煙煤快速加氫熱解的研究

第29卷第1期燃料化學(xué)學(xué)報Vol, 29 No I201年2月JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGYFeb. 2001文章編號:0253-240X2001)1004405煙煤快速加氬熱解的研究Ⅴ.煤和半焦中有機硫化學(xué)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(xué),上海200237)摘要∶采用ⅹ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(xué)形態(tài)。煤中有機硫一般為脂肪類(lèi)硫與噻吩類(lèi)硫其譜峰位置分別在163.1-163.5V和164.~-164.5V之間。噻吩類(lèi)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(lèi)硫溍峰位置在164.1-164.5-與對應煤中噻吩硫的譜峰位置是一致的。在加氫熱解過(guò)程中全部脂眆類(lèi)硫和部分噻吩類(lèi)硫被脫除脂眆類(lèi)硫表現岀很髙旳加氫反應活性關(guān)鍵詞:煤;快速加氫熱解;硫形態(tài);ⅹ中圖分類(lèi)號:TQ530.2文獻標識碼:A研究煤中有機硫的形態(tài)對于控制煤燃燒所引加氬熱解過(guò)程中的變化規律。起的硫氧化物污染具有重要意文。將電子能譜XPs X-ray Photoelectron Spectros運用到煤的分1實(shí)驗部分1.1實(shí)驗裝置與分析方法煤快速加氫熱解的實(shí)析上為煤中有機硫的化學(xué)形態(tài)非破壞性分析提供驗裝置見(jiàn)文獻11對煤樣和半焦進(jìn)行XFS分析了一種新的手段。Fm「2最早采用XPS分析了煤中采用PH5300FSCA譜儀使用MgKa為發(fā)射源,步硫的化學(xué)形態(tài)。Pem31研究的X譜圖中硫有兩長(cháng)O.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C,284.6eV為內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(lèi)硫與噻吩類(lèi)硫。Hit!φ對煤酸洗脫灰處理未改變煤中有杋硫用orin軟件根據優(yōu)化算法對岀峰進(jìn)行Gaus擬合。ⅹS出峰位置,并消除了無(wú)機硫的影響。國內學(xué)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(jìn)行了分柝3。煤的快其樣品粉碎到60~80目對其進(jìn)行快速加氫熱解。速加氫熱解是潔凈煤利用新技術(shù),該工藝具有顯著(zhù)為避免無(wú)機硫與有機硫同時(shí)岀峰對有機硫ⅹS譜圖的脫硫效果"。本文運用ⅹPS分析了我國以煙煤的干擾本實(shí)驗對所得半焦與煤樣在ⅫS分析前粉碎為主的七種煤并同時(shí)分析了加氫熱解后所得半焦至200目進(jìn)行酸洗脫灰份處理以。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(jiàn)表1各種形態(tài)硫的分析見(jiàn)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/% dafatom) CHS12.6229.6357.750.52486.263.821.511.556.8613.5819.2214.6171.550.7185.195.031.560.647.588.7364.940.77182,794.651.081.1110.3732.409.0258.580.79481.595.401.820.7110.4833.568.8257.620.72375.074.541.250.3118.8huangxian41.299.4149.301.10775.016.881570.591595關(guān) by difference收稿日期:20005-22;修回日期:20008-121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 Analysis of sulfur type in coalInorganic sulfuOrganic sulfurTotal sulfurCoalsulphate sulfur pyrite sulfur relative content organic sulfur relative contentW/%W/%2.4567.773.5232.2310.920.631.6240.543.301.182.0258.182.3164.933.5635.0710.151.702.2060,472.5539.530.160.542.102,800.1749.442實(shí)驗結果與討論般噻吩類(lèi)硫的含量較高脂肪類(lèi)硫含量較低我國2.1煤中的有機硫化學(xué)形態(tài)表3為煤中有機硫煤的分析與 george!的實(shí)驗結果相吻合。例如西含量與XPS譜圖數據。煤樣的ⅹ譜圖如圖1所山、曹家莊與陽(yáng)泉煤的噻吩類(lèi)硫都在85%左右,東示。由圖1和表3可見(jiàn)煤中有機硫一般存在兩個(gè)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(gè)出峰分別在164.0eV與164.5cV兩處。根據文獻←1B3可知前者對應脂肪165.leV前者對應于噻吩類(lèi)硫,后者應為氧化態(tài)的類(lèi)硫脂肪類(lèi)、硫醚和硫醇等)后者對應噻吩類(lèi)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370105062163164165166160706016264166168Binding energy E/evBinding energy E/eVBinding cncrgy E/cVtshan coaCaojiazhuang coal8016640160162164166rgy ElevBinding encrgy E/cVBinding cnergy F/eVBinding energy evHuangxian coal圖1煤中有機硫的XFS譜圖Figure 1 XPs of organic sulfur in coal2.2半焦中有機硫化學(xué)形態(tài)表4為加氫熱解半硫與煤樣中噻吩類(lèi)硫岀峰位置是一致的。這說(shuō)明焦中有機硫含量和ⅹⅣS譜圖數據,圖2為半焦的加氫熱解過(guò)程中脂肪類(lèi)硫具有較高的反應活性易XⅣSs譜圖。由圖、表可見(jiàn)半焦中有機硫一般只岀現被脫除而噻吩類(lèi)硫相對穩定,噻吩仍殘留在半焦燃料化學(xué)學(xué)報卷脂肪類(lèi)硫的存在。本研究在快速加氬條件下進(jìn)行,右。由表4可見(jiàn),半焦中存在的主要是噻吩類(lèi)硫。我國七種煤中的脂肪類(lèi)硫被全部地脫除噻吩硫化物非常穩定,難以分解,但在750℃、由表3與表4的比較可見(jiàn)煤中的脂肪類(lèi)硫含6.0MPa氬壓下的快速加氫熱解過(guò)程中煤中部分噻量越高則相應的有機硫脫除率也就越高如大同煤吩也參與加氬反應,表現岀噻吩含量旳明顯降低,脂肪類(lèi)硫的含量約50%其有杋硫脫除率接近∞% Elemenπ6也指岀400~700℃~溫度范圍內煤中噻吩左右華豐煤脫硫率也達到85%以上。由于半焦中類(lèi)硫也有一定的反應活性。東勝焦樣中存在兩個(gè)有機硫含量很低相應在大同和華豐半焦ⅹS譜圖峰,譜峰位置仍在164.1eV與165.1eV,氧化態(tài)有機上幾乎很難發(fā)現它們的譜峰而陽(yáng)泉、西山等煤中噻硫反應活性較低其脫除效果較差絞脂眆類(lèi)硫難脫吩類(lèi)硫含量較高則有機硫脫除率較低,僅55%左除。表3煤中有機硫的ⅹ分析Table 3 XPs analysis data of organic sulfur in coalOrganic sulfur content W/% Peak number Peak position Model compound Relative content W/%163.5thiophene163,1aliphatic sulfurXishan0.3302121212121164.5thiophene163.110.Caojiazhuang0.231164.5163.345.10Datong164.1thiophene54.90163.131.05Huafeng0.25568.95164.00.21029.23Huangxian0.262164.2表4半焦的有機硫XFS分析Table 4 XPS analysis data of organic sulfur in harf-cokeOrganic sulfur Peak peak ModelRelative content Removing rate ofHarf-cocontent W/% number positioncompouorganic sulfur w/%Ya0.18656.73Xishan0.21656.75Caojiazhuang0.135164,41000.0688,870.123165.1sulfur oxide310.11373.19期朱子彬等:煙煤快速加氫熱解的研究Ⅴ472s30人人BBinding energy E/evBinding energy E/evBinding energy E/evXishan half-cokeCaojiazhuang half-coke660人162164166168170Binding energy E/eV圖2半焦中有機硫XPS譜圖Figure 2 XPs of organic sulfur in half-coke3結論(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(lèi)硫和噻吩類(lèi)般僅為噻吩硫譜峰位置在164.1~164.5eV硫ⅨS譜峰位置分別在163.1-163.5cⅤ和164.1之間與對應煤樣中噻吩類(lèi)硫的譜峰位置是一致的。l64.5eV之間噻吩類(lèi)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]煤炭轉化,1994,172)1-9[ 2] David C Frost, William R Leeder, Robert L Tapping. 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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 thiophene content in coal increased with coal rank. The type of organic sulfur in semi-coke in flash hydropyrolysis 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 notable desulfurization effectKey words coal i flash hydropyrolysis sulfur type ; XPSFoundation item: National Natural Science Foundation of China( 29476232)