COREX系统用煤燃烧过程中含氧官能团的转变研究

COREX是现有熔融还原方法中的主要工艺流程,该系统对煤质量有严格的要求。我们对系统运行中所涉及的主要煤种大同煤和兴隆庄煤燃烧行为进行深入研究。利用同步热分析仪（TG．DSC）研究高温条件下煤的热分解行为;通过电子扫描显微镜（SEM）观察了煤的微观结构,进行了岩相分析;通过傅里叶红外光谱仪（Frm）和湿式化学分析法,定性及定量的研究了煤中含氧官能团,尤其是热解过程中有机含氧官能基团的组分、数量、化学结构和转化机理。全面评价煤炭的质量,为系统稳定运行选用煤种,提高块煤利用率提供了理论基础。     

烟煤化学链反应特性及机理分析

在固定床反应器中添加铁基载氧体Fe4Al6和铜基载氧体Cu4Al6,进行巨野(JY)烟煤化学链燃烧实验,通过气相色谱(GC)、红外光谱(FT-IR)等分析了JY煤化学链反应特性及表面官能团演变规律。结果表明,相对于Al2O3,Fe4Al6或Cu4Al6为床料时,JY煤中CO2含量分别提高了52.25%和59.16%,最大碳转化速率分别提高了8.93%和30.36%,Cu4Al6反应效果更好。添加Cu4Al6后,JY煤表面官能团演变进程加快,Cu4Al6对脂肪烃结构、芳香碳骨架和芳香族CH的转化均有明显促进作用。煤中脂肪烃?CH3和?CH2稳定性低、反应速率快,是化学链燃烧初期气相产物主要来源;芳香碳骨架和芳香族?CH稳定性高、反应活性低,反应速率较缓慢,是化学链燃烧中后期气相产物主要来源。     

活性官能团对煤/PAN复合材料导电性能的影响

通过原煤及氧化煤中的总酸性基的测定、FTIR分析及煤/PAN电导率变化研究,表明煤在氧化过程中,弱的醚键的水解及羧酸盐向羧酸的转化,增加了煤中的羧基和羟基含量。而羧基和羟基含量的增加有利于提高煤与苯胺的作用,从而提高复合材料的电导率,其值最高可达4.72×10-1S/cm。     

Investigation into the fate of mercury in bituminous coal during mild pyrolysis

Two high-volatile bituminous coal (Lower Freeport #6A and Pittsburgh #8), used primarily for electricity production, were tested to determine the fate of their mercury content during mild pyrolysis. Mono-sized samples of the well characterized coals were tested under nitrogen in a horizontal tube furnace at different residence times at different temperatures throughout the range 275–600°C. The resulting char was analyzed for mercury, and compared to the original parent coal concentration. The percent Hg removal was found to be a function of both residence time and temperature. The data for both coals have shown two distinct regimes; a low temperature chemical evolution mechanism which follows an Arrhenius form (apparent activation energies for the Lower Freeport #6A and the Pittsburgh #8 coals are 25.6±1.5 and 21.7±1.9 kcal/mol respectively), and a higher temperature regime where the Hg evolution dramatically decreases. This can be attributed to the changing structure of the coal at these higher temperatures. The results of bomb calorimetry analysis performed on the Lower Freeport #6A coal samples verify that the overall heating value of the coal is essentially unaffected by mild pyrolysis at temperatures lower than 400°C.     

煤燃烧过程中碳、氧官能团演化行为

采用X射线光电子能谱（XPS）系统研究燃烧过程中准格尔褐煤及其煤焦颗粒表面中碳、氧的存在形态及演化过程.研究结果表明，准格尔褐煤颗粒表面含碳官能团中石墨化碳含量非常低，但同时具有一定含量的双键碳;含氧官能团中无机氧含量较低，有机氧含量相对较高.随着燃烧的进行，颗粒表面碳、氧官能团呈现不同的变化趋势.     

低阶煤高温高压水热处理改性及其成浆特性

褐煤、亚烟煤等低阶煤内水、氧含量大,直接制备浆体燃料,成浆浓度低、粘度大、流动性差。通过高温高压对低阶煤进行水热处理(热水反应),可以在较短时间内提升其煤阶和热值,同时改变其理化特征,进而较大程度提高其成浆浓度。结果表明,热水反应后,小龙潭褐煤最大成浆浓度可以由44.6%(原煤)提高到64.55%;印尼MIP亚烟煤最大成浆浓度则由39.71%(原煤)提高到64.61%。不同反应终温对于热水反应产物的成浆性能改善程度不同,从含氧基团化学分析以及煤水界面接触角两个方面进行了机理探讨。     

聚乙烯与过渡金属介入对木质素热解过程中表面官能团演变的影响

木质素(LG)含氧量高,化学结构复杂,难于资源化利用。共混剂和催化剂的介入,能够强化LG分解,有效提高其利用效率,但具体机制尚待进一步剖析。本文基于原位红外手段,考察低密度聚乙烯(PE)和过渡金属(Ni、Fe、Mn)的添加对造纸黑液LG表面官能团演变的影响。研究结果显示,LG在200℃左右从C—C连接键开始逐渐分解(波数在2044 cm^-1处),而含氧表面官能团在500℃以后才开始减少(波数在1040～1645 cm^-1和3450～3600 cm^-1处的—OH、C—O、C—O—C和C＝O等)。PE的介入,在400℃左右即能开始促进LG含氧表面官能团的脱除,在500℃左右即能实现大部分含氧表面官能团的脱除。而Ni的添加,能够强化LG与PE之间的相互作用,使得LG中大部分含氧表面官能团在PE快速分解阶段(460℃左右)即脱除。另外,工艺参数,包括过渡金属种类、过渡金属浓度、LG与PE混合比例、升温速率等均对混合体系中LG和PE的相互作用存在不同程度的影响。本文从表面官能团变化的角度为LG的资源化利用提供了重要技术指导。     

Changes of oxygen-containing groups during thermal treatment and their influences on moisture readsorption of lignite

The changes in oxygen-containing groups in the thermal treatment process of lignite were analyzed and the moisture readsorption amounts of upgraded coals were related in this study. A chemical titration method was applied to determine the types and contents of oxygen-containing groups in raw lignite and upgraded coals obtained in the temperature range of 353–633 K under atmospheres of argon, air, and carbon dioxide. Experimental results showed that the oxygen-containing groups mainly involved carbonyl, phenolic hydroxyl, and carboxylic groups (including carboxyl and carboxylate), among which phenolic groups were dominant. These different oxygen-containing groups decomposed discriminatingly with temperature according to thermal stability. The removal of oxygen-containing groups proceeded more easily in a CO₂ atmosphere compared to in Ar. The oxidation reaction occurring on the surface of lignite exposed to air led to an increase in oxygen-containing groups. The different types of oxygen-containing groups possessed various combining abilities with water, among which carboxyl was considered the most important group for the moisture readsorption. Decomposition of oxygen-containing groups in the thermal treatment process of lignite mainly caused a reduction in monolayer water adsorption and further decreased the multilayer water.     

Effect of acid treatment on thermal extraction yield in ashless coal production

Coals of different ranks were acid-treated in aqueous methoxyethoxy acetic acid (MEAA), acetic acid (AA), and HCl. The acid-treated coals were extracted with polar N-methyl-2-pyrrolidinone (NMP) and nonpolar 1-methylnaphthalene (1MN) solvents at temperatures from 200 to 360 °C for 10-60 min. The thermal extraction yields with NMP for some acid-treated low-rank coals increased greatly; for example, the extraction yield for Wyodak coal (%C; 75.0%) increased from 58.4% for the raw coal to 82.9% for coal treated in 1.0 M MEAA. Conversely, the extraction yields changed minimally for all the acid-treated coals extracted in 1-MN. The type and concentration of acid affected the extraction yield when NMP was used as the extraction solvent. With increasing MEAA concentration from 0.01 to 0.1 M, the extraction yield for Wyodak coal increased from 66.3 to 81.4%, and subsequently did not change clearly with concentration. Similar changes in the extraction yield with acid concentration were also observed with AA and HCl. The de-ashing ratio for coals acid-treated in MEAA, AA, and HCl also increased greatly with concentration from 0.01 to 0.1 M, which corresponded to the change in the thermal extraction yield in NMP. For the acid-treated coals, high extraction yields were obtained at lower extraction temperatures and shorter extraction times than for the raw coal. The mechanisms for the acid treatment and thermal extraction are discussed.     

Changes in char reactivity and structure during the gasification of a Victorian brown coal: Comparison between gasification in O2 and CO2

Char reactivity is an important factor influencing the efficiency of a gasification process. As a low-rank fuel, Victorian brown coal with high gasification reactivity is especially suitable for use with gasification-based technologies. In this study, a Victorian brown coal was gasified at 800 °C in a fluidised-bed/fixed-bed reactor. Two different gasifying agents were used, which were 4000 ppm O₂ balanced with argon and pure CO₂. The chars produced at different gasification conversion levels were further analysed with a thermogravimetric analyser (TGA) at 400 °C in air for their reactivities. The structural features of these chars were also characterised with FT-Raman/IR spectroscopy. The contents of alkali and alkaline earth metallic species in these chars were quantified. The reactivities of the chars prepared from the gasification in pure CO₂ at 800 °C were of a much higher magnitude than those obtained for the chars prepared from the gasification in 4000 ppm O₂ also at 800 °C. Even though both atmospheres (i.e. 4000 ppm O₂ and pure CO₂) are oxidising conditions, the results indicate that the reaction mechanisms for the gasification of brown coal char at 800 °C in these two gasifying atmospheres are different. FT-Raman/IR results showed that the char structure has been changed drastically during the gasification process.     

Application of FT-i.r. spectroscopy to the determination of COOH groups in coal

FT-i.r. studies of acid-demineralized and cation-loaded lignites demonstrate that exchange methods presently being used to determine carboxylic acid groups in coal produce systematic errors. An i.r. method based on intensity measurements of the 1710 cm^?1 carboxylic acid C = 0 stretching mode is reported.     

Evolution of the organic sulfur and other components during nitric acid leaching of Mequinenza coal

In this work, desulfurization by nitric acid leaching is studied in Mequinenza coal, whose characteristics are very low contents of sulfide and sulfate sulfurs in comparison with a very high content of organic sulfur that allows the selective attack on organic sulfur with regard to carbon to be clearly determined. Organic matter is made soluble at high temperatures and there is a threshold temperature for the same. The reaction involves an increase of nitrogen and oxygen, and a decrease of carbon contents. These variations reach a limit as the solubility of the organic matter progresses. The attack on inorganic sulfur is very fast, producing an initial leap as in the attack on organic sulfur, while the solubilization of organic matter is slower, because of which shorter times should be applied for the purpose of desulfurization.     

The role of solvation on the conformational change during repeated freezing-thawing treatment to an extremely dilute aqueous solution of poly(vinyl alcohol)

The effect of solvation-desolvation process on the conformational change of poly(vinyl alcohol) in an extremely dilute aqueous solution during the repeated freezing-thawing treatment was investigated by a differential refractometer. It was found that the hydrodynamic volume of PVA decreased regularly and smoothly with the number of freezing-thawing cycles treatment increasing, as the intra-molecular entanglement points made the polymer chain contract, and even in a full compacted globule state, there were still some solvent molecules in the chain. The extraordinary phenomenon was successfully explained and treated by a quantitative theory in terms of accompanying solvation-desolvation process during the macromolecular chain having contracted.