煤油共炼残渣性质分析
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摘要
采用元素分析、工业分析、热重分析、X射线衍射、扫描电镜、红外光谱等手段对煤油共炼残渣的组成、微观结构、官能团进行分析表征,并通过红外谱图的分峰拟合对官能团含量进行半定量计算。结果表明:残渣的有机物由具有片层堆积结构碳质颗粒组成,无机物由煤油共炼催化剂和煤中的无机矿物质组成;残渣颗粒粒径呈10μm和2μm的两级分布,颗粒呈整体无序、局部有序的分布状态。分别采用工业分析和热重分析得到挥发分、固定碳和灰分的含量,两组数据一致:残渣的氢键中羟基自缔合结构占约47.5%;脂肪氢中亚甲基结构占约64%;含氧官能团主要以碳氧键和羰基形式存在,含有微量的硅氧键,没有羧基;芳香结构中烷基侧链取代基较多,五取代氢的芳香结构只占约4.5%。
The composition,microstructure and functional groups of coal-oil co-processing residue were analyzed by elemental analysis,proximate analysis,thermogravimetry,X ray diffraction,scanning electron microscopy and infrared spectroscopy.The content of functional groups was semi-quantitatively calculated by the peak fitting of infrared spectroscopy.The results showed that the organic matter of the residue are composed of lamellar stacking carbon particles,the inorganic matter of residue are composed of coal-oil co-processing catalyst fines and inorganic minerals in coal.The diameters of the residue particles are distributed in around 10μm and 2μm.The particles distribute disorderly in integer area and orderly in local area.Volatile,fixed carbon and ash contents were determined by proximate analysis;the results are close to that of thermogravimetric analysis.The hydroxyl self-associating groups in the hydrogenbond in the residue account for 47.95%,the methylene groups of the aliphatic-hydrogen account for 64%.The oxygen-containing functional groups exist in the form of carbon oxygen bonds and carbonyl groups mainly,and contained tiny silicon oxygen bonds,but without carboxyl group.The aromatic groups contain more alkyl-side-chain substituents,while the aromatic groups with five substituted hydrogen account for only 4.5%.
The composition,microstructure and functional groups of coal-oil co-processing residue were analyzed by elemental analysis,proximate analysis,thermogravimetry,X ray diffraction,scanning electron microscopy and infrared spectroscopy.The content of functional groups was semi-quantitatively calculated by the peak fitting of infrared spectroscopy.The results showed that the organic matter of the residue are composed of lamellar stacking carbon particles,the inorganic matter of residue are composed of coal-oil co-processing catalyst fines and inorganic minerals in coal.The diameters of the residue particles are distributed in around 10μm and 2μm.The particles distribute disorderly in integer area and orderly in local area.Volatile,fixed carbon and ash contents were determined by proximate analysis;the results are close to that of thermogravimetric analysis.The hydroxyl self-associating groups in the hydrogenbond in the residue account for 47.95%,the methylene groups of the aliphatic-hydrogen account for 64%.The oxygen-containing functional groups exist in the form of carbon oxygen bonds and carbonyl groups mainly,and contained tiny silicon oxygen bonds,but without carboxyl group.The aromatic groups contain more alkyl-side-chain substituents,while the aromatic groups with five substituted hydrogen account for only 4.5%.
引文
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[19]宋昱,朱炎铭,李伍.东胜长焰煤热解含氧官能团结构演化的13C-NMR和FT-IR分析[J].燃料化学学报,2015,43(5):519-529
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[2]李传,秦勇,杨腾飞,等.不同等级煤与油共炼的转化率差异及残渣分析[J].燃料化学学报,2017,45(4):436-441
[3]Moliner R,Suelves I,La Maro M J.Synergetic effects in the copyrolysis of coal petroleum residue mixtures by pyrolysis gas chromatography:Influence of temperature,pressure,and coal nature[J].Energy Fuels,1998,12(5):963-967
[4]刘朋飞,张永奇,房倚天,等.神华煤直接液化残渣临界溶剂萃取研究[J].燃料化学学报,2012,40(7):776-781
[5]程时富,张元新,常鸿雁,等.煤直接液化残渣的萃取和利用研究[J].煤炭转化,2015,38(4):38-42
[6]Chu Xijie,Li Wenhui,Li Baoqing,et al.Gasification property of direct coal liquefaction residue with steam[J].Process Safety and Environmental Protection,2006,84(6):440-445
[7]Taguchi N,Tsuji T,Shibata T,et al.Thermogravimetric analysis of coal liquefaction residues and their solvent extracts[J].Nippon Kagaku Kaishi,2001(10):581-586
[8]刘文郁,杜铭华,曲建思,等.神华煤直接液化残渣热解动力学研究[J].煤炭学报,2006,31(2):215-218
[9]周俊虎,方磊,程军,等.神华煤液化残渣的热解特性研究[J].煤炭学报,2005,30(3):349-352
[10]王国龙,徐蓉,张德祥,等.煤液化残渣加氢性能[J].石油学报(石油加工),2009,25(5):747-751
[11]盛英,李克建,李文博,等.煤直接液化残留物制备中间相沥青[J].煤炭学报,2009,34(8):1125-1128
[12]周颖,张艳,李振涛,等.以煤炭直接液化残渣为原料制备炭纳米管[J].煤炭转化,2007,30(3):41-44
[13]杨辉,梁朋,宋怀河,等.煤加氢液化残渣制备中间相沥青的研究[J].炭素技术,2014,33(5):26-30
[14]Cheng Xianglin,Li Guoning,Peng Yaoli,et al.Obtaining needle coke from coal liquefaction residue[J].Chemistry and Technology of Fuels and Oils,2012,48(5):349-355
[15]Rana M S.Changes in asphaltene structure during thermal cracking of residual oils-XRD study[J].Fuel,2015,150(12):558-564
[16]王海燕,樊少武,姚海飞.2种不同变质程度煤表面化学结构红外光谱分析[J].煤矿安全,2018,49(1):194-197
[17]姬新强,慧芳,李伟.韩成矿区构造煤红外光谱特征研究[J].煤炭学报,2016,41(8):2050-2056
[18]郑庆荣,曾凡桂,张世同.中变质煤结构演化的FT-IR分析[J].煤炭学报,2011,36(3):481-486
[19]宋昱,朱炎铭,李伍.东胜长焰煤热解含氧官能团结构演化的13C-NMR和FT-IR分析[J].燃料化学学报,2015,43(5):519-529
[20]周剑林,王永刚,黄鑫,等.低阶煤中含氧官能团分布的研究[J].燃料化学学报,2013,41(2):134-138