煤与生物质快速共热解协同效应的研究进展

文章对现有煤与生物质的共热解机理进行了简要概括,并对几种煤与生物质快速共热解常见设备中协同效应的研究现状进行了归纳。结果表明,反应器类型是煤与生物质共热解过程中的重要影响因素:在沉降炉以及气流床反应器内均未发现共热解过程有明显的协同效应,而在自由落下床反应器内则表现出较为明显的协同效应。本课题组在低变质烟煤与小麦秸秆快速流化床共热解研究过程中发现,混合物料的实际焦油收率明显大于理论焦油收率,即共热解过程展现出了明显的协同效应。最后,在总结现有研究文献的基础上,对快速共热解协同效应研究的不足进行了分析,并对该研究方向的未来进行了展望。     

生物质与塑料共热解技术的分析方法及反应器研究进展

共热解技术是生物质与塑料高质化转化和高值化利用的重要方向。掌握生物质与塑料共热解分析技术及发展趋势,有利于加快对生物质、废塑料等废弃物的处理和利用。通过介绍生物质与塑料共热解技术的最新研究进展,归纳共热解过程动力学模型以及各组分之间的协同效应,讨论生物质与塑料在不同方法和反应器下共热解的表征。生物质和塑料共热解可降低热转化所需活化能,共热解协同效应可促进液态和气态产物生成。热解温度、加热速率和热解时间是影响共热解过程和产物的主要因素。文章为生物质与塑料共热解反应器类型的选择和相关技术分析提供参考。     

煤和生物质共热解研究现状

煤和生物质共热解能够提高煤的利用效率,从而实现煤炭资源的综合、洁净和高效利用。生物质是富氢物质,煤和生物质共热解在某一温度发生同步热解,使生物质中富余的氢可能转移到煤中从而发生协同作用。本文综述了近年来国内外煤和生物质共热解的研究进展,考察升温速率对煤和生物质共热解协同作用影响研究及煤和生物质共热解对固、液、气体产物的影响研究。     

共热解过程中煤与生物质相互作用的研究进展

煤炭与生物质共热解是实现煤炭高效清洁利用的重要途径之一。共热解可改善煤炭单独热解产生的污染问题和生物质单独利用时能源密度低、季节性供应不平衡的问题,不仅能提高煤炭转化效率,还能获得更高品质油品。本文从煤与生物质共热解的影响因素、研究方法和共热解过程中组分间相互作用等方面出发,对近期国内外煤与生物质共热解的研究进行综述。总结了生物质种类、热解工艺参数和热解反应器的类型对煤与生物质共热解过程的影响规律以及煤与生物质在共热解过程中的相互作用过程,即半焦与挥发分间的相互作用、挥发分间的相互作用、生物质中碱金属对共热解的催化作用,并针对如何进一步认识煤与生物质相互作用机理、提高共热解效率等问题和发展方向作了展望。     

生物质与煤共热解研究现状

综述了近年来国内外煤与生物质共热解的研究现状。当生物质与煤共热解过程中存在协同反应时,能够将生物质中的氢有效地转移到煤热解过程中,改善煤热解过程中产物的性质,提高煤的热解效率。后续对生物质与煤共热解的研究可以考虑适当的方法,如添加合适的催化剂等来促进协同反应的发生。     

生物质与聚合物、煤共热解研究进展

综述了近几年来生物质与其它物质如煤和聚合物共热解的研究进展。通过对生物质、煤和聚合物的单独热解以及同煤和其它聚合物共热解的大量文献报道结果进行比较发现:生物质与许多聚合物共热解具有协同作用,可以降低液体产物的含氧量,提高热解液相产率等。显示出生物质与某些聚合物共热解比单独热解具有一定的优势;并比较了煤和生物质共热解产生的现象,得到煤和生物质共热解难以产生协同作用。本文作者结合现阶段的研究成果,提出生物质与煤采用两步法热解工艺的思路,使生物质材料的氢有可能转移到热解煤的产物中,以改善煤热解过程中液体的性质,对今后生物质与煤及聚合物共热解的研究方向提出了自己的建议。     

生物质热解和气化制取富氢气体的研究现状

随着世界能源和环境问题的发展,洁净的氢能源成为备受关注的新能源。目前,生物质热化学法作为制取富氢气体的有效方法而被广泛研究。本文系统地介绍了国内外通过生物质热解和气化制取富氢气体的研究现状,包括热解气化工艺、物料特性、热源类型、反应条件、气化剂及催化剂等对制取富氢气体的影响。重点介绍了不同类型催化剂在生物质热解和气化反应中的应用,以及催化剂在制取富氢气体方面的优势及其作用机理。提出生物质热解和气化制取富氢气体所面临的主要问题是寻求既高效又寿命长的新型或混合型催化剂,或者从工艺、反应器的改进入手,改善催化剂的催化环境,从而解决其失效问题。     

生物质与聚乳酸塑料共热解特性

生物质与塑料、煤等物料之间的共热解是环境友好、具有极大发展潜力的生物质热解升级处理方式。通过自制快速固定床热解反应器研究了玉米芯与聚乳酸的热解。结果表明,玉米芯与聚乳酸的共热解使热解油产率和热值增加,而水分含量降低。通过TGA/FTIR联用实时考察了玉米芯、聚乳酸及其二者混合条件下的热解气体析出特性,FTIR分析表明玉米芯与聚乳酸在共热解条件下存在明显的耦合作用。     

陕北油房梁煤与生物质共热解研究

在N2气氛下,利用热重分析仪对生物质与陕北油房梁煤混合热解特性进行研究,重点考察了生物质混掺比对煤热解的影响。结果表明:相同升温速率下,生物质与煤在热解过程中表现出明显不同的热解特征;生物质与煤以不同掺混比进行共热解时,得到的共热解曲线分段呈现出生物质与煤单独热解的特性,且热解残余固体量与掺混比呈线性关系;此外,对比混合物共热解的实际特征曲线与理论计算曲线,发现实际DTG曲线也与理论计算的DTG曲线基本重合。从上述结果可预测,在热重反应器同步升温情况下,生物质与煤在共热解过程中不存在协同作用。     

微负压系统中煤与橡胶共热解的协同作用

在热重分析仪及自制的微负压煤热解实验装置上,对陕北烟煤、橡胶及两者的混合物进行了实验研究。结果表明,煤与橡胶共热解时存在协同效应,并且随着热解温度增加,协同效应逐渐增强。橡胶是共热解反应的供氢物质,同时橡胶热解产生较多的甲烷,有利于煤中大分子的裂解,可提高煤热解的焦油收率。在热解温度为800℃时,任意橡胶质量分数的煤与橡胶混合物共热解的焦油收率均比线性叠加值高,当橡胶质量分数为20%时,协同作用最为显著。     

煤-合成气共热解特性的研究

选用山东黄县褐煤分别在高压热天平及10g固定床反应器中与合成气共热解对其热失重行为、不同热解终态温度下产物分布及热解半焦燃烧特性进行了详细考察。结果表明,煤－合成气共热解具有与加氢热解基本相似的热失重行为即具有较为明显的热分解和加氢热解失重峰。固定床热解总转化率、焦油收率及热解水分均随终态温度升高而增加,热解半焦燃烧着火点、燃尽温度均随热解终温升高而增加。     

Co-pyrolysis of bituminous coal and biomass in a pressured fluidized bed

An experimental study on co-pyrolysis of bituminous coal and biomass was performed in a pressured fluidized bed reactor. The blend ratio of biomass in the mixture was varied between 0 and 100 wt%, and the temperature was over a range of 550–650 °C under 1.0 MPa pressure with different atmospheres. On the basis of the individual pyrolysis behavior of bituminous coal and biomass, the influences of the biomass blending ratio, temperature, pressure and atmosphere on the product distribution were investigated. The results indicated that there existed a synergetic effect in the co-pyrolysis of bituminous coal and biomass in this pressured fluidized bed reactor, especially when the condition of bituminous coal and biomass blend ratio of 70:30(w/w), 600 °C, and 0.3 MPa was applied. The addition of biomass influenced the tar and char yields and gas and tar composition during co-pyrolysis. The tar yields were higher than the calculated values from individual pyrolysis of each fuel, and consequently the char yields were lower.The experimental results showed that the composition of the gaseous products was not in accordance with those of their individual fuel. The improvement of composition in tar also indicated synergistic effect in the co-pyrolysis.     

Characteristics of fast pyrolysis of biomass in a free fall reactor

Fast pyrolysis of four kinds of biomass (legume straw, tobacco stalk, pine sawdust and apricot stone) was conducted in a free fall reactor. Interest is focused on hydrogen-rich gas production. The experimental results verify the occurrence of the in-situ steam reforming of tar, the steam gasification of char and the water–gas shift reaction with the primary pyrolysis of the biomass at higher heating rate in the free fall reactor. These reactions influence greatly the products' distribution and dry gas compositions in fast pyrolysis, especially at higher temperature. The pyrolysis is mass and heat transfer controlled for biomass particle size of above 0.20 mm but kinetically controlled in the case of particle size smaller than 0.20 mm. Biomass composed of higher cellulose and hemicellulose favors hydrogen-rich gas production in fast pyrolysis than that composed of higher lignin. The pyrolysis characteristics of each type of biomass can be explained according to its chemical compositions.     

Copyrolysis of block polypropylene with waste wood chip

In this study, the copyrolysis of waste wood chip (WC) and block polypropylene (PP) was studied to investigate how the characteristics of bio-oils are affected by copyrolysis. The thermogravimetric analysis performed with a temperature rise of 20 °C/min, from room temperature to 600 °C, showed that the decomposition temperature of PP was a little higher via copyrolysis than the single-component pyrolysis. This result suggests that the characteristics of the pyrolysis of PP were affected by the pyrolysis products of WC. The Py-GC/MS analysis of the copyrolysis products detected some new compounds that had not been detected in the single-component pyrolysis products, indicating interactions between the products of WC and PP pyrolyses. The results of the experiments using a fixed bed reactor showed improved properties of the bio-oil obtained from the copyrolysis compared to those of the bio-oil obtained from the single-component pyrolysis: increased carbon and hydrogen contents, decreased water content and a significantly increased heating value.     

固定床烟煤与木屑共热解的协同反应性研究

在自制的固定床反应装置上对木屑和烟煤以及两者的混合物进行了热解特性研究,考察了木屑与烟煤在不同掺混比例和热解终温下的共热解反应特性。研究结果表明:协同作用发生的程度与热解反应条件有关,烟煤与木屑共热解的协同反应性不仅体现在气、液产物收率方面,同时对气体组成也有显著影响;因木屑灰分中的碱金属化合物对热解焦油的催化裂解作用,使得共热解反应在较高热解终温和较低木屑掺混比条件下表现出更为显著的协同作用;在木屑掺混比(木屑质量分数)为25%、终温540℃条件下,热解气产率的协同值达到22.6%,焦油产率协同值为-27.3%;H自由基与烟煤热解产生的自由基结合成CH4等烃类气体或转移到焦油组分,是一种重要的协同作用机理。     

炼焦煤尾煤热重动力学分析及热解产氢

基于热重分析和固定床热解实验,研究了升温速率和温度对高矿物质含量的炼焦煤尾煤热解特性的影响. 尾煤热解过程可分为室温至400, 400~600及600~950℃三个阶段. 尾煤与焦煤热解曲线基本吻合,尾煤热解特征温度略向高温区推移. 采用Coats-Redfern积分法拟合计算了尾煤热解的动力学参数,得出反应活化能为22.6~66.2 kJ/mol,热解过程可用3个二级反应描述. 30 g尾煤固定床实验结果表明,氢气在低于400℃析出很少,400~600℃缓慢析出,之后随温度升高析出增加,600℃后大量析出,900℃左右达到最大析出量. 终温950℃时,30 g尾煤热解产气4300 mL,氢气产量1722 mL;焦煤产气7950 mL,氢气产量2716 mL. 尾煤热解富氢气体产量达焦煤热解气产量的54%,具有较高的再利用价值.     

Co-pyrolysis of biomass and coal in a free fall reactor

An experimental study on co-pyrolysis of biomass and coal was performed in a free fall reactor under atmospheric pressure with nitrogen as balance gas. The coal sample selected was Dayan lignite, while the biomass used was legume straw. The operation temperature was over a range of 500-700 °C, and the blending ratio of biomass in mixtures was varied between 0 and 100 wt.%. The results indicated that there exist synergetic effects in the co-pyrolysis of biomass and coal. Under the higher blending ratio conditions, the char yields are lower than the theoretical values calculated on pyrolysis of each individual fuel, and consequently the liquid yields are higher. Moreover, the experimental results showed that the compositions of the gaseous products from blended samples are not all in accordance with those of their parent fuels. The CO₂ reactivities of the chars obtained from the co-pyrolysis under the higher blending ratio (around 70 wt.%) conditions are about twice as high as those of coal char alone, even higher than those of biomass alone.