperatures and crystallization half-time in composites were identical when compared with non-filled polymers. The investigations demonstrated that there were insignificant differences among composites containing straw from different varieties of rapeseed. The analysis of crystallization temperatures confirmed that rapeseed straw modification failed to change this parameter of the crystallization process. A similar tendency was observed in the case of changes of the half-time crystallization process. Moreover, the analysis of the crystallization temperature and crystallization half-time showed that the presence in composites of lignified rapeseed straw particles played an important role in the crystallization conditions.     

Preparation and properties of composites made from rice straw and poly(vinyl chloride) (PVC)

Rice straw was employed for the preparation of lignocellulosic‐poly(vinyl chloride) (PVC) composites. The effect of pretreatment of rice straw, concentration of PVC, pressure as well as pressing temperature on the mechanical properties and water absorption was studied. Also, the effect of lignin as coupling agent on the mechanical properties and water absorption of composite was studied. Composites of rice straw comprising both PVC and a coupling agent offer superior properties compared to those made from only rice straw and PVC. The extent of improvement in the mechanical properties and dimensional stability of composites depended not only on the pretreatment of rice straw, concentration of PVC and lignin but also on pressure and pressing temperature. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermal behavior of holo- and hemicellulose obtained from rice straw and bagasse

Thermal gravimetric analysis, and differential thermal behavior of holo- and hemicelluloses obtained from rice straw and bagasse were investigated. Degradation was found to be of first order reaction. The activation energy values and the rate constants were calculated from the kinetic of weight loss. Hemicellulose was found to be less stable than holocellulose, and the stability of the samples was arranged in the order, rice straw holo- > bagasse holo- > rice straw hemi- > bagasse hemicellulose. Degradation of rice straw (holo- as well as hemicellulose) was performed via two exothermic processes, whereas bagasse hemicellulose combustion was completed through three exothermic processes. The magnitude and the shape of the exotherms depend, mainly, on the chemical composition of the sample.