第29卷第1期燃料化學學報Vol, 29 No. 1200年2月JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGYFeb.2001文章編號:0253-240X2001)1004405煙煤快速加氫熱解的研究Ⅴ.煤和半焦中有機硫化學形態(tài)剖析朱子彬,朱宏斌,吳勇強,唐黎華,陳玲君,徐志剛(華東理工大學,上海200237)摘要∶采用ⅹ閃技術(shù)分析了我國以煙煤為主的七種煤樣以及對應的快速加氬熱解半焦中有機硫的化學形態(tài)。煤中有機硫一般為脂肪類硫與噻吩類硫其譜峰位置分別在163.~166.5V和164.~-164.5eV之間。噻昐類硫的相對含量隨煤化程度而増大。半焦中一般只殘留噻吩類硫溍峰位置在164.Ⅰ~164.5與對應煤中噻昐硫的譜峰位置是一致旳。在加氫熱解過程中全部脂眆類硫和部分噻昐類硫被脫除脂眆類硫表現(xiàn)岀很高的加氫反應活性關(guān)鍵詞:煤;快速加氫熱解;硫形態(tài);XPS中圖分類號:T0530.2文獻標識碼:A研究煤中有杋硫旳形態(tài)對于控制煤燃燒所引加氫熱解過程中的變化規(guī)律。起的硫氧化物污染具有重要意文。將電子能譜1實驗部分XPX- ray Photoelectron Spectroscopy)運用到煤的分1.1實驗裝置與分析方法煤快速加氬熱解的實析上為煤中有機硫的化學形態(tài)非破壞性分析提供驗裝置見文獻11]對煤樣和半焦進行XPS分析,了一種新的手段。Fms「2最早采用XPS分析了煤中的化學形態(tài)。Pemy3研究的XPs譜圖中硫有兩采用PH-53CSCA譜儀使用MgKa為發(fā)射源,步長0.leⅤ,最低分辨率為0.1%,粉末樣使用 Scotch峰分別對應為有機硫與硫酸鹽硫。 Kelemen[4-6]帶固定采用C284.6eV為內(nèi)標校正荷電位移并采的研究表明煤中有機硫分別為脂肪類硫與噻吩類硫。Hitl對煤酸洗脫灰處理未改變煤中有機用ongn軟件根據(jù)優(yōu)化算法對出峰進行Gs擬合。XS出峰位置并消除了無機硫的影響。國內(nèi)學者1.2試樣選用我國煤化程度不同的七種煤樣亦對我國煤中有機硫形態(tài)進行了分析,煤的快其樣品粉碎到60-8目對其進行快速加氫熱解。速加氫熱解是潔凈煤利用新技術(shù),該工藝具有顯蓄為避免無機硫與有機硫同時出峰對有機硫XS譜圖的脫硫效果。本文運用xS分析了我國以煙煤的干擾本實驗對所得半焦與煤樣在X分析前粉碎為主的七種煤并同時分析了加氬熱解后所得半焦至200目進行酸洗脫灰份處理2。煤樣的元素分析中的有機硫以考察我國煤中有機硫的形態(tài)以及在與工業(yè)分析見表1各種形態(tài)硫的分析見表2。表1煤樣的工業(yè)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中國煤化工Huangxian41.2941CNMHby difference收稿日期:20005-22;修回日期:20008-12基金項目:國家自然科學基金29476232)作者簡介萬40-)男浙江吳興人博士生導師教授化學工程期朱子彬等:煙煤快速加氫熱解的研究Ⅴ45表2煤樣中的各種形態(tài)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實驗結(jié)果與討論一般噻吩類硫的含量較高脂肪類硫含量較低我國2.Ⅰ煤中的有機硫化學形態(tài)表3為煤中有機硫煤的分析與 George的實驗結(jié)果相吻合。例如,西含量與XS譜圖數(shù)據(jù)。煤樣的X譜圖如圖1所山、曹家莊與陽泉煤的噻吩類硫都在85%左右東示。由圖1和表3可見煤中有機硫一般存在兩個勝、黃縣、華豐和大同等煤中的噻吩硫在70%或峰其峰位置均分別在163.1~163.5eV和164.1-70%以下。東勝煤的兩個出峰分別在164.0eV與164.5Ⅳ兩處。根據(jù)文獻4BB可知前者對應脂肪165.leV前者對應于噻吩類硫后者應為氧化態(tài)的類硫脂肪類、硫醚和硫醇等)后者對應噻吩類硫。有機硫。煤中有杋硫形態(tài)與煤化程度有關(guān)煤化程度高的煤370人人睡A162163164165166l60162|64166168Binding energy F/eVBinding energy E/eVBinding cncrgy E/cVYangquan coalXishan coal80風AA162163164165166Binding energy E/evBinding energy E/cVBinding cnergy F/cVBinding energy lev圖1煤中有機硫的XF中國煤化工CNMHG2.2半焦中有機硫化學形態(tài)表4為加氫熱解半硫與木叼類訓山畔山置是一致的。這說明焦中有機硫含量和ⅹⅣS譜圖數(shù)據(jù),圖2為半焦的加氫熱解過程中脂肪類硫具有較高的反應活性易XⅣSs譜圖。由圖、表可見半焦中有機硫一般只岀現(xiàn)被脫除而噻吩類硫相對穩(wěn)定噻吩仍殘留在半焦個峰停鶚41-104.5相對應為噻盼類中。 Element也指出經(jīng)熱解后焦樣中僅有微量的燃料化學學報29卷脂肪類硫的存在。本研究在快速加氬條件下進行,右。由表4可見半焦中存在的主要是噻吩類硫。我國七種煤中的脂肪類硫被全部地脫除。噻吩硫化物非常穩(wěn)定難以分解,但在750℃、由表3與表4的比較可見煤中的脂肪類硫含6.0MPa氬壓下的快速加氫熱解過程中煤中部分噻量越高則相應的有機硫脫除率也就越髙如大同煤吩也參與加氬反應表現(xiàn)岀噻吩含量的明顯降低脂肪類硫的含量約50%其有杋硫脫除率接近∞% Elemenπ°也指岀400~τ00℃~溫度范圍內(nèi)煤中噻吩左右華豐煤脫硫率也達到85%以上。由于半焦中類硫也有一定的反應活性。東勝焦樣中存在兩個有機硫含量很低相應在大同和華豐半焦ⅹⅣS譜圖峰譜峰位置仍在164.leV與165.eV,氧化態(tài)有機上幾乎很難發(fā)現(xiàn)它們的譜峰而陽泉、西山等煤中噻硫反應活性較低其脫除效果較差較脂肪類硫難脫吩類硫含量較高測有機硫脫除率較低僅55%左除。表3煤中有機硫的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半焦的有機硫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中國煤化工CNMHG0.123165.10.11373.19164.3衣數(shù)據(jù) hecked peak期朱子彬等:煙煤快速加氫熱解的研究Ⅴ482e30Binding energy E/evBinding energy ElevBinding energy E/cvXishan half-cokeCaojiazhuang half-cokeHuangxian half-coke人Yangquan hall-coke圖2半焦中有機硫XPS譜圖Figure 2 XPS of organic sulfur in half-coke3結(jié)論(2)快速加氫熱解半焦中有機硫的形態(tài)較為單1)煤中有機硫形態(tài)一般為脂肪類硫和噻吩類般僅為噻吩硫,譜峰位置在164.1~164.5eV硫NⅨ譜峰位置分別在163.1~163.5cⅤ和164.1之間盧與對應煤樣中噻吩類硫的譜峰位置是一致的。~164.5eV之間噻吩類硫的相對含量隨煤化程度3)加氫熱解能脫除全部的脂肪硫和部分的噻加深而增大吩硫脂肪硫表現(xiàn)岀了較高的加氫反應活性參考文獻[1]陳鷂.中國煤中硫的賦存特征及脫硫J]煤炭轉(zhuǎn)化,19)4,1K2):1-9[ 2] David C Frost, William R Leeder, Robert L Tapping. X-ray photoelectron spectroscopic investigation of coa[ J ] Fuel, 1974, 53 206-210[3] David L Perry Alan Grint. Application of XPS to coal characterizatio[ J ]. Fuel, 1983, 62: 1024-1028[4] Kelemen S R, George G N, Gorbaty M L. Direct determination and quantification of sulphur forms in heavy petroleum and coals IThe X-ray photoelectron spectroscopy(HJ].Fel,1990,69939-944[5] Kelemen S R, Gorbaty M L, George G N. Surface composition of iron and inorganic sulfur forms in argonne premium coals by X-rayphotoelectron spectroscop[ J]. Energy Fuels, 1991, 5 720-723[ 6] Kelemen S R, Gorbaty M L, George G N. Thermal reactivity of sulphur forms in coa[ J ] Fuel, 1991, 70 3)396-402[7] Lucinda R Hittle Andrew G Sharkey David C Frost. Determination of sulfur of coal surfaces by X-ray photoelectron spectroscop J]Fuel,1993,7x6)771-776[8]張蓬洲趙秀榮.用XN研究我國一些煤中有機硫的存在形Jn中國煤化工)205-210[9]陳鷂王景禹葛運培.兗州煤顯微組分中有機硫含量及其分和CNMHG3)238-24110] Cypres R, Furfari S, Ghodsi M. Hydropyrolysis-Third way for coal conversion J I. Erdol und Kohle- Erdgas-Pertro, 1983, 36( 10)471-476[1]朱子彬王欣榮馬智華,等.煤快速加氬熱解獲得液態(tài)烴和氣態(tài)烴的研究(Ⅲ)氣體停留時間的考察J].化工學報,1995,466):10-71612]cc有數(shù)據(jù)adML, Kelemen S R. Direct determination and quantification of sulfur forms in coals form the argo premium燃料化學學報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中國煤化工CNMHGFoundation item: National Natural Science Foundation of China( 29476232)Author introduction: ZHU Zi-bin( 1940-), male, Advisor of Dr. Postgraduate, Professor, chemical engineering