热重-红外联用分析塑料垃圾热动力学特性对多环芳烃生成的影响

本文采用热重-红外联用观察了由PE,PVC,PS等组成的混合塑料和单独的塑料组分的热动力学特性和热重逸出产物的分布特性。结果显示,在混合燃烧和热解时多环芳烃的排放特性和其各组份单独燃烧时的排放特性明显不同,这主要是由于混合燃烧和热解时各塑料组分因相互作用而引起热动力学性质发生了变化所致。     

多聚磷酸铵对再造烟叶热解行为与CO释放量的影响

应用热重分析研究多聚磷酸铵(APP)对再造烟叶热解行为的影响．热分析结果表明,APP降低再造烟叶热降解速率及其热释放量、促进了碳的形成,对再造烟叶的热降解起一定的阻碍作用．此外APP显著影响再造烟叶的热解过程中的气相产物,再造烟叶的CO单支释放量与单口释放量随着APP含量的增加快速下降．慢速热解与闪解实验结果显示升温速率是APP降低CO释放的关键因素．     

太湖藻及模型化合物的分级热解 (cited: 1)

以太湖藻为原料,通过分级热解来制备生物油,分别以棕榈酸、琼脂糖和蛋清粉模拟藻中的脂质、糖类和蛋白质,研究了藻分级热解生物油中主要组分的来源及热解过程中三大组分之间的相互作 用．结果表明,藻生物油中的烃类、十六酸及酯类均源自藻中脂质的热解,藻中蛋白质热解主要生成酚类、吲哚类、吡咯类和小分子酸;生物油中大部分的酰胺和腈类是脂质和蛋白质热解中间物相互作用的产物．藻组分中脂质和糖类的热解主要发生在473～573 K,而蛋白质的热解主要发生在523 K以上．藻生物油中仅有少量的糖类直接热解产物,可能是糖类热解产物在蛋白质热解产生的氨气等的作用下发生了聚合,使473和523 K所得生物油中有相当量的寡聚物;脂质与蛋白质的热解中间物相互作用生成了酰胺,酰胺再脱水又生成了腈类;而脂质与糖类之间相互作用不明显．     

TG-FTIR法研究低变质煤共热解过程气体的析出规律

采用热重-红外联用技术（TG-FTIR）对比研究了陕北低变质粉煤（SJC）与重油（HS）、焦煤（JM）、液化残渣（DCLR）共热解过程中气相产物的析出特性。研究表明,随热解温度升高,SJC与HS,JM,DCLR的共热解过程均可分为三个阶段。第一阶段表现为原料表面吸附物的释放,第二阶段发生解聚和分解反应,随温度继续升高,第三阶段形成更为稳定的半焦。在热解第二阶段中均存在煤与添加剂之间的协同效应,SJC作为主要的供氢体,热解产生的氢自由基与HS,JM,DCLR热解产生的小分子自由基碎片之间发生相互作用生成焦油和煤气。SJC和SJC+DCLR在450 ℃附近的温度区间内热解反应进行的更加充分,大部分N元素转移到了焦油组分中。热解过程气相产物中H₂O和酚类物质、含N杂环物质及CO的析出伴随着热解的整个温度区间,SJC+JM和SJC+HS热解过程含N物质的转移主要集中在400~650 ℃区间,CH₄和脂肪烃类物质的析出最高峰出现在450 ℃附近,而SJC+DCLR和SJC则出现在550 ℃。JM,HS及DCLR的添加可促使焦油中芳香族化合物的析出,SJC+JM与SJC+HS热解过程芳香族物质大量析出的温度区间在400~550 ℃。该研究结果为低变质粉煤的清洁转化与提质分级新技术的研究开发提供理论依据,对低变质煤的增值利用具有重要的意义。     

基于TG-FTIR分析的柳桉热解特性研究

以柳桉生物质为原料,利用红外光谱(FTIR)对其结构进行表征,获得主要官能团的分布信息。随后利用热重红外联用技术(TG-FTIR)研究柳桉的热解行为。柳桉主热解阶段存在由纤维素热解造成的主失重峰以及半纤维素和木质素热解引起的两个肩状峰。同时引入双高斯分布活化能模型(DG-DAEM)对柳桉的热解动力学参数进行计算,结果表明其表观活化能主要分布在第一高斯区间。此外通过在线FTIR分析进一步探讨了典型小分子气体产物的生成和演变机理。     

基于TG-FTIR的杨木热解过程中脲醛树脂影响机理的模型物研究

热解是废弃人造板高效回收利用的方式,人造板中所含胶黏剂是其不同于生物质的主要特征。为了有效环保地利用热解技术处理废弃人造板,解明人造板热解过程中其所含脲醛树脂胶黏剂(UF)对木材热解特性的影响,深入探索UF对人造板中木材各组分的作用机制,以杨木及木材的三种主要组分(纤维素、半纤维素、木素)为研究对象,创新性地依据杨木的化学组成,以纤维素、木聚糖和木素配制成模型物,并加入UF模拟人造板的构成。利用热重红外光谱联用(TG-FTIR)分析法,对比分析了加入UF前后模型物以及杨木各主要组分的热失重特性及气相演变规律。热重及红外结果表明,UF促进了纤维素热解过程中水和羧酸类物质的生成。UF与木素结合生成热不稳定的含氮结构,释放大量氨气,并且在200～300 ℃区间内参与了木素的热解并直接影响木素热解产物的生成。由此推测,在人造板热解过程中,木材三种主要组分中与UF作用的主要成分是木素。     

中温沥青超声萃取物的热解特性与分子结构间关联性的FTIR解析

沥青分子结构和沥青热转化行为的调控是制备高品质沥青基炭材料的关键。为进一步明晰沥青热解行为与沥青分子结构间的关联性,选用8种有机溶剂对中温沥青（AGMP）在常温下进行超声萃取处理得到8 种萃取物。利用 PeakFit v4.12 软件对各种萃取物的红外光谱吸收峰700~900,1 000~1 800,2 800~3 000和3 000~3 100 cm-1四个区域进行了分峰拟合处理,从而获得了萃取物所含各种官能团的精细结构信息,并引入6种分子结构参数（I₁~I₆）,表征萃取物分子结构与热解活化能的关系。傅里叶变换红外光谱(FTIR)谱图分析表明8种萃取物主要是以含氧、含氮等杂原子的脂肪烃侧链为主的缩合芳香环结构组成的复杂化合物。由于萃取剂结构差异,萃取物中的分子结构参数也略有差异。线性结构萃取剂所得萃取物链烃（I₅）含量较高,环结构萃取剂所得萃取物芳环（I₆）取代结构较多。利用热重分析法（TGA）在不同升温速率（3,6,10,15 K·min-1）下对8种萃取物的热失重行为进行了研究,在等转化率不考虑反应机理的情况下,依据Flynn-Wall-Ozawa法和Kissingr-Akahira-Sunose 法解析得出8 种萃取物的热解活化能（E_a）。结果表明8种萃取物热解活化能在78～116 kJ·mol-1之间,其值大小与官能团结构及含量密切相关。将红外光谱定量分析获得的萃取物红外结构参数与热解活化能进行关联,通过详细分析探讨不同萃取物结构参数与热解活化能的一元线性回归E_a=f(I_i)的分析结果发现,芳香性指数（I₃）和支链化程度（I₅）是决定萃取物热解活化能大小的主要指标,热解活化能与各单一指标（I_i）拟合结果的正负相关性,表示这一结构从体系中被热解破坏的难易程度。综合考虑各红外结构参数的共同作用,AGMP萃取物热解活化能与红外光谱结构指标之间的拟合关系模型为E_a=-4 294.53I₁+73 812.16I₂+207 673.32I₃-20 324.20I₄-168.56I₅+857.86I₆。结合红外分析得到的这一结果,揭示了更多关于煤沥青的热解特性和动力学的细节信息,有助于理解煤沥青的热解过程和热转化行为。     

煤模型化合物混合热解时HCN和H2的析出特性

以吡啶、吡咯为煤的含氮模型化合物,利用红外烟气分析仪和气相色谱研究二者在873～1473 K下混合热解时产物的析出规律.结果表明:吡啶和吡咯的热解是两种不同的热解开环方式,吡啶的热稳定性强于吡咯,其氢气产率高于吡咯,但其氰化氢产率较低;混和热解时的氰化氢产率明显小于单独热解,氰化氢产率在1073 K时随混合物中吡啶含量增大而减小,在1373 K时随吡啶含量增大而增大;氢气随温度和混合物中吡啶含量的变化趋势与氰化氢相似,并且热解产物中还检测到少量的甲烷.     

稻壳热解的动力学模拟

生物质热解过程的动力学行为研究对于热化学转化过程机理的掌握和热化学转化技术的开发具有重要意义.本文采用Miller模型对稻壳在低升温速率下的热解进行了动力学模拟,并利用热重分析实验结果对模拟过程的有效性进行了对比验证.模拟计算结果显示气体百分含量在650～780K范围内随温度升高迅速增加,炭含量在500～680K之间随温度升高迅速下降,焦油含量随着温度升高在650K左右达到最高值.同时升温速率的提高可以抑制炭的生成,增加气体和焦油最大产量,在100K/min的升温速率下,气体产量在780K达到最大56.3%,焦油产量在678K左右达到最大26.8%.     

三聚氰胺-甲醛气凝胶模板的结构与热稳定性

采用溶胶-凝胶法合成出三聚氰胺-甲醛（MF）有机气凝胶,并通过N2吸附、红外光谱以及热重-质谱联用等实验技术对该气凝胶的多孔形态、结构特性和热稳定性进行了表征。结果表明:MF气凝胶是一种连续的、相互贯通的3维多孔网络结构材料,比表面积约842 m2/g,平均孔径为16 nm左右;热解产生了NO, H2O, NH3, NO2, CO2和CH4气体,很好地诠释了各阶段失重,其总失重高达97%,有望作为制备3维nm级多孔材料的模板。     

城市垃圾与煤在CFBC试验台上的混烧试验

城市垃圾的焚烧处理一直是人们关注的研究领域。本文详细报告了一种城市垃圾与劣质煤在0.15兆瓦CFBC试验台上的混烧试验。试验结果表明,城市垃圾与劣质煤在循环流化床中的混烧可以很好地满足稳定和高温燃烧的要求,通过添加石灰石等含钙物料可以有效地在燃烧过程巾控制SO2、HCl和二(?)英类污染物的生成。     

Experimental and modeling study on centimeter pine char combustion in fast-heating Macro TGA

Biomass energy is an important renewable resource, and thermochemical conversion, including pyrolysis and combustion, is one of the main methods of biomass energy utilization. In industrial reactors, the biomass particles will experience a fast heating (∼1000 °C/min) process during pyrolysis. The particle size of biomass applied in industry has a wide range (from millimeter to centimeter scale). The study of the reaction characteristics of biomass pyrolysis and combustion is helpful for optimizing furnace design and working condition selection. In this research, the combustion of centimeter-scale pine char was studied with a newly built fast-heating Macro Thermal Gravimetric Analyzer (Macro TGA). This Macro TGA is able to conduct the pyrolysis and combustion of large biomass samples (up to 40 mm) with a fast heating rate (∼1000 °C/min), which is able to reflect the working conditions in industrial-scale reactors such as grate furnaces and dual fluidized beds. This Macro TGA can measure the online sample weight, temperature and sample size simultaneously during pyrolysis and combustion experiments. The combustion characteristics of different sizes of pine chars were investigated at various temperatures and oxygen concentrations. A zero-dimensional model was established to predict the sample weight loss, temperature change and sample shrinkage during the pine char combustion process. Three kinetic parameters α, A and E were applied in the model, and the values of the kinetic parameters were optimized by a genetic algorithm. The model prediction and experimental results are consistent with each other. Compared with previous studies, this study developed a new experimental method to measure the reaction characteristics (including sample weight, temperature and size) of centimeter-scale biomass under similar pyrolysis and combustion reaction conditions compared to industrial reactors, and a zero-dimensional model was established to describe the pine char combustion process.     

On the rank-dependence of coal tar secondary reactions

The secondary reactions of volatile compounds, including coal tar and light gases, accounts for a great portion of soot formation and the subsequent heat release and pollutant emissions in the combustion zone. While coal primary pyrolysis has been extensively studied over the last few decades and several network pyrolysis models has been developed to describe this process, coal secondary pyrolysis is still not well understood. The Babcock and Wilcox Company has been investigating coal secondary pyrolysis in order to develop a comprehensive mechanism for inclusion in predictive computational fluid dynamics and coal combustion models. Supportive experiments were carried out in an entrained-flow reactor. Tar was extracted from the pyrolysis byproducts of seven coals of widely-distributed rank at temperatures ranging from 923 to 1473 K, and analyzed by ¹³C NMR. Tars formed from higher rank coals generally demonstrated higher sooting propensities. This rank-dependent sooting propensity is associated with tar’s chemical structure properties. With increased heat treatment severity, tar molecules lose a substantial amount of aliphatic attachments, and the average size of substitution per cluster decreases. Compared to tars formed from high-rank bituminous coals, those formed from low-rank sub-bituminous coals have a larger attachment portion, higher averaged substitution, and higher oxygen-containing functional groups. These differences contribute to the higher cracking propensity observed for low-rank coal tars.     

Determination of pyrolysis temperature for charring materials

An energy and mass balanced method of determining the pyrolysis temperature is proposed. The concept is to find the pyrolysis temperature that consumes the same amount of energy to produce the same amount of mass when using the pyrolysis front model as when using finite rate kinetics models for the entire charring process. The resulting pyrolysis temperature has the form of pyrolysis rate weighted average temperature. Comparisons between finite rate kinetics and pyrolysis front models for various boundary conditions, geometries, heats of decomposition, kinetic parameters and assumptions used in the literature were made to assess the proposed method. Models using energy and mass balanced pyrolysis temperature show good agreement with finite rate models and the experiments. Extensive numerical studies on various factors influencing the charring material pyrolysis show that heat flux, sample size, heat of decomposition and kinetic parameters are the most important factors for determining an appropriate pyrolysis temperature. Thermal conductivity, specific heat and density have a lesser effect on the pyrolysis temperature. For practical application, a non-dimensional correlation is developed to determine the appropriate pyrolysis temperature without solving the problem by using finite rate models. With this correlation the energy and mass balanced pyrolysis temperature can be determined with a standard deviation of 7.6 K. These predictions are validated by comparison with measurements of wood cylinder pyrolysis. A good agreement suggests that simpler pyrolysis front models yield practically useful and accurate results given an appropriate pyrolysis temperature.     

采用铁基催化剂在V型热解火焰中合成碳纳米管的实验研究

催化剂的选取对于V型热解火焰合成碳纳米管具有重要的影响.实验中分别采用五羰基铁、二茂铁、纳米铁粉等作为催化剂,取样时间为10 min,温度约为1150 K,催化剂的引入方式为喷雾热解方法,利用扫描电镜和透射电镜对合成的碳纳米管进行形态和结构表征分析.实验结果表明:利用V型热解火焰合成碳纳米管时的关键物质是纳米氧化铁颗粒...     

聚乙烯与水反应的高温高压实验及热力学探讨

 在金刚石压腔设备中进行聚乙烯的高温高压裂解实验研究。实验分含水和不含水两种情况。在显微镜下观察反应过程中的变化并显微照相记录有关现象,在高压下就位测定反应过程中荧光的变化。用气相色谱方法测定气相产物组成。含水实验中CH₄占烃类气体产物的92%并有CO₂生成,固体残余物非常少,表明水直接参与了化学反应,为烃类气体的形成提供氢源,为CO₂的形成提供氧源。不含水实验中烃类气体的产率相对较低并有较多的固相残余物存在。用热力学理论探讨了实验中有关反应的机制。根据聚乙烯与干酪根结构的可比性,推测在水参与条件下有利于提高有机质裂解成烃的产率。     

“Three-dimensional analysis of the pyrolysis behavior of solid fuel by ultra high-speed X-ray CT”

In this research, microscopic visualization of pyrolysis in woody biomass was conducted by using the BL20B2 beamline at “SPring-8,” a large synchrotron radiation facility. Changes in shape and internal structure of the woody biomass were visualized by ultra high-speed CT. The samples were made of Japanese cypress wood; they had a height and a diameter of 5 mm. We used radiation as the heat source to achieve a high heat flux. When the heat flux was high, the samples expanded. Gaps were observed inside the samples. By comparing our results with the experimental results obtained under a low heat flux in a previous study, we could observe an entirely different aspect. Considering that the increase in pressure due to the rapid generation of pyrolysis gas created gaps in the samples, the samples were drilled, and experiments were performed on them. The hole in the center of the wood alone did not create an escape route for the pyrolysis gas, and the pyrolysis behavior was the same as that observed in the unprocessed wood.     

非碳化热厚固体逆流水平火蔓延热解特性

根据反应边界层理论,解析热解表面传热传质过程,依据热厚固体内部温度分布,给出其热解表面传质数B-number函数以及热解模型。并以4 mm厚PMMA平板为对象,进行不同送氧量和不同车速燃烧实验,通过记录火焰长度、火焰距离热解表面的高度、蔓延速度、质量损失率以及底板温度等数据,推演热解表面热通量,表面传质数等热解动力学参数的变化规律,研究结果为解释热厚固体表面燃烧的发生、发展以及状态转条件奠定理论基础。     

微生物接种堆肥胡敏酸三维荧光特性研究

为提高堆肥效率,试验采用接种微生物堆肥技术,通过对堆肥样品中胡敏酸三维荧光光谱特性进行动态分析,探讨了微生物接种对堆肥腐殖化进程的影响。在堆肥初期,胡敏酸只产生一个类富里酸荧光峰(peak a,Ex/Em为330/440)。在堆肥的336 h,与对照(RUN_ck)相比,接种微生物堆肥(RUN_mic)胡敏酸三维荧光光谱中类富里酸特征峰(peak a,Ex/Em约为350/440)荧光强度明显减少,而类胡敏酸荧光峰(peak b,Ex/Em约为390/470)强度则略有增加;并且peak a和peak b对应的激发、发射波长均有一定程度的红移。胡敏酸元素分析表明,堆肥336 h,RUN_ck胡敏酸分子中C/H和O/C依次增加9.68%和10.91%;RUN_mic中胡敏酸C/H和O/C依次增加了11.11%和20.37%,表明RUN_mic中胡敏酸分子缩合度明显。以上结果证实,接种微生物可明加快堆肥腐殖化进程,进而提高堆肥效率。     

玉米芯流化床快速热解制取生物油试验研究

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