第29卷第1期燃料化學(xué)學(xué)報(bào)Vol, 29 No I201年2月JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGYFeb. 2001文章編號(hào):0253-240X2001)1004405煙煤快速加氬熱解的研究Ⅴ.煤和半焦中有機(jī)硫化學(xué)形態(tài)剖析朱子彬,朱宏斌,吳勇強(qiáng),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(guó)以煙煤為主的七種煤樣以及對(duì)應(yīng)的快速加氬熱解半焦中有機(jī)硫的化學(xué)形態(tài)。煤中有機(jī)硫一般為脂肪類硫與噻吩類硫其譜峰位置分別在163.1-163.5V和164.~-164.5V之間。噻吩類硫的相對(duì)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164.1-164.5-與對(duì)應(yīng)煤中噻吩硫的譜峰位置是一致的。在加氫熱解過(guò)程中全部脂眆類硫和部分噻吩類硫被脫除脂眆類硫表現(xiàn)岀很髙旳加氫反應(yīng)活性關(guān)鍵詞:煤;快速加氫熱解;硫形態(tài);ⅹ中圖分類號(hào):TQ530.2文獻(xiàn)標(biāo)識(shí)碼:A研究煤中有機(jī)硫的形態(tài)對(duì)于控制煤燃燒所引加氬熱解過(guò)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XPs X-ray Photoelectron Spectros運(yùn)用到煤的分1實(shí)驗(yàn)部分1.1實(shí)驗(yàn)裝置與分析方法煤快速加氫熱解的實(shí)析上為煤中有機(jī)硫的化學(xué)形態(tài)非破壞性分析提供驗(yàn)裝置見(jiàn)文獻(xiàn)11對(duì)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(zhǎng)O.leV,最低分辨率為0.1%粉末樣使用 Scotch峰分別對(duì)應(yīng)為有機(jī)硫與硫酸鹽硫。 Kelemen[4-6]帶固定采用C,284.6eV為內(nèi)標(biāo)校正荷電位移并采的研究表明煤中有機(jī)硫分別為脂肪類硫與噻吩類硫。Hit!φ對(duì)煤酸洗脫灰處理未改變煤中有杋硫用orin軟件根據(jù)優(yōu)化算法對(duì)岀峰進(jìn)行Gaus擬合。ⅹS出峰位置,并消除了無(wú)機(jī)硫的影響。國(guó)內(nèi)學(xué)者1.2試樣選用我國(guó)煤化程度不同的七種煤樣亦對(duì)我國(guó)煤中有機(jī)硫形態(tài)進(jìn)行了分柝3。煤的快其樣品粉碎到60~80目對(duì)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),該工藝具有顯著為避免無(wú)機(jī)硫與有機(jī)硫同時(shí)岀峰對(duì)有機(jī)硫ⅹS譜圖的脫硫效果"。本文運(yùn)用ⅹPS分析了我國(guó)以煙煤的干擾本實(shí)驗(yàn)對(duì)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(jī)硫以考察我國(guó)煤中有機(jī)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(yàn)結(jié)果與討論般噻吩類硫的含量較高脂肪類硫含量較低我國(guó)2.1煤中的有機(jī)硫化學(xué)形態(tài)表3為煤中有機(jī)硫煤的分析與 george!的實(shí)驗(yàn)結(jié)果相吻合。例如西含量與XPS譜圖數(shù)據(jù)。煤樣的ⅹ譜圖如圖1所山、曹家莊與陽(yáng)泉煤的噻吩類硫都在85%左右,東示。由圖1和表3可見(jiàn)煤中有機(jī)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(jù)文獻(xiàn)←1B3可知前者對(duì)應(yīng)脂肪165.leV前者對(duì)應(yīng)于噻吩類硫,后者應(yīng)為氧化態(tài)的類硫脂肪類、硫醚和硫醇等)后者對(duì)應(yīng)噻吩類硫。有機(jī)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(jī)硫的XFS譜圖Figure 1 XPs of organic sulfur in coal2.2半焦中有機(jī)硫化學(xué)形態(tài)表4為加氫熱解半硫與煤樣中噻吩類硫?qū)绶逦恢檬且恢碌?。這說(shuō)明焦中有機(jī)硫含量和ⅹⅣS譜圖數(shù)據(jù),圖2為半焦的加氫熱解過(guò)程中脂肪類硫具有較高的反應(yīng)活性易XⅣSs譜圖。由圖、表可見(jiàn)半焦中有機(jī)硫一般只岀現(xiàn)被脫除而噻吩類硫相對(duì)穩(wěn)定,噻吩仍殘留在半焦燃料化學(xué)學(xué)報(bào)卷脂肪類硫的存在。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硫。我國(guó)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(jiàn)煤中的脂肪類硫含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(yīng)的有機(jī)硫脫除率也就越高如大同煤吩也參與加氬反應(yīng),表現(xiàn)岀噻吩含量旳明顯降低,脂肪類硫的含量約50%其有杋硫脫除率接近∞% Elemenπ6也指岀400~700℃~溫度范圍內(nèi)煤中噻吩左右華豐煤脫硫率也達(dá)到85%以上。由于半焦中類硫也有一定的反應(yīng)活性。東勝焦樣中存在兩個(gè)有機(jī)硫含量很低相應(yīng)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(jī)上幾乎很難發(fā)現(xiàn)它們的譜峰而陽(yáng)泉、西山等煤中噻硫反應(yīng)活性較低其脫除效果較差絞脂眆類硫難脫吩類硫含量較高則有機(jī)硫脫除率較低,僅55%左除。表3煤中有機(jī)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(jī)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(jī)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(jī)硫的形態(tài)較為單1)煤中有機(jī)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ⅨS譜峰位置分別在163.1-163.5cⅤ和164.1之間與對(duì)應(yīng)煤樣中噻吩類硫的譜峰位置是一致的。l64.5eV之間噻吩類硫的相對(duì)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(yīng)活性。參考文獻(xiàn)[1]陳鷂,中國(guó)煤中硫的賦存特征及脫硫J]煤炭轉(zhuǎn)化,1994,172)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 characterization[ 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( XPS )approacH J ]. Fuel, 1990, 69 939-944[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, 703)396-402[7] Lucinda R Hittle, Andrew G Sharkey, David C Frost. Determination of sulfur of coal surfaces by X-ray photoelectron spectroscop[ J]Fe,1993,7x6):71-776[8]張蓬洲趙秀榮.用ⅪFS研究我國(guó)一些煤中有機(jī)硫的存在形氮冂]燃料化學(xué)學(xué)報(bào),1993,2K2)205-210.[9]陳鷂王景禹葛運(yùn)培.兗州煤顯微組分中有杋硫含量及其分J.燃料化學(xué)學(xué)報(bào),1997,2(3)38-24110 Cypres R, Furfari S, Ghodsi M. Hydropyrolysis-Third way for coal conversion[ J ]. Erdol und Kohle- Erdgas- Pertro, 1983, 3( 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(shí)間的考J]化工學(xué)報(bào)燃料化學(xué)學(xué)報(bào)卷sumple progran[ J ] Energy &e Fuels, 1991, 5 93-9813 Martin L Gorbaty Simon R Kelemen, Graham N George. Characterization and thermal reactivity of oxidized organic sulphur formscoal[ J].Fiel,1992,71:255-1261RESEARCH 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 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)