煤瀝青對不同變質(zhì)程度煤成焦性能的影響

第36卷第2期煤炭轉化Vol. 36 No. 22013年4月COAL CONVERSIONApr. 2013煤瀝青對不同變質(zhì)程度煤成焦性能的影響白永建"許德平2) 王 永剛2)摘要為了考察煤瀝青與不同變質(zhì)程度煤的共炭化特性,利用40 kg小焦爐模擬煉焦試驗，進(jìn)行了單種煤5%與10%的煤瀝青添加的各煤種的炭化研究.研究結果表明，瀝青對不同變質(zhì)程度煤生成焦炭的顯微結構影響不同.對低變質(zhì)程度的中低黏結性煤,增加了焦炭光學(xué)組織指數OTI;對黏結組分充足的中等變質(zhì)程度煤的OTI影響較小;對高變質(zhì)程度煤OTI影響顯著(zhù).瀝青對不同變質(zhì)程度煤生成焦炭的機械性能影響不同.對低變質(zhì)程度的中低黏結性煤,溶解作用較明顯,對機械強度有較大改善;對黏結組分充足的中等變質(zhì)程度煤的成焦性能影響較小;對高變質(zhì)程度煤成焦性能影響最為明顯,可顯著(zhù)改善焦炭機械性能和熱性質(zhì).關(guān)鍵詞煤瀝青,變質(zhì)程度,熱性質(zhì),結焦性能中圖分類(lèi)號TQ520. 60引言1實(shí)驗部分煤焦油瀝青是高度縮聚的碳環(huán)和雜環(huán)化合物組1.1實(shí)驗用煤成的高分子有機物,具有與煤同源的組成和結構,但在環(huán)構化程度和分子組成上存在差異，炭化時(shí)體現選用不同變質(zhì)程度的6種煤,全部為洗精煤,分較高的流動(dòng)性,可用于增強原料煤的黏結性.在配煤別來(lái)自山西各煤礦和陜西(長(cháng)焰煤),其分析數據見(jiàn)或單種煤添加煤瀝青后,能提高焦化過(guò)程中煤料塑表1.由表1可知,兩種低變質(zhì)程度的長(cháng)焰煤和氣性物的流動(dòng)度,促進(jìn)不熔融煤粒的濕潤,使煤質(zhì)均勻煤,其黏結指數G較低,分別為13和68.兩種中等化,改善煤的成焦性.[18]利用煤瀝青良好的潤濕性變質(zhì)程度的肥煤和焦煤,其黏結指數較高,具有較高及結焦能力,煉焦工業(yè)可用作配煤的活性黏結劑以的黏結性和結焦性.而較高變質(zhì)程度的瘦煤和貧瘦提高配煤中的活性組分.煤瀝青與煤共炭化時(shí)的相煤,其黏結指數較低,分別為56和16.互作用程度,取決于瀝青和煤的性質(zhì).如果煤瀝青與表1實(shí)驗用煤的性質(zhì)Table 1 Proximate and ultimate analysis of coals煤共炭化時(shí)是相互獨立的，就不會(huì )對煤發(fā)生改性作SampleAses/% Vau/% Sas/% GRI Y/mm Rmx/%用,而只是我們理解上的物理熔融黏結.如果瀝青在Long flame coal 5.37 39.47 0.42 13.0 00. 534與煤共炭化時(shí)能溶解煤的組分,經(jīng)過(guò)中間相生成焦Gas coal5.52 40.19 0.52 68.011.00.712炭,則是我們理解上的化學(xué)作用.化學(xué)作用的結果使28.5 1.088Coking coal 10.43 21.76 1.06 88.5 18.9 1. 253得焦炭的顯微結構發(fā)生改變,使得生成焦炭的各向Lean coal8.97 17.33 1.09 56.012.7 1. 611異性程度增加.瀝青的供氫性以及其塑性物的流動(dòng)Meager lean coal 10.21 13.43 0.43 16.001.797度是體現這一作用程度的重要參數,而煤的性質(zhì)也1.2 煤瀝青決定相互作用的程度.[7:9]本研究在選定的瀝青條件下,系統考察瀝青與不同變質(zhì)程度煤炭化的配伍性，本實(shí)驗用煤瀝青來(lái)自山西某焦油加工企業(yè),其通過(guò)測定共炭化焦炭的顯微結構和組成,分析煤瀝灰分為0.11% ,揮發(fā)分為56. 21%,硫分為0. 44%.青對不同變質(zhì)程度煤的作用程度和機理，更好地指煤瀝青單獨成焦焦炭塊度大,呈銀灰色光澤,氣孔.導實(shí)際煉焦生產(chǎn)實(shí)踐.多,呈蜂窩狀，-中國煤化工應性CRI為*國家自然科學(xué)基金資助項目(21076222).YHCNMHG1)博士生;2)教授,中國礦業(yè)大學(xué)(北京)化學(xué)與環(huán)境工程學(xué)院, 10083北京收稿8期:2012-10-19;修回日期:2012-12-30.6煤炭轉化2013年71.7,反應后強度CSR為29. 6.瀝青焦的光學(xué)顯微溫為1050C,結焦時(shí)間控制為10h.焦炭Moo,Mzs組織特征見(jiàn)表2.由表2可以看出,瀝青焦的光學(xué)組和M。按GB/T2006-94《冶金焦炭機械強度的測織異性程度較高,主要是中粗粒鑲嵌結構,光學(xué)組織定方法》測定，焦炭光學(xué)顯微結構按YB/T077-指數OTI接近200.1995<焦炭光學(xué)組織的測定方法》測定,焦炭反應性表2煤瀝青焦的光學(xué)組織結構和反應后強度按GB/T 4000- -2008《 焦炭反應性及Table 2 Optical structure of coal tar pitch反應后強度試驗方法》測定.Medium and FlowDis continuousIsotropicgrain set corse mosicsrDomaindomnainZIso oT12結果與討論3.190.8 1.5 2.1.95.0 196.91.3 實(shí)驗過(guò)程將單種煤粉碎至<3 mm,混勻搗固至密度為2.1煤瀝青與低變質(zhì)煤的共炭化0.95 g/cm ,水分調整至9.5%.利用40 kg小焦爐煤瀝青分別與低變質(zhì)程度的長(cháng)焰煤和氣煤共炭模擬煉焦,按照煤瀝青5%與10%的比例分別添加化成焦,瀝青的添加量分別是0%,5%和10%.炭化到低、中、高變質(zhì)程度的煤中進(jìn)行焦化實(shí)驗.炭化終成焦后的光學(xué)顯微結構和機械強度見(jiàn)表3.表3煤瀝青與低變質(zhì)程度煤共炭化焦炭性質(zhì)Table 3 Properties of coke from cor-carbonization of coal tar pitch and low rank coalMedium andBasicSamplelorop Fine mosis Corse mosaiesFlow typeDormain Fusiniteaisitopio2Iso OTI Mo Mzs MoLong flame coal80.71..796.6 8.5 0 0 100Long flame cal+5% coal tar pich 67.0.2.028.795.7 10.7 11.8 26.5 64.7Long flame coal+ 10% col tar pich 71.06..9.10.18.489.4 17.0 70.0 83.13.Gas coal2.92.4.61.:45.680.510.Long flame col2045.187.1 23.8 69.4 83.5 5.Long fame coal+5% coalarpich_ 69.4..320.689.9 21.8 76.0 85.8.由表3可見(jiàn)，與原煤?jiǎn)为毺炕啾?低變質(zhì)程度別為29.6,31.5和22.0,反應性和反應后強度變化長(cháng)焰煤中配人不同比例的瀝青后,光學(xué)各向同性組沒(méi)有呈現明顯的規律.分含量明顯減少,細粒鑲嵌組分含量增加.盡管不同從以上結果可以看到，瀝青明顯改善了長(cháng)焰煤各向異性程度的組分隨瀝青添加量增加呈現一些不的炭化特性,提高了焦炭顯微組分的各向異性程度規則的波動(dòng),但總體趨勢是光學(xué)組織指數OTI逐漸和機械性能.低變質(zhì)煤含有較高的含氧官能團,交聯(lián)增加,由8.5分別增加到10.7和17.反應性較強,單獨炭化時(shí)不容易生成穩定的液相組值得注意的是瀝青添加明顯提高了生成焦炭的分,因而沒(méi)有黏結性,或呈現較弱的黏結性.與瀝青機械性能.瀝青添加量為5%和10%時(shí),生成焦炭的共炭化,瀝青將煤熱解組分有效溶解,促進(jìn)了中間相抗碎強度M。由0分別提高到11.8和70,M25也有的生成,使焦炭的光學(xué)性能得到改善.同時(shí),也改善相同的規律.耐磨強度Mo由100 改變?yōu)?4.7和了焦炭的機械性能.13. 0,耐磨性能顯著(zhù)提高.2.2煤瀝青與中等變質(zhì)程 度煤共炭化由表3還可見(jiàn)，與原煤?jiǎn)为毺炕啾?低變質(zhì)程第61頁(yè)表4是煤瀝青與中等變質(zhì)程度兩種煤度氣煤中配人不同比例的瀝青后,光學(xué)各向同性組共炭化的焦炭性質(zhì).由表4可知,添加瀝青進(jìn)行炭化分含量略有增加，細粒鑲嵌和粗粒鑲嵌組分含量有后，肥煤的焦炭的各向同性組分含量略有下降,細粒些波動(dòng),光學(xué)組織指數OTI隨瀝青添加量增加也呈鑲嵌含量上升,中粗粒鑲嵌和流動(dòng)性組分略有下降，現一些不規則的波動(dòng).整體結果是焦炭的光學(xué)指數OTI沒(méi)有明顯變化.從瀝青添加對低變質(zhì)程度氣煤的機械性能影響不生成焦炭的機械性能來(lái)看,Mso和M25略有下降,M1o明顯,M。o呈現增加的趨勢,由單獨炭化的57.2分略有上升.焦煤與瀝青的共炭化,大致呈現相同的規別增加到69.4和76,M2s略微增加,Mo變化不明律，只是有些數據的波動(dòng).其光學(xué)顯微組分含量變化顯;此外,還測定了瀝青與氣煤共炭化焦炭的熱性不明顯,光學(xué)MH中國煤化工有變化，M。和質(zhì),對應于瀝青添加量為0%,5%和10%,其反應性M2s略有降佴CNMH G青對中等變質(zhì)CRI分別為53.0,55.8和46.5;反應后強度CSR分程度的肥煤、焦煤的成焦性能修飾無(wú)明顯作用..62煤炭轉化2013年數OTI,如瘦煤添加較大量的煤瀝青時(shí)可發(fā)展到流強度.與同屬低變質(zhì)程度的氣煤共炭化,盡管增強了動(dòng)型組分.同時(shí)瀝青也能改善界面的結合狀態(tài),提高焦炭的各向異性程度,但對機械性能的改變不大.瀝了結焦性能.青與黏結組分充足的中等變質(zhì)程度煤共炭化時(shí),對生成焦炭的光學(xué)顯微組分影響較小,對焦炭的機械性能也影響較小.煤瀝青與高變質(zhì)程度煤共炭化,改.善或瀝青的修飾效果較明顯，焦炭的光學(xué)顯微結構改變較大,焦炭的機械性能改善明顯.煤瀝青與煤共炭化具有改變焦炭顯微結構與增加焦炭裂紋和空隙的雙重效應,兩者對機械性能的貢獻是相反的,兩者可以相互補償.當瀝青對焦炭光學(xué)各向異性的影響較強時(shí),體現為顯微強度的增強，這在低變質(zhì)和高變質(zhì)煤與瀝青的共炭化時(shí)都得到了圖2中 粗粒鑲嵌組分Fig.2 Component inlaid by middle and coarse grain體現.當瀝青對焦炭光學(xué)各向異性的影響較弱時(shí),則觀(guān)察不到顯微強度的明顯增強,這在中等變質(zhì)程度煤與瀝青的共炭化時(shí)得到了體現.3結.論1)瀝青對不同變質(zhì)程度煤生成焦炭的顯微結構影響不同.對低變質(zhì)程度的中低黏結性煤,增加了焦炭組織指數OTI,對黏結組分充足的中等變質(zhì)程度煤的OTI影響較小，對高變質(zhì)程度煤OTI增加明顯2)瀝青對不同變質(zhì)程度煤生成焦炭的機械性圖3 流動(dòng)型組分Fig. 3 Component of flow model能影響不同.對低變質(zhì)程度的中低黏結性煤,溶解作煤瀝青與不同變質(zhì)程度煤共炭化呈現了不同的用較明顯,對機械強度有較大改善;對黏結組分充足規律.由以上結果可以看出,在煉焦配煤中,煤瀝青的中等變質(zhì)程度煤的成焦性能影響較小;對高變質(zhì)與低變質(zhì)程度的長(cháng)焰煤共炭化時(shí),熱溶解作用較明程度煤炭化性能影響最為明顯,可改善焦炭機械性顯,增強了焦炭的各向異性,同時(shí)提高了焦炭的機械能和熱性質(zhì).參考文獻[1]肖瑞華.煤焦油化工學(xué)[M].北京:冶金工業(yè)出版社.2002:240-257.[2]申峻,鄒綱明,王志忠.煤與各種舔加物共碳化的研究進(jìn)展[J].煤炭轉化,1999,22(3):6-9.[3]李顏冰，吳斌譯.各種煤加入煤焦油瀝青的碳化[J].國外煉焦化學(xué),1995(5):261-266.[4] 任先順,白永建,楊雙鳳等.貧煤與煤瀝青共炭化研究[J].燃料與化工,2010,41(2):15-17.[5] Mochida I,Matsuoka H,Korai Y et al. Carbonization of Coals to Produce Anisotropic Cokes 1: Modifying Activities of SomeAdditives in the Co-carbonization of Low-rank Coals[J]. Fuel, 1982 ,61(7):587-594.[6] Iyama S, Yokono T ,Sanada Y. Development of Anisotropic Texture in Co-carbonization of Low Rank Coal with Pitch-evalua-tion from Hydrogen Donor and Acceptor Abilties of Coal and Pich[J]. Carbon, 1986,24(4) :423-428.[7] Gonzalez M J, Patrick J W , Walker A. Influence of Pitch Aditions on Coal Carbonization:Characterization of Pitches[J]. Fu-el,1987 ,611):1522-1526[8] Gonzalez M J, Partrick J W ,Walker A et al. Influence of Pitch Additions on Coal Carbonization:Coke Strength and StructuralProperties[J]. Fuel,1987 ,66(8) :1019-1023.[9] 鄭明東，王曉燕.影響焦炭熱態(tài)性質(zhì)的因素探討[J].燃料與化工,2008,39(2):1-4.中國煤化工78頁(yè))MHCNMH G.78煤炭轉化2013年STUDY ON INFLUENCE OF HEAT BINDER ON PROPERTIESOF BRIQUETTE FROM LOW RANK BITUMINOUS .COALS UNDER HOT STATEHuang Shanxiu and Ma Mingjie(School of Materials Science and Engineering, He' nan PolytechricUniversity, 454000 J iaoruo, He' nan)ABSTRACTTwo different materials such as coal tar pitch, fat coal with high adhesion werechosen as the heat binder, which were mixed into the powder of low rank bituminous coals fromShenmu or Yuzhou and other raw materials to make coal briqutte in different ration. The deter-mination results show that the thermal strength of coal briquette with tar pitch is higher than thatof coal briquette with fat coal. Further analysis of micro-structure of coal briquette by electronmicroscopic also verifies that the cohesion and water resistance of coal briquette with tar pitch isstronger, and it is because that interaction of air bubble poduced by volatile separated under hotstate through colloid pressures the colloid and form the stronger net -structure on coal granulessurface. Moreover, the particle size of tar pitch also have certain effect on thermal strength ofcoal briquette.KEY WORDS low rank bituminous coal ，coal briquette, thermal strength, heat binder, mi-cro-structrue, particle size of pitch(上接第62頁(yè))EFFECT OF COAL TAR PITCH ON THE COKING PERFORMANCESFROM DIFFERENT RANK OF COALSBai Yongjian Xu Deping and Wang Yonggang(School of Chemical and Environmental Engineering，China Universityof Mining and Technology, 100083 Beijing)ABSTRACT To study the co-carbonization between coal tar pitch and different rank of coal,experiments of charring between 5% and 10% of coal tar pitch and coals were studied, whichwere test in coke oven of 40 kg. The results showed that, the microstructures of cokes charredfrom different rank of coals and coal tar pitch were different. The pitch increased the OpticalTexture Index (OTI) of the coke from low rank of coals and high rank of coals, and had littleeffect on that from middle rank of coals. The mechanical behaviors of cokes charred from different rank of coals and coal tar pitch were also different. The cokes from low rank of coals hadhigh mechanical strength because of obviously dissolution; the cokes from middle rank of coalshad little effect with pitch; however, the pitch obviously improves the mechanical capacities andthermal properties of the coke charred from high rank of coals.中國煤化工KEY WORDS coal tar pitch, rank of coal, thermal proper|,MHCNMH G.