烟煤快速加氢热解的研究

第29卷第1期燃料化学学报Vol, 29 No. 1200年2月JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGYFeb.2001文章编号:0253-240X2001)1004405烟煤快速加氢热解的研究Ⅴ.煤和半焦中有机硫化学形态剖析朱子彬,朱宏斌,吴勇强,唐黎华,陈玲君,徐志刚(华东理工大学,上海200237)摘要∶采用ⅹ閃技术分析了我国以烟煤为主的七种煤样以及对应的快速加氬热解半焦中有机硫的化学形态。煤中有机硫一般为脂肪类硫与噻吩类硫其谱峰位置分别在163.~166.5V和164.~-164.5eV之间。噻昐类硫的相对含量随煤化程度而増大。半焦中一般只残留噻吩类硫溍峰位置在164.Ⅰ~164.5与对应煤中噻昐硫的谱峰位置是一致旳。在加氢热解过程中全部脂眆类硫和部分噻昐类硫被脱除脂眆类硫表现岀很高的加氢反应活性关键词:煤;快速加氢热解;硫形态;XPS中图分类号:T0530.2文献标识码:A研究煤中有杋硫旳形态对于控制煤燃烧所引加氫热解过程中的变化规律。起的硫氧化物污染具有重要意文。将电子能谱1实验部分XPX- ray Photoelectron Spectroscopy)运用到煤的分1.1实验装置与分析方法煤快速加氬热解的实析上为煤中有机硫的化学形态非破坏性分析提供验装置见文献11]对煤样和半焦进行XPS分析,了一种新的手段。Fms「2最早采用XPS分析了煤中的化学形态。Pemy3研究的XPs谱图中硫有两采用PH-53CSCA谱仪使用MgKa为发射源,步长0.leⅤ,最低分辨率为0.1%,粉末样使用 Scotch峰分别对应为有机硫与硫酸盐硫。 Kelemen[4-6]带固定采用C284.6eV为内标校正荷电位移并采的研究表明煤中有机硫分别为脂肪类硫与噻吩类硫。Hitl对煤酸洗脱灰处理未改变煤中有机用ongn软件根据优化算法对出峰进行Gs拟合。XS出峰位置并消除了无机硫的影响。国内学者1.2试样选用我国煤化程度不同的七种煤样亦对我国煤中有机硫形态进行了分析,煤的快其样品粉碎到60-8目对其进行快速加氢热解。速加氢热解是洁净煤利用新技术,该工艺具有显蓄为避免无机硫与有机硫同时出峰对有机硫XS谱图的脱硫效果。本文运用xS分析了我国以烟煤的干扰本实验对所得半焦与煤样在X分析前粉碎为主的七种煤并同时分析了加氬热解后所得半焦至200目进行酸洗脱灰份处理2。煤样的元素分析中的有机硫以考察我国煤中有机硫的形态以及在与工业分析见表1各种形态硫的分析见表2。表1煤样的工业分析和元素分析Table 1 Analysis data of coalProximate analysis W/% dry H/CUltimate analysis w/%daf12.6229.6357.750.52486.263.821.511Xishan13.5819.22670.70985.665980.696.6113.8414.6171.550.7185.195.031.560.647.58Datong6.338.7364,940.77182.794.651.081.1110.3732.409.0258.580.79481.595.401.820.7110.4833.568.8257.620.723中国煤化工Huangxian41.2941CNMHby difference收稿日期:20005-22;修回日期:20008-12基金项目:国家自然科学基金29476232)作者简介万40-)男浙江吴兴人博士生导师教授化学工程期朱子彬等:烟煤快速加氢热解的研究Ⅴ45表2煤样中的各种形态硫分析Table 2 anal-Inorganic sulfurOrganic sulfurTotal sulfurCoalte sulfur relative content organic sulfur relative contentW/%W/%2.467.773.522.2310.920.6340.543.30Caojiazhuang1.1858.182.314.9364.933.5635.0710.15Hu1.700,472.5539.53Dongsheng0.160.5475.002.805.322实验结果与讨论一般噻吩类硫的含量较高脂肪类硫含量较低我国2.Ⅰ煤中的有机硫化学形态表3为煤中有机硫煤的分析与 George的实验结果相吻合。例如,西含量与XS谱图数据。煤样的X谱图如图1所山、曹家庄与阳泉煤的噻吩类硫都在85%左右东示。由图1和表3可见煤中有机硫一般存在两个胜、黄县、华丰和大同等煤中的噻吩硫在70%或峰其峰位置均分别在163.1~163.5eV和164.1-70%以下。东胜煤的两个出峰分别在164.0eV与164.5Ⅳ两处。根据文献4BB可知前者对应脂肪165.leV前者对应于噻吩类硫后者应为氧化态的类硫脂肪类、硫醚和硫醇等)后者对应噻吩类硫。有机硫。煤中有杋硫形态与煤化程度有关煤化程度高的煤370人人睡A162163164165166l60162|64166168Binding energy F/eVBinding energy E/eVBinding cncrgy E/cVYangquan coalXishan coal80风AA162163164165166Binding energy E/evBinding energy E/cVBinding cnergy F/cVBinding energy lev图1煤中有机硫的XF中国煤化工CNMHG2.2半焦中有机硫化学形态表4为加氢热解半硫与木叼类训山畔山置是一致的。这说明焦中有机硫含量和ⅹⅣS谱图数据,图2为半焦的加氢热解过程中脂肪类硫具有较高的反应活性易XⅣSs谱图。由图、表可见半焦中有机硫一般只岀现被脱除而噻吩类硫相对稳定噻吩仍残留在半焦个峰停鹗41-104.5相对应为噻盼类中。 Element也指出经热解后焦样中仅有微量的燃料化学学报29卷脂肪类硫的存在。本研究在快速加氬条件下进行,右。由表4可见半焦中存在的主要是噻吩类硫。我国七种煤中的脂肪类硫被全部地脱除。噻吩硫化物非常稳定难以分解,但在750℃、由表3与表4的比较可见煤中的脂肪类硫含6.0MPa氬压下的快速加氢热解过程中煤中部分噻量越高则相应的有机硫脱除率也就越髙如大同煤吩也參与加氬反应表现岀噻吩含量的明显降低脂肪类硫的含量约50%其有杋硫脱除率接近∞% Elemenπ°也指岀400~τ00℃~温度范围内煤中噻吩左右华丰煤脱硫率也达到85%以上。由于半焦中类硫也有一定的反应活性。东胜焦样中存在两个有机硫含量很低相应在大同和华丰半焦ⅹⅣS谱图峰谱峰位置仍在164.leV与165.eV,氧化态有机上几乎很难发现它们的谱峰而阳泉、西山等煤中噻硫反应活性较低其脱除效果较差较脂肪类硫难脱吩类硫含量较高测有机硫脱除率较低仅55%左除。表3煤中有机硫的ⅩⅣ分析Table 3 XPS analysis data of organic sulfur in coalOrganic sulfur content W/% Peak number Peak position Model compound Relative content W/%Yal64.1Xishan0.330212121212aliphatic sulfurCaojiazhuang163.345.10Datong0.356thiophene163.1aliphatic sulfur68.95Dongshen165.1sulfur oxide163.2aliphatic sulfurH0.262164.2 thiophene 70.77表4半焦的有机硫X分析Table 4 XPS analysis data of organic sulfur in harf-cokeModelRelative contentHarf-cokePeak peakemoving rateontent W/% number posirganic sulfur w/%0YangquanXishan164.5Caojiazhuanthiophene0.055中国煤化工CNMHG0.123165.10.11373.19164.3衣数据 hecked peak期朱子彬等:烟煤快速加氢热解的研究Ⅴ482e30Binding energy E/evBinding energy ElevBinding energy E/cvXishan half-cokeCaojiazhuang half-cokeHuangxian half-coke人Yangquan hall-coke图2半焦中有机硫XPS谱图Figure 2 XPS of organic sulfur in half-coke3结论(2)快速加氢热解半焦中有机硫的形态较为单1)煤中有机硫形态一般为脂肪类硫和噻吩类般仅为噻吩硫,谱峰位置在164.1~164.5eV硫NⅨ谱峰位置分别在163.1~163.5cⅤ和164.1之间卢与对应煤样中噻吩类硫的谱峰位置是一致的。~164.5eV之间噻吩类硫的相对含量随煤化程度3)加氢热解能脱除全部的脂肪硫和部分的噻加深而增大吩硫脂肪硫表现岀了较高的加氢反应活性参考文献[1]陈鹞.中国煤中硫的赋存特征及脱硫J]煤炭转化,19)4,1K2):1-9[ 2] David C Frost, William R Leeder, Robert L Tapping. 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Hydropyrolysis-Third way for coal conversion J I. Erdol und Kohle- Erdgas-Pertro, 1983, 36( 10)471-476[1]朱子彬王欣荣马智华,等.煤快速加氬热解获得液态烃和气态烃的研究(Ⅲ)气体停留时间的考察J].化工学报,1995,466):10-71612]cc有数据adML, Kelemen S R. Direct determination and quantification of sulfur forms in coals form the argo premium燃料化学学报29卷nple progran[ J ] Energy Fuels, 1991, 5 93-9813 Martin L Gorbaty, Simon R Kelemen, Graham N George. Characterization and thermal reactivity of oxidized organic sulphur forms incoal[ J].Fel,1992,71:1255-1261RESEARCH OF COAL FLASH HYDROPYROLYSISV. CHEMICAL TYPE ANALYSIS OF ORGANIC SULFUR IN COAL AND SEMI-COKEZHU Zhi-bin ZHU Hong-bin WU Yong-qiang, TANG Li-hua, CHENG Ling-jun XU Zhi-gangEast China University of Science and Technology Shanghai 200237, ChinaAbstract: Using XPS analyses the organic sulfur of seven different Chinese coals and their semi-cokesfrom flash hydropyrolysis were studied. The result showed that organic sulfur in coal was alkyl sulfur andthiophene with the peak of xps located in 163. 1-163 5ev and 164.1- 164. 5ev. The relative thio-phene content in coal increased with coal rank. The type of organic sulfur in semi-coke in flash hydropy-rolysis was generally thiophene species. Its XPs peak also located in 164 1-1645ev, and was in accord with its corresponding coal. Total alkyl sulfur and some thiophene sulfur were removed during flashhydropyrolysis process. Alkyl sulfur had very high activity in hydrogenation reaction. Flash hydropyrolysiswas a new important clean-coal technique and had notableKey words coal i flash hydropyrolysis i sulfur type ; XPS中国煤化工CNMHGFoundation item: National Natural Science Foundation of China( 29476232)Author introduction: ZHU Zi-bin( 1940-), male, Advisor of Dr. Postgraduate, Professor, chemical engineering