生物质废弃物在回转窑内热解研究--Ⅱ.热解终温对产物性质的影响

考察了不同热解终温下木块和稻壳在回转窑内热解产物－燃气、焦油和炭的成分和性质的变化。在试验温度范围内,热解气体热值约10．0－15．9MJ／Nm^3,密度1.21-1.52Nm^3/kg,且随热解终温变化呈规律性变化,木块炭的热值为29.0-33.9MJ／kg,稻壳炭则为17.6-20.8MJ/kg,热解终温的提高使炭中挥发份的降低,灰分增多,从而导致热值的降低;炭的C含量高于原始物料的C含量,而H、O则相反;元素残留率的计算表明,热解过程中H和O元素的脱除易于C元素。热解终温对焦油中饱和烃、芳香烃成分含量的影响不大,饱和链烃成分主要集中为C14－C34正构烷烃和含末端双链烯烃的碳分子链,芳香烃主要为蒽（菲）、芘、萤蒽及各自衍生物的稠环芳烃。     

生物质热解气化制取氢气

该文对生物质的热化学方法(主要是气化和热解)制取氢气进行了归纳总结，在此基础上研究了用热解方法从生物质原料中制取氢气的技术路线并介绍了催化制氢的实验室研究结果。研究的结果表明：催化剂的添加对热解过程的最终产品气及富氢气体的产率有影响；催化剂的负荷量对富氢气体的产率有显著影响，其值存在一个优化范围；同样的催化剂对稻杆和锯末热解获得的富氢气体的产率影响不同。     

城市垃圾在回转窑中热解：热解焦油特性研究

利用自行设计制造的外热式回转窑以ＰＥ塑料、废轮胎和木块为试验物料进行了一系列热解试验。对热解焦油进行了旋分分析,元素分析和ＧＣ－ＭＳ分析。考察了热解终温对焦油产量、焦油族分及Ｃ、Ｈ等元素的含量的影响,并对ＰＥ塑料的热解焦油的化合物组成进行了分析,研究表明,在试验温度范围内,热解终温对试验物料的焦油产量和焦油族分有明显影响;ＰＥ塑料和废轮胎焦油的Ｃ／Ｈ原子比为０．４２－０．８２,具有较好的加工性能,     

稻壳和褐煤热解特性的初步研究

利用TG-DSC联用分析稻壳与褐煤热解过程中热失重规律及吸放热情况,结果发现,稻壳的热失重率较大,共热解失重过程相当于二者单独热失重过程的叠加。通过DSC曲线分析稻壳与褐煤热解过程的吸放热量显示,与二者单独热解过程不同的是共热解在高温热分解阶段须吸收大量的热量。利用气相色谱分析不同温度下稻壳与褐煤热解气体产物各组分比例,并与热失重过程相对应分析气体产物变化规律,结果发现,H2和CH4气体组分变化规律相同;与褐煤热解相比,稻壳热解气体产物中CO气体组分较多。总体而言,共热解产物是二者单独热解产物的简单加和,但共热解过程吸放热量变化却显示二者存在热量交换和相互影响。     

移动床中热气体渗流传热对煤粒热解反应过程的影响

针对移动床内热气体对煤颗粒预热处理工艺,分析了颗粒料层中热气体渗流传热对煤热解反应过程的影响,建立了多孔介质渗流传热与煤热解反应相互作用的物理数学模型。研究了不同情况下移动床内气固温度和压力分布以及煤热解反应规律,计算结果表明,高温热气对移动床煤颗粒料层的热量渗透主要发生在渗透入口端区域,热解反应发生在热渗流作用区域,煤的热解反应对应酬内温度场分布有较大的影响,改变运行参数可以调整热渗透作用区域推移速度和物料温度水平,从而控制煤热解反应过程,在热解反应区域,孔隙率对流场,压损和煤热解过程有很大的影响。图9参11     

纤维素热解的TG-FTIR分析

以生物质主要组分纤维素为原料,在热重-红外光谱联用仪上对纤维素分别以5,10,20,40℃/min的升温速率进行了热解实验研究,考察了纤维素的热解特性及轻质气体析出规律。结果表明:较高的升温速率能促进热解反应的进行,升温速率可作为影响最大热解失重速率对应温度(Tp)的一个重要因素,Tp会随着升温速率的增大而升高;纤维素热解过程中,热解气体的最大析出峰都对应于给定升温速率下的DTG失重峰;4种主要轻质气体(H2O,CO,CO2和CH4)均表现为双峰特性,且CO气体在热解后期的析出规律与CO2,H2O和CH4气体的析出规律不同;不同官能团键的断裂和重整,致使小分子气体组分和析出量的差异很大,热解过程中,羰基(C=O)和醚键(C-O-C)的断裂对CO2的生成影响显著;在低温区间CO的析出主要源于C-O-C的断裂,而在高温区间二芳基醚的分解则是CO产生的主要原因;CH4气体的析出主要由甲氧基(CH3O-)的伸缩振动引起。     

稻壳粉燃烧过程中颗粒尺寸和形态的演变

以颗粒尺寸为250 ~ 300 μm的稻壳粉为研究对象,通过高温沉降炉中的热解和燃烧实验结合颗粒样品的扫描电子显微镜图像分析方法,研究了稻壳粉燃烧过程中颗粒尺寸和形态的变化及热解、燃烧条件的影响。结果表明,热解时颗粒宽度等尺寸参数均缩小,温度的影响较小;焦燃烧时颗粒尺寸因破碎明显减小,温度、气氛等燃烧条件通过影响破碎进而影响尺寸变化。对于形态参数,热解和燃烧后横纵比的变化及实验条件对其变化的影响与尺寸参数相似;热解和燃烧后圆形度几乎无变化;圆度在热解后变化也较小,而燃烧后明显减小;实验条件对圆形度、圆度的变化几乎无影响。     

存在可变残留层的固体可燃材料热解数值模型

采用偏微分数值模型，使用热解界面预估循环迭代的方法，对存在可变残留层材料的热解过程进行了详细研究．将数值结果同准确解以及积分模型结果进行了比较，模拟并分析了材料残留率对材料热解速率的影响．结果表明，积分模型中温度分布采用二次三项式假设在热解发生初期将带来很大误差，热解速率结果高于微分模型结果．并且残碳率的高低对热解速率及相应的外表面温度变化有很大的影响．模型过程具有相当高的准确性和可靠性。     

超细石灰石热解的数学模拟和试验研究

采用缩核模型对超细石灰石热解进行了模拟。由于颗粒较小，模型忽略了传热对热解影响，假定石灰石热解过程由二氧化碳扩散和反应界面处反应速度决定，反应速率与反应界面处二氧化碳的压力成反比，结合热解过程中由于烧结所引起的比表面积的变化，计算热解率随温度、比表面积、粒径等变化规律以及界面处压力对热解率的影响，并由试验对计算结果进行了验证。图6表1参10     

热辐射下木材热解与着火特性实验

对几种木材在不同辐射热流下的热解与着火特性进行了研究,且研究了含水率对木材热解与着火过程的影响.分析热解与着火过程中木材试样不同深度的温度变化与失重变化,对木材的着火时间与着火温度进行记录,并着重分析水分对木材温度分布、着火时间与着火温度的影响.通过间接的方法从实验的着火数据中获得了木材的临界着火热流值约为25 kW/m2.     

木质类生物质的热重分析研究

在常压热重分析仪和加压热重分析仪上对木屑进行了热解实验，利用热重分析法对其热解行为特性和动力学规律进行了分析．得到了升温速率、压力等因素对木屑热解过程的影响规律。实验表明：常压下，随着升温速率的增加，反应激烈程度增加；与常压相比，加压状态下，活化能明显减小；随着热解压力的提高，挥发分初析温度和DTG峰值温度升高，最大失重速率减小；活化能E与频率因子A之间存在动力学补偿效应，升温速率不变，改变压力或者压力不变，改变升温速率，得到的利、偿效应表达式不同。     

Technoeconomic analysis of the production of biocrude from wood

The production of biomass-derived oil (biocrude) has been studied to determine the technoeconomic characteristics of the process. A detailed process model was developed for the production of biocrude from wood chips. The process consists of a silo dryer for the removal of water from the feed wood, a vortex reactor for the pyrolysis of the wood, a furnace to provide the required sensible heat and heat of reaction for the pyrolysis reaction, a steam turbine to convert excess thermal energy into electric power, and a biocrude recovery section.

Results of the simulation were used to size and cost major equipment items. Technoeconomic evaluation of the process was conducted to develop an understanding of the important parameters and to identify missing or incomplete data. Studies were conducted to illustrate the importance of economic parameters on the perceived viability of a process. Plant size and production capacity were examined, as were a number of process development strategies.     

Characteristic of hydrogen and syngas evolution from gasification and pyrolysis of rubber

The characteristics of syngas evolution during pyrolysis and gasification of waste rubber have been investigated. A semi-batch reactor was used for the thermal decomposition of the material under various conditions of pyrolysis and high temperature steam gasification. The results are reported at two different reactor temperatures of 800 and 900 °C and at constant steam gasifying agent flow rate of 7.0 g/min and a fixed sample mass. The characteristics of syngas were evaluated in terms of syngas flow rate, hydrogen flow rate, syngas yield, hydrogen yield and energy yield. Gasification resulted in 500% increase in hydrogen yield as compared to pyrolysis at 800 °C. However, at 900 °C the increase in hydrogen was more than 700% as compared to pyrolysis. For pyrolysis conditions, increase in reactor temperature from 800 to 900 °C resulted in 64% increase in hydrogen yield while for gasification conditions a 124% increase in hydrogen yield was obtained. Results of syngas yield, hydrogen yield and energy yield from the rubber sample are evaluated with that obtained from woody biomass samples, namely hard wood and wood chips. Rubber gasification yielded more energy at the 900 °C as compared to biomass feedstock samples. However, less syngas and less hydrogen were obtained from rubber than the biomass samples at both the temperatures reported here.     

Impact of a pressurized hot water treatment on the quality of bio-oil produced from aspen

The bio-oil produced by fast pyrolysis is a genuine alternative to fossil resources. However an improvement of its quality is required in order to improve its application.To upgrade the quality of bio-oil, Pressurized Hot Water Treatment (PHWT) has been applied on trembling aspen whole wood chips prior to fast pyrolysis process. The pyrolysis was then performed in an auger reactor at the temperature of 723 K. The effects of PHWT on yields, physicochemical properties, and composition of bio-oils were investigated.Although PHWT does not seem to influence the bio-oil yield, which remains around 56% for both untreated and pre-treated wood, it does improve its quality. The main effect of pre-treatment is the lower water content of the oil obtained from pre-treated wood, which is thus meeting the requirements of ASTM D7544 Standard. Moreover, PHWT appeared to favor the levoglucosan production and to decrease the syringol derivatives content of the bio-oil. The elementary composition revealed an increase of the C/O ratio when the biomass was pre-treated. This is in agreement with the heating value of bio-oil from pre-treated biomass which was found to be higher than that of bio-oil from untreated biomass.     

城市固体废弃物典型组分的快速热解产气特性研究

选取城市固体废弃物中的常见六种组分(纸屑、厨余、织物、木屑、塑料、橡胶)作为实验物料进行快速热解实验。在所得实验数据的基础上对热解气体产物的组成以及变化情况进行了分析，并研究了热解混合气的热值随时间变化的情况。通过研究有助于对热解产物进行预测，且能够深入地了解热解机理。     

Carbonization of some fast-growing species in Sudan

Four wood species, indigenous Acacia seyal (talh) and exotic fast-growing Conocarpus lancifolius (damas), Eucalyptus microtheca (kafur) and Prosopis chilensis (mesquite) grown in Sudan, were assessed and compared as raw materials for charcoal making. The effects of production method (traditional earth mound and improved metal kiln) and the physical and chemical properties of the wood and bark on the yield and quality of charcoal produced were assessed. Regression analyses of wood properties and heat value data indicated high negative correlations of the wood heat value with holocellulose and ash, and high positive correlations with wood density, lignin, and alcohol-benzene and hot-water solubles. Carbonization with the Tropical Products Institute metal kiln produced higher yields (33%) than the traditional earth mound (27%), although the difference in energy transformation yields was found to be insignificant both between appliances and species. Charcoal produced by the earth mound had a slightly higher density and was more resistant to shatter, but no significant differences were recorded with respect to the water boiling test or the gross heat value. The exotic species studied gave equal or better charcoal, in terms of yield and quality, compared with the traditionally preferred talh.     

The influence of drum chipper configuration on the quality of wood chips

The efficiency of adequately chosen and monitored technology during the production of wood chips is shown by the quantity of energy stored within the wood fuel, and in the manufacture and preparation costs per product unit. Several influential material, construction, and technological parameters have to be encountered during the production of wood chips when using a mobile drum chipper. A set of different experiments regarding the production of wood chips using a drum chipper were made in order to find the more suitable combinations of production parameters (technological and constructional) for different types of inputted materials (hard round wood, soft round wood, and branches).By monitoring the energy contents within different kinds of wood chips, it was determined that soft wood biomass having rougher structures and hard wood biomass having finer structures are more suitable for larger systems. Dust particles within the wood fractions are undesirable; however constant forms and size–structures regarding wood chips are welcome.The aim of our research was to build a decision model that would help a user to choose the right combination of parameters on a drum chipper, thus ensuring the production of wood fuel with characteristics close to the desired optimum, yet at minimum production costs.     

Industrial supply chains and production machinery of forest chips in Finland

Metsäteho Oy surveyed the industrial supply chains used in the production of forest chips in 2006 in Finland. The Metsäteho study also conducted a survey of the production machinery of forest chips used by energy plants in 2007, and provided an estimate of industrial supply chains and future machinery requirements for forest chip production in Finland.The majority of the logging residue chips and chips from small-sized thinning wood were produced using the roadside chipping supply chain in 2006. The chipping at plant supply chain was also significant in the production of logging residue chips. The majority of all stump wood chips consumed were comminuted at the plant, and with only around one fifth comminuted at terminals. The role of the terminal chipping supply chain was also significant in the production of chips from logging residues and small-sized wood chips. It was predicted that the roles of both terminal chipping of logging residues and chipping at the plant will increase by the year 2010. Regarding the production of chips from small-diameter wood, it was estimated that the role of chipping at the plant will also increase in coming years. The proportion of roadside chipping in the production of small-sized wood chips and logging residue chips is expected to decrease.The study estimated that a total of 1100 machine and truck units were employed in the production of forest chips for energy plants in 2007. Increasing forest chip consumption will create considerable demand for additional forest chip production resources in the future.     

Modelling anhydrous weight loss of wood chips during torrefaction in a pilot kiln

Beech and spruce chips were torrefied in a batch rotating pilot kiln. For each torrefaction the temperature curve of the moving chips bed was recorded. The anhydrous weight loss (AWL) of each torrefaction was measured. Effect of torrefaction temperature and duration on the AWL was studied. In order to optimise short time torrefaction, models that can estimate the AWL from the chips temperature curve are required. Three phenomenological models were successfully applied. They all gave good correlations between experimental and calculated AWL. These three models can be employed to optimise industrial torrefaction. However, the more complex they are, the more difficult it is to understand their physical meaning. It is thus preferable to use simple model for the industrial control of torrefaction.     

Experimental investigation of pyrolysis process of woody biomass mixture

This paper describes an experimental investigation of pyrolysis of woody biomass mixture. The mixture consists of oak, beech, fir, cherry, walnut and linden wood chips with equal mass fractions. During the experiment, the sample mass inside the reactor was 10 g with a particle diameter of 5-10 mm. The sample in the reactor was heated in the temperature range of 24-650℃. Average sample heating rates in the reactor were 21, 30 and 54 ℃/min. The sample mass before, during and after pyrolysis was determined using a digital scale. Experimental results of the sample mass change indicate that the highest yield of pyrolytic gas was achieved at the temperature slightly above 650℃ and ranged from 77 to 85%, while char yield ranged from 15 to 23%. Heating rate has sig- nificant influence on the pyrolytic gas and char yields. It was determined that higher pyrolysis temperatures and heating rates induce higher yields of pyrolytic gas, while the char mass reduces. Condensation of pyrolytic gas at the end of the pyrolysis process at 650℃ produced 2.4-2.72 g of liquid phase. The results obtained represent a starting basis for determining material and heat balance of pyrolysis process as well as woody biomass pyrolysis equipment.