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。     

呼伦贝尔煤与3种富氢有机物共热解相互作用研究

通过考察呼伦贝尔煤与3种富氢有机物(纤维素、聚乙烯吡咯烷酮(PVP)、高密度聚乙烯(HDPE))共热解过程热失重、自由基浓度、固定床热解产物产率变化,并与单独热解对比,解析共热解过程中不同原料热解产生的自由基碎片在逸出床层过程中的相互作用。试验发现,煤/纤维素、煤/PVP、煤/HDPE共热解在150~600℃的失重量分别为61.18%、60.26%和64.31%,均低于计算值62.55%、63.53%和66.76%;温度高于400℃时,共热解过程自由基浓度试验值均低于计算值(单独热解结果平均值);固定床热解试验中,固体产率分别为37.9%、39.0%和34.0%,与计算值(37.5%、36.5%和33.6%)相当或略高,液体(包含水和焦油)产率试验值分别为33.3%、44.9%和53.2%,均低于计算值(39.8%、51.3%和57.1%),气体产率试验值分别为28.8%、16.1%和12.9%,均高于计算值(22.7%、12.2%和9.3%)。因此共热解过程中,不同原料热解产生的自由基碎片在逸出床层过程中会相互作用,挥发性自由基和稳定自由基之间的结合最明显,挥发性自由基逸出阻力增加,二次反应增大。     

生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理

生物质与废塑料共催化快速热解是制取轻质芳烃的重要途径。 采用不同种类的分子筛催化剂,首先研究了分子筛种类对杨木、生物质三组分和低密度聚乙烯（LDPE）单独催化快速热解轻质芳烃产率的影响,其次研究了生物质三组分与LDPE在共催化热解过程中的协同作用机理。结果表明：在杨木、生物质三组分和LDPE单独催化快速热解时,HZSM-5（25）催化剂体现出最高的轻质芳烃产率;在杨木和LDPE共催化快速热解时,随着LDPE质量的增加,轻质芳烃的产率呈先升高后降低趋势;在生物质三组分和LDPE共催化快速热解时,纤维素和半纤维素热解的呋喃类中间产物与LDPE热解的轻烯烃中间产物易发生“双烯合成”反应,表现出较强的协同催化作用,促进轻质芳烃的生成,而木质素则抑制轻质芳烃生成。     

生物质与塑料催化共热解制芳烃研究进展

芳烃是多用途的化学品,主要来源于石油和煤焦油等。以生物质和塑料为原料制取芳烃,可以缓解能源短缺和环境污染,实现生物质和塑料的资源化利用。催化剂能够增强共热解的协同效应,生物质与塑料进行催化共热解可以提高产物品质,改善热解产物分布,提高轻质芳烃的产率和选择性,抑制焦炭的生成。本文综述了生物质与塑料催化共热解制取芳烃的协同热解机理及影响因素,总结了不同种类催化剂的共热解研究进展,以期为生物质与塑料催化共热解定向调控制备芳烃工艺的改进和优化提供参考。     

农业生物质与塑料共热解技术进展

共热解技术是将多种原料通过热化学方法转化为清洁能源的重要手段。本文综述了以农业生物质为主要原料与塑料(聚丙烯PP、高密度聚乙烯HDPE、低密度聚乙烯LDPE、聚氯乙烯PVC、聚苯乙烯PS、聚对苯二甲酸乙二醇酯PET等)共热解技术的发展现状和研究进展。分析农业生物质与塑料共热解的动力学模型以及各组分之间的协同效应,阐述农业生物质与塑料的共热解机理;总结了温度、升温速率、滞留时间、原料混配比等因素对共热解协同作用的影响规律;探究生物质与塑料共热解固、液、气三相产物特性及分布规律,总结共热解技术优势及存在问题,展望未来发展方向,可为生物质与塑料共热解制备高附加值产品提供参考,同时也为农业生物质和农膜处理问题提供新方法、新思路。     

生物质与塑料共热解协同特性研究进展

通过梳理最新的生物质与塑料共热解技术研究进展,对共热解过程中协同效应、热重特性、动力学机理、气液固三相产物特性进行综述,归纳了生物质与塑料共热解的协同特性和优势特点,为生物质废弃物与废塑料共热解技术提供理论依据,为环境治理提供方案参考,有利于创造经济效益和生态效益,加快实现社会可持续发展的目标。     

生物质与塑料催化共热解技术研究进展

生物质是唯一一种可再生碳源，其高效利用是解决能源与环境问题的纽带。近年来，基于化石能源的塑料制品使用和废弃量快速增加，其难于自然降解，对环境造成严重威胁。生物质与塑料的催化共热解技术能够得到选择性更高的产品，进而提升高附加值产物的产率和品质，是生物质与塑料规模化利用的重要方向。本文从生物质与塑料高效转化的角度出发，梳理了生物质与塑料催化共热解技术研究进展，对生物质与塑料共热解机理、ZSM-5基催化剂共热解、过渡金属基催化剂共热解、碱/碱土金属催化剂共热解、多催化剂共热解等不同种类的催化共热解研究前沿进行了综述，并对比了原位催化和非原位催化的共热解方式，展望了生物质与塑料催化共热解的主要技术和发展方向，以期为生物质与塑料的高效协同转化提供方法参考和研究思路。     

四种原料生物油-酚醛树脂胶粘剂特性研究

利用生物质快速热解液化产物制备燃料或化工产品已成为国内外的研究热点。将四种生物质原料(落叶松、杨木、棉秸秆和玉米秸秆)快速热解液化产物作为苯酚替代物,由此制备出不同种类的热解生物油-PF(酚醛树脂)胶粘剂,并探讨了胶粘剂胶接强度与热解生物油组成的关系。结果表明:落叶松热解生物油-PF胶粘剂的胶接强度最大(1.277 MPa),玉米秸秆热解生物油-PF胶粘剂的胶接强度最小(1.021 MPa);胶粘剂的胶接强度主要与热解生物油中酚类物质含量有关。     

热解过程中生物质内部碱金属的析出规律

用水平管式炉和热重分析仪热解稻杆和谷壳,用原子吸收光谱仪检测热解产物中碱金属浓度,分析碱金属的析出规律。结果表明,随着热解温度提高,生物质的热解转化率增加,生物质内部碱金属具有很强的挥发性,热解终止时,碱金属元素析出量为65%⁷5%。     

ReUSY分子筛催化热解聚烯烃塑料性能

构建基于稀土超稳Y型分子筛的催化热解体系，并对多种聚烯烃塑料进行催化热解实验。结果表明，ReUSY分子筛表现出最优催化性能。利用热重-红外联用实时在线产物分析技术，发现加入ReUSY分子筛显著降低了聚烯烃的热解初始和终止温度，同时减少了产物中芳烃与积炭的比例，有效提高了低碳烃产率。通过Coats-Redfern法对催化热解反应动力学进行研究，分析催化热解在不同阶段的活化能，表明催化热解反应的平均活化能为(56.23～69.12) kJ·mol^-1。相较传统热解实验，ReUSY显著降低了催化热解反应的活化能。     

Pyrolysis properties and kinetics of mandarin peel

The thermal property of the pyrolysis reaction of mandarin peel was studied using thermogravimetric analysis (TGA). Thermogravimetric analyses with temperature increases of 10, 20 and 40 °C/min showed large weight losses within the temperature range 150–590 °C. Differential thermogravimetric (DTG) analysis curves illustrated that the pyrolysis of mandarin peel was a multi-step process, consisting of water desorption, the decomposition of pectin, hemicellulose, cellulose and lignin, and devolatilization of the residual char. The apparent activation energies ranged between 119 and 406 kJ/mol, depending on the pyrolytic conversion. The pyrolysis products were analyzed, using pyrolyzergas chromatography/mass spectrometry (Py-GC/MS), to evaluate mandarin peel as a renewable source of valuable industrial chemicals. The pyrolysis products of mandarin peel contained high portions of methanol and acetic acid, as well as valuable compounds, such as limonene and vitamin E.     

十溴二苯醚热解动力学及在聚苯乙烯中的热解行为

十溴二苯醚(decaBDE)是多种聚苯乙烯(PS)类塑料阻燃添加剂,其热解动力学对开发新型高效的电子塑料安全处置技术具有十分重要的意义,为此采用普适积分法成功关联了氮气中decaBDE的热解动力学参数。结果表明:固体decaBDE在306℃时熔融为液相并在400~450℃进一步汽化为气相,热重/红外(TG/IR)分析表明,其气相产物组成具有与decaBDE相同的红外特征;decaBDE热解过程可用三维扩散模型关联。进而通过对比分析decaBDE、PS和含decaBDE的阻燃PS样品的TG实验结果,发现阻燃塑料样品在热解时存在decaBDE与PS间的相互作用,表现为热解起始温度的降低和终止温度的升高。TG/IR分析表明:阻燃塑料样品的热解气相产物中不存在游离的HBr,decaBDE热解时产生的活性基团改变了PS的降解反应历程,使其气相产物具有与1,3-二苯基丁烷类似的红外特征。     

Thermal decomposition characteristics of poly(ether imide) by TG/MS

Thermal degradation of poly(ether imide) (PEI) was studied by the combination of pyrolysis/gas chromatography/mass spectrometry (Py-GC/MS) and thermogravimetric analysis/mass spectrometry (TG/MS) techniques. The composition of evolved gases was determined by Py-GC/MS and the real-time formation curves were obtained through TG/MS. The thermal degradation mechanisms of PEI were resolved through TG/MS methods. The major pyrolysis mechanisms with the two-stage reaction regions were main chain random scission and carbonization. In the first stage pyrolysis, the decomposition of the hydrolyzed-imide, ether and isopropylene groups caused the evolution of CO₂ and phenol as major products accompanied by a chain transfer of carbonization to form partially carbonized solid residue. In the second stage pyrolysis, the decomposition of partially carbonized solid residue and the remaining imide group produced CO₂ as a major product along with benzene and small a amount of benzonitrile. Afterward, the chain transfer of carbonization dominated the decomposition of solid residue in higher temperatures to produce a high char yield. A kinetic model was proposed from the calculation of two flat regions in the activation energy curve. The theoretical pyrolysis curve from the proposed model was calculated and compared with the experimental curve, which were quite well matched.     

Thermogravimetric characteristics and kinetic study of biomass co-pyrolysis with plastics

The pyrolysis of pure biomass, high density polyethylene (HDPE), polypropylene (PP) and polyethylene terephthalate (PET), plastic mixtures [HDPE+PP+PET (1: 1: 1)], and biomass/plastic mixture (9: 1, 3: 1, 1: 1, 1: 3 and 1: 9) were investigated by using a thermogravimetric analyzer under a heating rate at 10 °C/min from room temperature to 800 °C. Paper was selected as the biomass sample. Results obtained from this comprehensive investigation indicated that biomass was decomposed mainly in the temperature range of 290–420 °C, whereas thermal degradation temperature of plastic mixture is 390–550 °C. The percentage weight loss difference (W) between experimental and theoretical ones was calculated, which reached a significantly high value of (−)15 to (−)50% at around 450 °C in various blend materials. These thermogravimetric results indicate the presence of significant interaction and synergistic effect between biomass and plastic mixtures during their co-pyrolysis at the high temperature region. With increase in the amount of plastic mixture in blend material, the char production has diminished at final pyrolysis temperature range. Additionally, a kinetic analysis was performed to fit with TGA data, the entire pyrolysis processes being considered as one or two consecutive first order reactions.     

TGA-FTIR与Py-GC/MS分析医用硅橡胶

用热重分析(TGA)-傅里叶变换红外光谱(FTIR)联用和裂解(Py)-气相色谱(GC)/质谱(MS)联用对两个医用硅橡胶试样的热分解过程进行分析。研究表明:通过FTIR分析,推断两个医用硅橡胶试样的主要成分为甲基取代硅氧烷,其中一个试样的填料可能为硫酸钡和白炭黑,而另一个试样的填料可能仅为白炭黑;两个医用硅橡胶试样的裂解产物均为环状二甲基硅氧烷,主要成分为六甲基环三硅氧烷和八甲基环四硅氧烷;裂解温度越高,越易出现相对分子质量较大的环状二甲基硅氧烷。TGA-FTIR和Py-GC/MS分析可以为医用硅橡胶的鉴定和裂解回收提供依据。     

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.     

Thermal degradation mechanisms of poly[diethyl 2-(methacryloyloxy)ethyl phosphate] by Py-GC/MS

Thermal decomposition properties of poly[diethyl 2-(methacryloyloxy)ethylphosphate] (PDMP) were studied using a stepwise pyrolysis-gas chromatography/mass spectrometry (stepwise Py-GC/MS) method. The individual mass chromatograms of the various pyrolysates were correlated with the pyrolysis temperature in order to elucidate the degradation mechanisms. The scission of PDMP in helium atmosphere showed the presence of two-stage pyrolysis regions. Triethylphosphate reached maximum evolution at the initial pyrolysis temperature, indicating that scisson of PDMP was initiated by the selective cleavage at the chain end and phosphate ester side chain as the dominant pyrolysis mechanism in the first stage. This local instability at chain end and phosphate ester side chain might explain the thermal instability of PDMP at lower pyrolysis temperatures. Acetaldehyde and water, as major products, were formed in significant amounts above 300 °C, indicating that random chain scission became the dominant pyrolysis mechanism in the second stage. Thus, the random chain scission reaction favored the occurrence of crosslinking and cyclization through chain transfer of carbonization catalyzed by phosphate ester along with the evolution of the arylene-containing and cyclic compounds. From mechanism analysis of PDMP pyrolysis, the introduction of a chemically bonded phosphorous-containing pendant group could promote its fire retardancy to form the high char yield of solid residue.     

木粉填充HDPE/PVC复合材料的热稳定性及流变行为

以聚磷酸铵(APP)和Al(OH)3为阻燃剂,通过熔融挤出制备了具有阻燃性能的高密度聚乙烯/聚氯乙烯(HDPE/PVC)基木塑复合材料,研究了PVC对木塑复合材料热稳定性及流变行为的影响。热失重分析结果表明:APP和PVC均可促进木粉成炭,同时提高了HDPE的热稳定性;流变测试结果表明:PVC与木粉的相容性较HDPE要好,并能促进木粉在体系中均匀分散,改善木塑复合材料体系的加工流动性;锥形量热测试结果表明:PVC脱氯、Al(OH)3热分解均吸收大量热量,可降低复合材料的热释放速率与热释放总量。     

PET黏合剂及其弹性体热解与推进剂热解相关性研究

采用差示扫描量热/热重(DSC/TG)和裂解气相色谱质谱联用(Py-GC/MS)分析技术研究了PET黏合剂体系、PET/TDI弹性体以及含PET黏合剂体系的简单组分推进剂的热分解特性和热裂解产物状况,探索了PET弹性体的热分解与含PET黏合剂体系的推进剂热解性能之间的相关性.研究结果表明,混合硝酸酯增塑的PET黏合剂体...     

生物质颗粒孔隙结构在热解过程中的变化

利用氮气等温吸附/脱附法（-196℃）和扫描电镜（SEM）等研究了热解过程中生物质颗粒孔隙结构的演化规律,并用分形维数来描述焦颗粒内部孔隙表面形态的复杂程度。结果表明,热解温度对生物质焦的孔结构和表面形态有显著影响。热解过程中孔网络结构在发生演变,孔的形状发生了一定变化,且孔径有先变小后变大的趋势。高温导致焦颗粒发生塑性变形,使得孔隙扩大和孔表面更加光滑。随着温度的升高,生物质焦的BET比表面积先增大后减小,500℃以前,孔容积的变化规律与比表面积相近。通过分形FHH方程回归得到的分形维数能较好地表征颗粒内部孔隙表面的分形特征。其分形特征与热解温度密切相关,分形维数的变化与BET比表面积有一定关联。