热裂解-气相色谱质谱联用法快速检测聚丙烯材料中5种抗氧剂

采用热裂解气质联用仪,建立了一种无需任何样品前处理、全程无溶剂的、同时对5种常用塑料抗氧剂的定量分析方法.结果表明:通过该方法分析的5种常用抗氧剂,在0.2～1μg之间有很好的线性关系,且该方法操作简单、 快速准确,填补了热裂解气质联用技术在塑料助剂定量分析的空白.     

塔里木盆地煤岩在不同介质条件下热模拟实验中烷烃系列有机地球化学特征

对塔里木盆地侏罗系煤岩在不同介质下的热模拟实验和正构烷烃系列色质测试分析结果表明,在400℃前后煤岩成烃机理不同。结合对峰型、ΣC21-/ΣC22+值、OEP指数和P r/Ph值等地球化学参数的研究,指出了不同热演化阶段的成烃机理:在低温阶段(<350℃)煤岩主要是裂隙、晶格间吸附烃和结构边缘烃的排出;在350~400℃之间,脱甲基及链断裂效应使得煤岩排烃进入高峰期;在高演化阶段(≥450℃),大量内部结构烃发生断裂重排,550℃以上温度达到第二个热降解高峰,产出烃发生脱甲基、链断裂和开环效应。模拟实验还表明,OEP指数变化较大,其每次变化都伴随一次生烃高峰;P r/Ph值随着热演化程度呈降低趋势;有水、伊利石和蒙脱石存在时,会改变煤岩在热演化过程中高碳数烃的热降解速率,有利于液态烃的形成。     

ATP技术用于褐煤热解提质的技术经济分析

介绍了ATP(A lberta-Taciuk Processor)技术的发展历程及应用领域,提出利用ATP技术加工处理内蒙古褐煤的设想,并进行了技术经济分析,得出利用ATP技术处理褐煤的可行性结论。     

原油裂解气在天然气勘探中的意义

从油气生成理论和古油藏演化过程的讨论中引申出原油裂解气的问题。一般所说的原油裂解气主要是指古油藏演化中的原油裂解气 ,油藏中的原油由于后期深埋 ,必然发生裂解而形成天然气和沥青。这种原油裂解气只有在特定的地质条件下才能形成 ,如塔里木盆地巴楚隆起的和田河气田的天然气 ,主要是由于构造运动使早期形成的油藏埋藏很深导致原油裂解的产物。塔北隆起东部桑塔木断垒带的天然气与和田河气田的天然气同是源自寒武系烃源岩 ,但桑塔木天然气主要为干酪根裂解气 ,而和田河天然气主要为原油裂解气 ,因此二者在天然气组成和天然气组分碳同位素特征上存在差异 ,如虽然二者成熟度一致 ,但和田河气田天然气的非烃气体含量高于桑塔木天然气 ,其甲烷碳同位素值则比桑塔木天然气的轻。对于古油藏而言 ,原油裂解既对油藏起破坏作用 ,同时又可形成天然气藏的特殊气源。图 6参 1 2     

Evaluation of production yield and thermal processing of switchgrass as a bio-energy crop for the Mediterranean region

Switchgrass, a warm-season perennial grass, could play an important role for Europe in supplying sustainably produced lignocellulosic biomass, as its establishment cost is low and its productivity high under low input conditions. The aim of this study was to evaluate the adaptability and biomass productivity of switchgrass under the Greek climatic conditions and furthermore its suitability for heat and electricity applications, by performing fuel analyses, pyrolysis and combustion tests. Three-year field trials with different irrigation and fertilization levels showed that each level of irrigation had a significant effect on dry matter yields, while nitrogen effect was not pronounced. Yields were similar in the second and third year and ranged from 15.4% to 24 tons/ha.Fuel characterization showed a high volatile content and calorific value, whereas low ash, sulphur, nitrogen and chlorine contents. Ashes were rich in Si, K and P and some micronutrients, such as Zn. The ash fusion temperatures of the stems, which were richer in alkali, were low for combustion processes, revealing slagging/fouling problems in boilers without crop pre-treatment. However, their ash content was very low. The thermochemical reactivity of the stems was higher than that of the leaves, especially in air. The greater amount of minerals in the leaves inhibited the reaction rates in either nitrogen or air atmospheres. A first-order parallel reactions model for pyrolysis and a power low model for combustion fitted the experimental results accurately and kinetic parameters were derived. Irrigation/fertilization treatment had a positive effect on the combustion performance of the stems.     

Emission of polycyclic aromatic hydrocarbons from the pyrolysis of liquid crystal wastes

A liquid crystal display can be described as a panel consisting of two plates of glass with liquid crystals in the space between. Generally, the liquid crystal wastes are extracted and separated into various fractions. Some recyclable materials, i.e., metals, glass, plastics, etc., are recycled, but the liquid crystals are incinerated. The emission factors for 16 U.S. EPA priority polycyclic aromatic hydrocarbons (PAHs) from the combustion of liquid crystal are approximately 390 and 1520 times higher than that of waste terephthalic acid and biological sludge combustion, respectively. In this study, we determined the emission of PAHs from the liquid crystals pyrolysis. We also investigated the fragments and gas compositions using on-line thermogravimetry–mass spectrometry (TG–MS). A temperature series of 14 fragments was analyzed in nitrogen, and was found to include m/z: 30, 32, 42, 44, 55, 57, 67, 81, 95, 109, 128, 166, 178, and 202. The fragments at m/z 32 represents formaldehyde and the fragment at m/z 44 is carbon dioxide. The fragments at m/z 55, 57, 67, 81, 95, and 109 represent hydrocarbon components, all of which may be liquid crystal by products. The TG–MS as analyzed above can offer a better understanding of the mechanisms of byproduct formation in liquid crystal waste pyrolysis.Experimentally, not detected (n.d.) −5.98 and n.d. −20.2 μg/g of 16 PAHs, in the particulate and gas phases, respectively, are determined from the emission of liquid crystal waste pyrolysis. The PAH profiles showed a predominance of naphthalene (42.6%) and phenanthrene (13.5%). The total PAH emissions for the 16 species were 7.75 and 44.05 μg/g in the particulate and gas phases, respectively, significantly lower than the values associated with liquid crystal combustion. From the viewpoint of PAH emission control, our results suggest that the pyrolysis is a better option for the disposal of liquid crystal wastes than that of combustion.     

Monolithic carbon structures including suspended single nanowires and nanomeshes as a sensor platform

With the development of nanomaterial-based nanodevices, it became inevitable to develop cost-effective and simple nanofabrication technologies enabling the formation of nanomaterial assembly in a controllable manner. Herein, we present suspended monolithic carbon single nanowires and nanomeshes bridging two bulk carbon posts, fabricated in a designed manner using two successive UV exposure steps and a single pyrolysis step. The pyrolysis step is accompanied with a significant volume reduction, resulting in the shrinkage of micro-sized photoresist structures into nanoscale carbon structures. Even with the significant elongation of the suspended carbon nanowire induced by the volume reduction of the bulk carbon posts, the resultant tensional stress along the nanowire is not significant but grows along the wire thickness; this tensional stress gradient and the bent supports of the bridge-like carbon nanowire enhance structural robustness and alleviate the stiction problem that suspended nanostructures frequently experience. The feasibility of the suspended carbon nanostructures as a sensor platform was demonstrated by testing its electrochemical behavior, conductivity-temperature relationship, and hydrogen gas sensing capability.     

Pyrolysis kinetics and multi-objective inverse modelling of cellulose at the microscale

The chemistry of pyrolysis, together with heat transfer, drives ignition and flame spread of biomass materials under many fire conditions, but it is poorly understood. Cellulose is the main component of biomass and is often taken as a surrogate for biomass. Its chemistry of pyrolysis is simpler and dominates the pyrolysis of biomass. Many reaction schemes with corresponding kinetic parameters can be found in the literature for the pyrolysis of cellulose, but their appropriateness for fire is unknown. This study investigated inverse modelling and blind predictions of six reaction schemes of different complexities for isothermal and non-isothermal thermogravimetric experiments. We used multi-objective optimisation to simultaneously and separately inverse model the kinetic parameters of each reaction scheme to several experiments. Afterwards we tested these parameters with blind predictions. For the first time, we reveal a set of equally viable solutions for the modelling of pyrolysis chemistry of different experiments. This set of solutions is called a Pareto front, and represents a trade-off between predictions of different experiments. It stems from the uncertainty in the experiments and in the modelling. Parameters derived from non-isothermal experiments compared well with the literature, and performed well in blind predictions of both isothermal and non-isothermal experiments. Complexity beyond the Broido-Shafizadeh scheme with seven parameters proved to be unnecessary to predict the mass loss of cellulose; hence, simple reaction schemes are most appropriate for macroscale fire models. Modellers should, therefore, use simple reaction schemes to model pyrolysis in macroscale fire models.     

Thermal cracking and combustion kinetics of asphaltenes derived from Fosterton oil

Thermal behavior of crude oil (Fosterton) asphaltenes mixed with reservoir sand was investigated using thermogravimetric analysis (TGA), in nitrogen and air atmospheres for different heating rates up to 800 °C. In this study, four sets of TGA runs were performed to examine the thermal behavior of Fosterton asphaltenes and the coke derived from the asphaltenes. The parameters studied were heating rate (10, 15 and 20 °C min^− 1) and the type of purge gas (N₂ and air) employed for the process of thermal degradation of asphaltenes. Distributed activation energy model (DAEM) has been applied to study the asphaltene pyrolysis kinetics. It was observed that the activation energy was distributed from 46.16 to 72.17 kJ/mol, for the conversion range of 0.1 to 0.4. The general model for nth order reaction was used to obtain the kinetic parameters of coke oxidation reaction from the TGA data. From the model, the calculated activation energy, E, was 93.46 kJ/mol and the pre-exponential factor was 9.59 × 10⁵ min^− 1 for the coke combustion. The apparent order of combustion reaction gradually increased from 0.7 to 0.8 for different temperatures.     

EFFECT OF DRYING METHOD ON MESOPOROSITY OF RESORCINOL-FORMALDEHYDE DRYGEL AND CARBON GEL

Resorcinol-formaldehyde hydrogels were synthesized by sol-gel polycondensation of resorcinol with formaldehyde in a slightly basic aqueous solution. RF cryogels, RF xerogels, and RF xerogels (MW gels) were respectively prepared from RF hydrogels by freeze drying, hot air drying, and microwave drying. Carbon cryogels, carbon xerogels and carbon MW gels were subsequently obtained by pyrolyzing RF drygels in an inert atmosphere. Freeze drying and microwave drying were effective to prepare mesoporous RF drygels and carbon gels. RF cryogels and carbon cryogels showed high mesoporosity over wide ranges of the molar ratio of resorcinol to catalyst (R/C) and the ratio of resorcinol to water (R/W) used in sol-gel polycondensation. Although RF xerogels had a few mesopores, carbon xerogels had no mesopores. RF MW gels and carbon MW gels showed mesoporosity if appropriate values of R/C and R/W were selected.