On-probe pyrolysis desorption electrospray ionization (DESI) mass spectrometry for the analysis of non-volatile pyrolysis products

An on-probe pyrolyzer has been constructed and interfaced with desorption electrospray ionization (DESI) mass spectrometry (MS) for the rapid analysis of non-volatile pyrolysis products. The detection and analysis of non-volatile pyrolysis products of peptides, proteins and the synthetic polymer poly(ethylene glycol) were demonstrated with this instrument. The on-probe pyrolyzer can be operated off-line or on-line with the DESI source and was interfaced with a tandem MS (MS/MS) instrument, which allowed for structure characterization of the non-volatile pyrolytic products. Advantages of this system are its simplicity and speed of analysis since the pyrolysis is performed in situ on the DESI source probe and hence, it avoids extraction steps and/or the use of matrices (e.g., as in MALDI–MS analyses).     

Comparison of Pyrolysis and Microwave Acid Digestion Techniques for the Determination of Mercury in Biological and Environmental Materials

 Microwave digestion reduction-aeration and pyrolysis combined with cold vapour atomic absorption and cold vapour atomic fluorescence are compared for the determination of total mercury in several biological and environmental matrices. The biological samples were digested in a mixture of HNO₃/H₂O₂, the environmental samples in a mixture of HNO₃/HClO₄. After reduction with SnCl₂, the mercury was collected by two-stage gold amalgamation. After microwave digestion reduction-aeration, detection limits of 1.4 ng g⁻¹ and 0.6 ng g⁻¹ were obtained for cold vapour atomic absorption spectrometry (CVAAS) and cold vapour atomic fluorescence spectrometry (CVAFS), respectively, for 250 mg of environmental samples. For biological samples (500 mg) the detection limits were 0.7 ng g⁻¹ (CVAAS) and 0.4 ng g⁻¹ (CVAFS). After pyrolysis, detection limits of 3.5 ng g⁻¹ and 1.6 ng g⁻¹ for CVAAS and CVAFS, respectively, were obtained for a 10 mg sample. Pyrolysis can only be applied when the organic content of the sample is not too high. Accurate results were obtained for 8 certified reference materials of both environmental and biological origin. In addition, a real sludge sample was analysed. Author for correspondence. E-mail: richard.dams@rug.ac.be Received September 18, 2002; accepted December 3, 2002 Published online May 5, 2003     

New method for determination of heats of thermal gas-phase reactions yielding intermediates

A new procedure for the determination of the heats of thermal gas-phase reversible reactions leading to intermediates in the framework of the adiabatic compression method is proposed. A model problem is solved, and the error of the method is evaluated (-1 %). The validity of the method was confirmed using the reversible formation of the I,2-biradical from tetrafluoroethylene as an example. Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 64–67, January, 1996.     

Temperature-controlled combustion and kinetics of different rank coal samples

Differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG) has been used to obtain information on the temperature-controlled combustion characteristics of seventeen coals of different origin from Thrace basin of Turkey. Experiments were performed in air atmosphere up to 600°C at a heating rate of 10°C min^-1. The DSC/TG curves clearly demonstrate distinct transitional stages in the entire coal samples studied. Reaction intervals, peak and burn-out temperatures of the coal samples are also determined. Two different kinetic methods known as, Arrhenius and Coats-Redfern, were used to analyze the kinetic data and the results are discussed.     

硬木热解过程中颗粒内部二次反应的数值研究Ⅱ.数值模拟结果

为了研究生物质（硬木）热解过程中颗粒内部的二次反应，对流化床环境下单颗粒生物质热解模型进行了求解。计算针对典型大颗粒和典型小颗粒在流化床反应器反应条件下的热解过程，对不同大小颗粒内部各种产物的生成、消耗、积累以及逃逸行为进行了定量描述。计算结果表明：对于直径为2mm的小颗粒，颗粒内二次裂解的份额可以忽略，但是对于直径10mm的大颗粒，热争过程中有超过20%的一次焦油参加了颗粒内部二次反应，颗粒内二次裂解显著地改变了热解产物分布，改变了热解产物的品质。     

热处理及与KOH共炭化对深度脱除煤中无机矿物质的促进作用

研究了煤经热处理（炭化）以及煤与ＫＯＨ共炭化对酸洗脱灰的影响。结果表明，煤经炭化再用盐酸洗涤，可以在缓和的条件下大幅度提高酸洗脱灰率；煤与ＫＯＨ共炭化后再酸洗，不仅对煤中的粘土、黄铁矿等无机矿物质有很好的效果，还特别适于脱除在一般情况下都难以除去的石英矿物。     

几种烟煤及其热处理后的溶胀性能研究

研究了四种不同变质程度烟煤及其二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂(1∶1,vol)的抽提物在不同溶剂中的溶胀性能，同时考察了四种煤样不同温度热处理后其溶胀性能的变化。结果表明，煤的溶胀率随煤化度增加而有所降低;变质程度较低的烟煤在极性溶剂中的溶胀率大于非极性溶剂，随着煤化度的增加，两者溶胀度差距减小;四种烟煤经混合溶剂抽提后，其抽余煤的交联密度降低，溶胀率增加。四种煤样150℃热处理后在CS2中的溶胀率均有所增加，表明热处理可以降低煤的交联密度。随着热处理温度提高至240℃，除气煤外，其余三种煤样在NMP和CS2中溶胀率均进一步增大，说明其交联密度进一步降低。这一结果与热处理煤样在混合溶剂中抽提率的变化趋势一致，如240℃热处理后瘦煤的抽提率由原煤的6.9%提高到17.3%。红外光谱研究表明，经过适当温度的热处理，可以脱除煤分子中的羰基和羟基等含氧官能团，破坏煤结构中的氢键，从而降低煤的交联密度，提高煤的溶胀率及其在混合溶剂中的抽提率。     

聚对苯乙烯磺酸钠添加剂的分子量对水煤浆浆体性质的影响

选用了变质程度不同的八种煤和三种不同分子量的聚对苯乙烯磺酸钠（PSS）添加剂，详细考查了该添加剂的分子量对水煤浆浆体性质的影响。结果发现，在考查PSS相对分子量的范围内（质均分子量为5.34×104～33.39×104），八种煤的水煤浆成浆性随着分子量的增大而增加，水煤浆成浆性与PSS添加剂的平均分子量的关系可归因于添加剂在煤粒上的吸附，分子量小的PSS在煤粒上的吸附量大于分子量大的PSS；PSS分子量的增加有利于水煤浆的流变性由胀性向假塑性转变；PSS分子量的增加使水煤浆的静态稳定性得到显著的改善。     

Pyrolysis Analysis and Kinetics of Crude Oils

This research presents the results of an experimental study on the determination of pyrolysis behaviour and kinetics of six crude oils by differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). Crude oil pyrolysis indicated two main temperature ranges where loss of mass was observed. The first region between ambient to 400°C was distillation. The second region between 400 and 600°C was visbreaking and thermal cracking. Arrhenius-type kinetic model is used to determine the kinetic parameters of crude oils studied. It was observed that as crude oils gets heavier (°API decreases) cracking activation energy increases. Activation energy of cracking also show a general trend with asphaltene content. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation of pyrolysis of chinese coals using thermal analysis/mass spectrometry

TA/MS (thermal analysis coupled with mass spectrometry) was applied to the pyrolysis of Chinese coals with different ranks. A total of 13 Chinese coals were investigated. The samples were deliberately chosen to represent the 13 types of Chinese coals according to the Chinese coal classification system. The experiments were carried out in an argon atmosphere with a flow rate of 150 ml min^-1. The samples were heated from 40 up to 1200°C with a constant heating rate of 10 k min^-1. The main evolved pyrolysis products were identified through the on-line recorded mass spectra. The thermal and evolution behavior was compared between the coals. The results showed a strong thermal and evaluation behavior dependence on the coal rank. Different aliphatic fragments and also some aromatic substances, which are of environmental concern (BTX, PAHs), were found to be released depending on the different types of coal. This revised version was published online in July 2006 with corrections to the Cover Date.