生物质热解油气化试验研究

生物质是一种环境友好可再生资源，可以通过多种途径转化为液体燃料。生物质热解液化即是在缺氧状态下对生物质进行快速加热，然后再对热解产物进行快速冷凝，最后获得一种称为生物油的液体燃料的技术。该技术以及生物油的特点主要有：热解液化温度为500℃，远低于生物质热解气化所     

升温速率对生物质热解的影响

稻壳、稻秆及麦秆是中国主要的农业废弃物,如何综合、有效地利用这些农业废弃物进行资源化研究显得十分必要。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。目前,国内外对生物质及其组分的热解已有大量的研究,但对中国主要的农业废弃物稻壳、稻秆及麦秆的研究较少。本研究利用热重和红外联用技术深入研究了升温速率对三种典型生物质热解气体产物的影响,并对生物质的热解动力学及热解气体产物的析出规律进行实时在线分析。     

Experimental study on tar destruction in a two stage fixed-bed reactor

通过两段式固定床反应器实验,研究了热裂解、部分氧化和炭层转化三种方法对焦油脱除的效果,并研究了生物质种类、反应温度、停留时间、生物质焦的粒径及种类等因素对热解焦油的脱除和转化规律.结果表明,随着温度的升高,三种脱除方法中焦油生成量下降,且降幅逐渐减小,实验过程中无论采取何种方法,都难以将焦油完全脱除;部分氧化和炭层转化对焦油的脱除效果都较相同温度条件下的热裂解要好,且在焦油脱除效果上,炭层转化＞部分氧化＞热裂解;联合部分氧化和炭层转化可达最高的焦油脱除效率,三种生物质热解焦油经1000℃联合脱除后产量分别为,稻秆0.43％、玉米秆0.61％和杉木屑1.15％,转化率分别达到98.28％、97.23％和96.29％;相同实验条件下稻秆的热解焦油最容易脱除,这与其物料中含氧量较高有关;生物质焦种类对焦油的脱除效果影响较小.     

生物质主要组分低温热解研究

利用热重分析仪和裂解气质联用仪进行生物质主要组分低温热解特性研究。热重实验结果表明,生物质主要组分的热稳定性为：纤维素>木质素>半纤维素。半纤维素主要热解温度在210℃～320℃,而纤维素和木质素的主要热解温度分别在310℃～390℃和200℃～550℃。裂解气质联用实验考察不同温度对生物质主要组分低温热解产物的影响。半纤维素热解产物主要有乙酸、1-羟基-丙酮和1-羟基-2-丁酮,纤维素热解产物主要包括左旋葡聚糖和脱水纤维二糖,而木质素热解产物主要是邻甲氧基苯酚。     

两段式固定床反应器中焦油脱除的实验研究

通过两段式固定床反应器实验,研究了热裂解、部分氧化和炭层转化三种方法对焦油脱除的效果,并研究了生物质种类、反应温度、停留时间、生物质焦的粒径及种类等因素对热解焦油的脱除和转化规律。结果表明,随着温度的升高,三种脱除方法中焦油生成量下降,且降幅逐渐减小,实验过程中无论采取何种方法,都难以将焦油完全脱除;部分氧化和炭层转化对焦油的脱除效果都较相同温度条件下的热裂解要好,且在焦油脱除效果上,炭层转化>部分氧化>热裂解;联合部分氧化和炭层转化可达最高的焦油脱除效率,三种生物质热解焦油经1 000 ℃联合脱除后产量分别为,稻秆0.43%、玉米秆0.61%和杉木屑1.15%,转化率分别达到98.28%、97.23%和96.29%;相同实验条件下稻秆的热解焦油最容易脱除,这与其物料中含氧量较高有关;生物质焦种类对焦油的脱除效果影响较小。     

不同生物质热解特性及气体产物释放规律研究

研究了竹屑、棉籽壳和棉秆三种生物质的热解特性及差异。采用热重质谱联用技术,对比并分析了三种生物质原料在热裂解中气体产物(CO、H_2、CH_4、CO)随温度变化的释放规律。结果表明:相比于棉籽壳和竹屑,棉秆的失重率最大约为84%。其次,由热解阶段的产物可知,虽然棉秆在热解时的气体离子流(CH_4和CO_2)释放强度高于棉秆和棉籽壳,但是对于生物质混合气体(H_2和CO)的离子流强度,竹屑的离子流强度高于棉秆和棉籽壳。最后,在热解性能方面,挥发分初始析出的温度和热解特性指数的大小排列结果一致,均为竹屑棉籽壳棉秆,其表观活化能分别48、52和66 kJ/mol,这与热重实验结果一致,在相同条件下竹屑的热解性能最好。     

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。     

基于TG-FTIR的生物质催化热解试验研究

运用热重－傅里叶红外光谱联用技术(TG-FTIR)，以麦秸为研究对象，探讨催化与非催化条件下生物质的热解挥发分析出特性，分析研究热解温度、催化剂种类对生物质热解主要析出产物的影响。通过热重TG和DTG曲线，获得了相关热解特性参数及动力学参数。结果表明，添加NiO和CaO存在两个失重峰，并促进麦秸热解反应进行，降低表观活化能，其中NiO对提高热解析出产率作用更显著。通过红外光谱对热解产物实时测量的分析表明，CO与CO2的析出与失重峰基本一致，而CH4的析出滞后于前两者。添加NiO和CaO有利于减少热解产物中的CO2的浓度，促进挥发分产物CO、CH4的生成。其中CaO更有利于生物质在温度800℃以下的热解性能改善，而NiO在800℃以上具有更好的催化作用。     

煤与生物质热重分析及动力学研究

利用热重分析仪对稻秆、麦秆、木屑和煤单独及混合热解特性进行了研究。通过对不同混合比例热解与单独热解对比表明,混合热解中不同生物质起始热解温度、生物质挥发分最大析出温度、煤挥发分最大析出温度随着煤混合比例的变化呈规律性变化。对混合热解实验数据与单独热解参数按混合比例后特性参数分析表明,混合热解导致固体产物产率提高。实验通过对稻秆两种方式的脱灰及脱挥发分处理后混合热解分析,脱挥发分稻秆与脱灰分稻秆对煤的热解都起到了促进作用,证明了生物质中的碱/碱土金属能促进煤在较低温度下热解,硅元素对热解速率起抑制作用。推测生物质与褐煤的共热解中存在协同作用。     

污泥微波高温热解条件下富氢气体生成特性研究

分别采用单模微波炉和电加热管式炉对污泥热解过程进行了实验研究,分析了污泥粒径、含水率、热解温度和微波吸收剂形态等参数对热解产物分布特性和气体组分浓度的影响规律和机理。结果表明,在粒径0~5.00 mm,污泥粒径大小对污泥微波热解产物分布无明显影响,但粒径减小可以提高H₂和CO浓度,当粒径从2.50~5.00 mm减小至小于0.45 mm,H₂和CO体积分数分别从31%和17%上升至34%和22%;污泥含水率和微波热解温度对热解产物分布和热解气组分浓度分布都有显著影响,提高污泥含水率或微波热解温度都可以显著提高H₂和CO浓度,当污泥含水率从0上升至83%,H₂和CO体积分数分别从32%和20%上升至42%和31%;相比粉末态吸波剂,固定形态的微波吸收器可以提高挥发分向热解气的转化,提高热解气产量,同时还能略微提高H₂和CO产率,但效果并不明显。     

Mechanism of Xylan Pyrolysis by Py-GC/MS

In order to investigate the decomposition behavior of hemicellulose, xylan was chosen as the representative of hemicellulose to study the fast pyrolysis on the combination system of analytical pyrolyzer and gas chromatograph coupled with mass spectrometer(Py-GC/MS). The main condensable products of xylan pyrolysis consisted of acids, aldehydes, and ketones; while gas products contained CO₂, CO, CH₄ and H₂. Acetic acid and furfural were the most abundant products with the highest contents of 20.11% and 20.24% respectively. While furfural and acetic acid were formed competitively with residence time and temperature increases, the distribution of xylan pyrolysis products did not vary with the residence time and temperature, while the total content of several kinds of products changed a lot. According to the analysis of experimental data, a reaction pathway of xylan decomposition was deduced so as to illustrate the formation mechanism of main products.     

Sulphur distribution in the products of waste tire pyrolysis

The aim of the presented work was to investigate the distribution of sulphur in tire pyrolysis products as well as the influence of process parameters (temperature and residence time) on sulphur distribution due to environmental concerns. Among modern methods used for waste tire recycling, pyrolysis is one of the most reasonable alternatives meeting current environmental standards. However, waste tire sulphur content can be a potential drawback for pyrolysis products utilisation as fuels. Sulphur is present in tires in different concentrations, depending on the type and age of the tires. Typical sulphur content in tires is about 1.6 mass %. In this paper, the distribution of sulphur in tire pyrolysis products was investigated. Tire pyrolysis yields three different products: liquid, gaseous, and solid residue composed mostly of carbon black (chars). Temperature and residence time are the two most important parameters affecting the yield and composition of the volatile fraction and they are therefore expected to affect the sulphur content in residues. Pyrolysis experiments were carried out in a laboratory pyrolysis reaction unit in the temperature range of 650°C to 750°C at different residence times: 88.6 s, 80.2 s, and 73.9 s. Liquid and solid products were analysed by elemental analysis and the distribution of total sulphur in tire pyrolysis products was calculated.     

Devolatilization behaviour and pyrolysis kinetic modelling of Spanish biomass fuels

The basic pyrolysis behaviour of eight different biomass fuels has been tested in a thermogravimetric analyser under dynamic conditions (5, 20 and 50 °C min^?1 heating rates) from room temperature up to 1,000 °C. Their decomposition was successfully modelled by three first-order independent parallel reactions, describing the degradation of hemicellulose, cellulose and lignin. Hemicellulose would be the easiest one to pyrolyse, while lignin would be the most difficult one. Experimental and calculated results show good agreement. The reactivity of the different biomass type functions of various thermal, kinetic and composition parameters are discussed. The effect of the heating rate on pyrolysis behaviour was studied, and a comparison between slow and fast heating rate reveals a small displacement of the DTG profiles to higher temperatures. The heating rate not only affects the highest mass loss rate temperature but also influences the mass loss rate value.     

Pyrolysis of waste materials using TGA-MS and TGA-FTIR as complementary characterisation techniques

Pyrolysis of waste materials, biomass wood waste, waste tyre, refuse derived fuel (RDF) and waste plastic was performed using two thermogravimetric analysers (TGA). One TGA was coupled to a mass spectrometer (MS) and the other to an infrared spectrometer (FTIR). The kinetic parameters of the pyrolysed waste materials obtained for TGA-MS and TGA-FTIR were compared using a model based on first-order reactions with a distribution of the activation energies. A further comparison of the volatile species evolved by thermal degradation (TGA) and the subsequent characterisation by the MS and FTIR spectra was performed. The first-order reaction pathways and subsequent activation energies calculated from the differential TGA data presented good repeatability between the TGA-MS and TGA-FTIR. The TGA-MS and TGA-FTIR produced a broad spectrum of qualitative data characterising the volatile gaseous fraction of the waste materials pyrolysed. TGA-MS and TGA-FTIR are shown to be valuable techniques in corroborating the respective thermograms and spectrograms of the volatile species evolved during the pyrolysis of waste materials. However both techniques are prone to interference and careful interpretation of the spectra produced is required.     

神府烟煤快速热解特性研究

利用高频电炉对神府煤进行快速热解,研究了不同热解温度和停留时间下,固相和气相产物的性质。结果表明,煤焦的失重率及真密度随温度升高和时间的延长而增长。红外光谱结果表明,热解过程中,煤中含氢/含氧官能团分解,生成H₂、CO、CO₂、CH₄等气体,并且其分解程度随温度的升高和时间的延长而加深。气相产物中H₂和CO的释放量随温度的升高和时间的延长而增加,而CO₂和CH₄存在释放量的峰值。气相产物随温度的升高和时间的延长而增多,导致高温煤焦出现大量的孔隙和裂缝。     

Effect of particle size on pyrolysis characteristics of Elbistan lignite

In this study, the relationship between particle size and pyrolysis characteristics of Elbistan lignite was examined by using the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. Lignite samples were separated into different size fractions. Experiments were conducted at non-isothermal conditions with a heating rate of 10°C min⁻¹ under nitrogen atmosphere up to 900°C. Pyrolysis regions, maximum pyrolysis rates and characteristic peak temperatures were determined from TG/DTG curves. Thermogravimetric data were analyzed by a reaction rate model assuming first-order kinetics. Apparent activation energy (E) and Arrhenius constant (A _r) of pyrolysis reaction of each particle size fraction were evaluated by applying Arrhenius kinetic model. The apparent activation energies in the essential pyrolysis region were calculated as 27.36 and 28.81 kJ mol⁻¹ for the largest (−2360+2000 μm) and finest (−38 μm) particle sizes, respectively.     

Molecular-beam mass-spectrometric analysis of lignocellulosic materials : I. Herbaceous biomass

A rapid analytical technique has been developed to qualitatively screen and quantitatively analyze biomass feedstocks for conversion into hydrocarbon fuels and chemicals. In this rapid analytical pyrolysis approach, herbaceous biomass feedstocks stored in the open without cover for 6 to 9 months were characterized using the molecular-beam mass spectrometer (MBMS). The biomass materials were pyrolyzed at 600°C and the volatile pyrolysis products were analyzed in real time by the MBMS. The mass spectral data were further analyzed by multivariate statistical techniques (Factor Analysis). The contents of nitrogen compounds, pentosans and hexosans estimated from the pyrolysis mass-spectrometric/multivariate analysis techniques correlated well with the results obtained by conventional wet chemical methods. However, lignin correlation was very weak because of the presence of microbial degradation products of biomass (humic material) that interfered with the Klason lignin analysis.

This rapid analytical technique was used to analyze various fractions of the stored biomass feedstocks. A comparison of exposed surface biomass materials and the unexposed materials showed that the exposed fraction lost 30% (wt) of the carbohydrate component of the biomass relative to the fresh material.     

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。     

粉粒流化床中松木生物质热解特性的研究

通过冷模实验考察了双颗粒流化床的流化特性。结果表明,在适宜的气速范围内,双颗粒流化床层内部可保持较好的流化状态。松木生物质在粉粒流化床反应器中的热解和催化热解实验结果表明,生物质热解时挥发分的释放存在一个最快的温度区域,生物质中约92%的挥发分在723 K时即可释放完全。773 K时,生物质热解产物中的无机气体(IOG)、低碳烃气体(HCG)和碳氢化合物液体(HCL)的收率之和只有3.1%。随着热解温度的升高,IOG、HCG和HCL的收率均逐渐增加,1 173 K时,其收率之和达到58.7%,且产物主要以CO为主。CoMo-B催化剂可有效促进生物质催化加氢热解产物的二次气相反应,在863 K下可得到6.3%,轻质芳烃化合物(苯、甲苯、二甲苯和萘)是1 173 K下非催化过程的两倍。