Coal characterization by on-line pyrolysis-field ionization mass spectrometry

Summary Pyrolysis-field ionization mass spectrometry (Py-FIMS) was used for the first time to directly characterize Chinese coals and their extracts. The summed mass spectra (about 30 magnetic scans) of four coal samples and the dimethylformamide extracts of two very different coals were registered between 50° and 750°C using linear heating in high vacuum (10^–3 Pa) and approximately 6 min temperature rise time. Utilizing temperature-programmed pyrolysis and FI as soft ionization mode, the spectra displayed almost exclusively molecular ions of the evolved products. The thermograms, i.e. the intensities of the total ion current and selected ions were plotted versus the scan number, heating time and temperature. In general, two maxima in these thermograms were observed, which were different for the coals and reflected their carbon/hydrogen content. Comparing the mass spectra of the low temperature part (first maximum) with summed spectra of the extracts shows an interesting similarity. In contrast, the high temperature part (second maximum) indicates the products of thermo-degradation. The applied method is a fast and convenient tool for the characterization of evolved volatiles and thermal degradation products of coals and coal extracts.

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Kennzeichnung von Kohlen mit direkter Pyrolyse und Feldionisations-Massenspektrometrie

     

逐级酸处理对锡盟褐煤的结构及热解特性的影响：气相产物的生成

为了考察逐级酸处理对锡盟褐煤热解过程中气相产物生成的影响,对锡盟褐煤进行了HF-HNO₃-HCl逐级处理,原煤和酸处理煤样采用固定床热解-气相色谱法在线分析气相产物释放行为和变化的研究。结果表明,逐级酸处理过程对锡盟褐煤热解过程中含氢气体、含氧气体和含硫气体的释放有着明显的影响。不同气体的形成途径、形成阶段和温区不同,导致酸处理过程对其的影响有明显的差异。逐级酸处理的煤样,除因矿物质对煤热解气相产物的影响减弱外,HNO₃处理样还因其氧化作用引起了气相产物释放趋势的变化,使得含氢气体的释放量降低、含氧气体释放量增加;降低了H₂S的累积释放转化率而促进COS的释放。     

XANES技术探究酸处理对义马煤中硫形态及其热变迁行为的影响

利用XANES技术研究了酸处理对义马煤的比表面积、体相及表面硫形态分布和热解过程中硫变迁行为的影响。结果表明,由于酸处理过程中部分镶嵌于有机质中的矿物质被脱除导致部分闭合孔打开,煤的比表面积有所增大。HCl-HF和HCl-HF-HNO_3处理脱除了煤中大部分矿物质和无机硫,由于HNO_3的强氧化性,YMN中亚砜和砜硫化物的相对含量均高于YMR和YMD。相比煤样体相,酸处理过程对表面形态硫的分布产生了更为明显的影响。酸处理煤样热解含硫气体释放量减少,但由于大部分碱性矿物质的脱除和煤中易分解形态硫相对含量的增加,含硫气体释放率增加。不同形态硫之间的内部转化使得酸处理煤焦中主要形态硫的分布更为均匀。通过HCl-HF-HNO_3处理可以有效地脱除煤中矿物质及无机硫,并改变煤中形态硫分布,从而为高灰分、富含黄铁矿的高硫煤的利用提供指导。     

The additivity principle in pyrolysis—gas chromatography of brown coal

Pyrolysis—gas chromatography of brown coal exhibits additive properties and it is therefore possible to construct the pyrogram of the original coal from the individual pyrograms of the bitumen, humic acids, lignin and humin fractions. The contents of phenols in the pyrograms are typical for all of the above classes except bitumen and are in agreement with the contents of the individual groups in the original coal. The results suggest that the separation does not bring about significant chemical changes in individual brown coal fractions.     

用热重红外光谱联用技术研究混煤热解特性

用热重分析仪和傅里叶红外光谱仪，对混煤在惰性气氛中的慢速热解特性进行了动态分析，考察了煤种、掺混比例以及加热速率对热解的影响。结果表明，混煤的热解与单煤的热解有相似之处，热解组分的析出随温度的变化规律一致，但其组分析出量并不是单煤热解析出量的简单叠加。由于掺混煤种间的相互作用，混煤热解气体在析出时间和析出量上均发生了变化。通过对红外吸收光谱的分析，发现混煤热解气体析出规律受掺混煤种的影响很大，高活性煤种的存在会降低混煤热解的初析温度，增加热解气体的析出量，其掺混比例越高，影响也越明显。     

Analysis of plasma-polymerized hydrocarbons by pyrolysis/gas chromatography

Plasma-polymerized oils, films and powders obtained from ethylene, acetylene, butadiene, and benzene were characterized by flash pyrolysis and gas chromatography (P/GC). None of the pyrograms resembled those of commercial polyethylene, polybutadiene, or polystyrene. Each of the plasma-polymer pyrograms did exhibit essentially the same fragments up to C₈, albeit in a different distribution, indicating that all samples are structurally similar. Analysis of the P/GC data shows these materials to contain a random arrangement of side chains, crosslinks, double bonds, and aromatic structures. Changes in the fragment distribution were obvious when the sample was a powder, solid film, or oily film produced from the same monomer. It was shown that powder products generally have a higher concentration of branches and/or crosslinks than the oil or film products. There are also differences in the pyrograms of products of the same form derived from dissimilar monomers. The results obtained from P/GC generally support those derived from infrared or NMR measurements performed earlier.     

煤焦分形维数及其对比热容的影响研究

比热容是煤炭热物理性质之一,在煤矿的矿井防火、防止煤与瓦斯突出、井下降温设计及煤炭加工利用(如煤炭的燃烧、气化、焦化、液化等)等方面是关键参数之一,对提高煤炭热能利用率、提高经济效益、减少环境污染等,具有非常重要的意义。比热容的影响因素很多,如煤化程度、水分质量分数、热解温度等,煤焦微观结构的影响也是其中很重要的一方面。分形几何由Mandelbrot 1982年创立,是定量描述自相似或自相关等不规则形体的工具。研究表明,煤焦微观结构具有分形特征。在煤焦分形的研究中,常用的实验技术方法为吸附法、小角度X射线散射法和孔度法,采用扫描电子显微镜和数字图象处理方法研究煤焦的分形结构,能更加深入地理解其分形维数与性能的关系。     

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.     

低熟煤中常量、微量元素与煤生烃潜力参数的相关性研究

应用电离耦合等离子体原子反射光谱（ICP AES）和X射线荧光光谱（XRF），对新疆准噶尔六道湾侏罗纪低熟煤中36种微量元素的质量分数进行了测定，同时作岩石热解分析，有机碳测定，并对获取的各种数据进行回归分析，以考察它们之间的相关性。实验结果表明，除个别具有一定化学催化能力的元素外，多数常量元素及其所形成的矿物质，由于其对成煤有机物质的负增量作用，会明显降低煤的生烃潜力；微量元素对煤的生烃性能影响则较为复杂,既与其对煤的各种化学组成的有机亲和性之差异有关，亦与其在煤的大分子热裂解成烃中的某种化学催化作用有关。此外，由于某些微量元素所特有的古气候、古成煤沼泽类型的“指相”作用，亦能间接地指示煤的生烃潜力。其中Cu既是一个有着与煤的大分子物质较强亲和力的元素，又是一个可以显示古气候古成煤沼泽类型的“指相”元素，因而在指示煤的生烃潜力方面可能具有普适性。     

煤热解过程中含氮气相产物转化规律的实验研究

为了研究煤在热解过程中含氮气相产物的生成规律,在滴管炉反应系统中对四种原煤以及两种脱除矿物质煤样分别在500℃、700℃、900℃和1100℃进行了实验研究。结果表明,随着温度的升高,作为NO前驱物的HCN和NH3的收率随之增加,N2的收率也增加。煤种对含氮气相产物的生成规律也有着较大的影响,煤化程度比较低的煤在热解过程中,燃料氮向气相含氮产物的转化率较高;煤化程度比较高的煤转化率则偏低,大部分的氮缩聚在多环芳香结构中,成为焦炭氮。煤中的矿物质对燃料氮向N2的转化起到了促进作用,而对燃料氮向HCN和NH3的转化起到了抑制作用。     

煤高温快速热解规律研究

利用高温滴管炉在1000℃～1400℃考察了彬县烟煤在高温快速热解过程中失重的变化,同时比较了埃塞俄比亚褐煤和晋城无烟煤的热解规律。结果表明,热解失重率随温度的升高而增加,而且各种煤种的最大失重率在高温下大于工业分析的失重率。对于不同变质程度的煤种其热解特性也不相同,较低的热解温度对高阶煤的影响较小。彬县原煤经过热解后比表面积增加,且随着热解温度的提高而增大,当热解温度超过灰熔点时,总比表面积降低。通过数据回归,得到了三种煤的失重率和热解温度的关联式。     

CO_2气氛对煤热解过程中硫逸出的影响

采用热解-质谱(Py-MS)与热解-气相色谱(Py-GC)相结合的方法对平朔(PS)和义马(YM)原煤、脱灰煤及其脱黄铁矿煤进行了热解实验,考察了CO_2气氛对煤热解过程中硫逸出行为的影响。并采用质谱在线分析H_2S、COS和SO_2的逸出曲线,利用气相色谱分析H_2S、COS和SO_2在气相中的逸出量。结果表明,CO_2气氛有利于H_2S、COS和SO_2进入气相,且逸出量增加,而COS增加幅度更大。同时,CO_2气氛有利于H_2S和SO_2最大逸出峰温提前。另外,CO_2气氛对原煤的H_2S、COS和SO_2逸出温度影响较大,但对脱灰煤的影响较小。在较高的温度下,CO_2有利于煤中稳定有机硫的分解。这进一步验证了在较高温度下COS形成与CO相关,而在较低温度下与CO无关。     

A kinetic analysis of the pyrolysis of some australian coals by non-isothermal thermogravimetry

The pyrolysis of a suite of brown coal samples and bituminous coal maceral concentrates is investigated by non-isothermal thermogravimetry. The TG data for these coals reveal a two-stage pyrolysis process. The activation energy for the primary pyrolysis stage is considerably higher than that for the secondary pyrolysis stage. It is evident that a particular coal may be characterised by the weighted mean apparent pyrolysis activation energy which correlates with the corresponding specific energy of the coal.

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Zusammenfassung Mittels nichtisothermer Thermogravimetrie wurde die Pyrolyse einer Reihe von Braunkohlenproben und Mazeralkonzentrate aus bituminösen Kohlen untersucht. Die TG-Daten dieser Kohlen weisen einen zweischrittigen Pyrolyseprozeß auf. Die Aktivierungsenergie für den ersten Pyrolyseschritt ist erheblich höher als die des zweiten Pyrolyseschrittes. Es ist offensichtlich, daß eine gegebene Kohle durch den gewichteten Mittelwert der scheinbaren Aktivierungsenergie der Pyrolyse charakterisiert werden kann, welcher mit der entsprechenden spezifischen Energie der Kohle korreliert.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday     

Coal analysis by application of the partial least squares method to infrared spectra

Summary A method for the rapid characterization of brown coals based on the application of a powerful method of principal component analysis, the Partial Least Squares method (PLS), is described. A data catalogue of 44 brown coals from different deposits of East European and Asian countries was used, which lists analyses of several coal parameters. Infrared spectra of brown coals were recorded and different coal properties were predicted with the help of PLS. The results show that, with the PLS-method used, several coal properties can be predicted and it is possible to describe the classification of a coal for several technological processes. The developed method is useful because of the multiplicity of information obtained within a short time and because it is possible to replace lengthy classical methods.     

裂解气相色谱—裂解毛细柱气相色谱联用仪

设计了一种裂解气相色谱--裂解毛细柱气相色谱联用仪。在第一级裂解气相色谱仪把聚合物裂解并分离裂解产物,分离了的产物用六通气体进样阀选取并逐个在第二级裂解气相色谱仪裂解,得到聚合物裂解产物的裂解气相色谱图。与低分子化合物的标准指纹图比较,这些裂解产物就得到确认,这样,就可以充分肯定地推断复杂聚合物的组成。     

澳大利亚高盐煤中钠在热解过程中的形态变迁

通过对高钠煤进行水洗以及0.1 mol/L的HCl洗涤,并在固定床上考察了不同洗煤热解后的半焦中Na的挥发性及其形态变迁。热解后的半焦用水和0.1 mol/L的HCl逐级萃取,将热解半焦中的钠分为水溶态钠,水不溶但酸溶态钠以及酸不溶态钠。研究结果表明,实验煤中的钠大部分是以水溶态的NaCl盐形式存在,在500℃~550℃由于以羧酸盐形式存在的有机钠以钠原子的形式释放使得在该温度范围内钠的挥发性出现极大值,而酸洗煤由于在600℃以上有一部分酸不溶态的钠转化为水不溶但酸溶态的钠,使得钠的挥发性又有所增加。原煤中的可挥发钠热解后少部分在高温下会转化为水溶态的钠,而水洗煤中的钠随着热解温度的升高与SiO2反应转化为硅酸盐形式存在的酸不溶态的钠。     

煤热解过程中含氮产物的析出及金属离子的催化特性研究

选择3种典型煤种为研究对象,通过脱灰和添加含Fe、Ca、Na等金属盐,研究煤热解过程中金属离子对含氮气相产物析出特性的影响以及与煤种和温度的交互关联。结果表明,脱灰煤HCN和NH3的产率均比原煤样下降,而随温度的升高HCN的产率逐渐增大,NH3的产率则先增加后减小,在800℃有最大值。金属离子对不同变质程度煤的含氮气相产物析出的催化作用不同;Fe和Na抑制中等变质程度煤HCN的析出,而对低变质程度煤起促进作用,Ca则对HCN的析出均有一定的促进作用。而对于NH3的形成,3种离子均对中等变质程度煤有抑制作用,而对低变质程度的煤则有促进作用。不同金属离子对HCN和NH3析出的催化作用均有一定的范围。煤热解时含氮气相产物的析出是煤中固有多种金属离子共同作用的结果。     

High-energy (neodymium) laser pyrolysis of U.S. coals

As part of a study exploring conditions that influence coal pyrolysis, the effects of neodymium laser heating upon five different rank coals have been studied. Gaseous products from neodymium-laser pyrolysis of all coal types can be explained by condensation reactions during the cooling of high-temperature systems. The use of neutral or reducing atmospheres (helium, hydrogen or deuterium at two atmospheres) does not significantly alter the product distributions, although some deuteration of products was observed. High-speed photography was used to determine the dynamics of the laser interactions.     

煤岩有机显微组分热解过程中HCN和NH3生成规律的研究

经等密度梯度离心分离，从褐煤、长焰煤、气煤和贫煤四种不同变质程度煤中获得了高纯度的有机显微组分。用石英管式反应器在600 ℃～900 ℃考察了煤岩有机显微组分热解过程中HCN和NH3的生成规律。实验结果表明，在显微组分热解过程中HCN主要是挥发分二次裂解的产物。在镜质组热解过程中，煤的变质程度越高，HCN的生成率越低，热解温度越高，HCN的生成率越高；同一种煤三种有机显微组分热解过程中，HCN的生成不仅与显微组分挥发分的质量分数有关，而且与显微组分中氮的存在形态有关，在较低温度热解时吡咯型氮质量分数高的煤样HCN的生成率较高。显微组分热解过程中NH3来自于挥发分的二次热裂解，与焦的热裂解有关，随煤变质程度增高，镜质组热解过程中NH3的收率降低；对同一种煤三种煤岩有机显微组分，由于其黏结性不同，含氮官能团和氢自由基的接触几率不同，生成NH3的能力也不同，惰质组的NH3生成率最高，壳质组最低；温度对NH3的生成也有影响，800 ℃NH3的生成率最高，惰质组NH3的生成率为11.8%，壳质组NH3的生成率为5.2%。     

低品质煤提质后快速热解大分子挥发分产物的析出特性

对3种低品质煤进行200、250和300℃下的水热提质实验。将水热提质前后的煤样进行氮吸附测试和红外光谱测定,获得其孔隙分布和含氧官能团的变化规律。结果表明,水热提质后,各煤种平均孔径、比孔容明显降低,煤中羟基、羧基减少,环化程度升高,单环芳烃结构向多环芳烃转化,煤中有机质逐渐成熟,煤阶升高。利用快速热解仪在升温速率5000℃/s、终温1000℃条件下进行实验,获得低品质煤热解大分子挥发分的析出规律。结果表明,随着反应终温的升高,各煤种热解产生的脂肪烃含量减小、芳香烃的含量升高、酸类和酚类减少、酯类变化规律不明显。