合成煤中钠对煤燃烧及灰特性影响
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摘要
准东煤中钠含量高,燃用时锅炉会出现严重结渣问题。通过向准东煤为原料制取的超纯煤中添加灰的模型化合物,得到合成煤。并在此基础上利用热重-差示扫描量热分析法(TG/DTG/DSC)、X射线衍射仪(XRD)和灰熔融温度测定分析手段,研究Na_2O含量对煤燃烧特性和灰熔融性的影响。结果表明:钠主要影响合成煤的着火温度(Ti)与焦炭燃烧阶段,钠含量增加使Ti升高,并且Na_2O在灰中质量分数由5%升高至8%后,钠含量增加使焦炭燃烧速率先减小后加快,并能够改善煤粉燃尽特性。钠能够降低灰熔融温度,并在Na_2O质量分数高于5%后,温度下降更加明显。在三元相图中钠对莫来石的助熔作用是造成灰熔融温度降低的重要原因。XRD分析表明Na_2O含量增加,充当骨架作用的石英在钠的助熔作用下与难熔矿物硅钙石、MgO等生成低熔点长石类矿物,这类矿物在高温下有助熔作用,能够降低灰熔融温度。同时还生成助熔性含钠矿物霞石,加剧了灰熔融。
The sodium content of Zhundong coal is high and the boiler will face severe slagging problems during the combustion.Synthetic coals were obtained by adding ash model compounds to ultrapure coal which was obtained from the Zhundong coal.And the effects of Na2O on the combustion performance and ash fusion characteristics of coal were studied by using thermogravimetric-differential scanning calorimetry(TG/DTG/DSC),X-ray diffraction(XRD)and ash fusion temperature test.The results showed that:sodium mainly affected the ignition temperatureand the stage of char combustion of the synthetic coal.The increasing of sodium would rise the Ti.When the mass fraction of Na_2O increased from 5%to8%,the rate of char combustion decreased first and then accelerated.Sodium could improve the burnout characteristics of coal and would decrease ash fusion temperature which was more obviously when5%.The fluxing effect of sodium to mullite in the ternary phase diagram was the important reason of the decreasing ash fusion temperature.XRD analysis showed that quartz,which acts as a framework in ash,can react with refractory minerals(such as xonotlite and MgO)to generate low-melting feldspar minerals under the fluxing action of sodium.These feldspar minerals would promote ash melting under high temperature and decrease ash fusion temperature.At the same time,the generated nepheline could intensify ash fusion.
The sodium content of Zhundong coal is high and the boiler will face severe slagging problems during the combustion.Synthetic coals were obtained by adding ash model compounds to ultrapure coal which was obtained from the Zhundong coal.And the effects of Na2O on the combustion performance and ash fusion characteristics of coal were studied by using thermogravimetric-differential scanning calorimetry(TG/DTG/DSC),X-ray diffraction(XRD)and ash fusion temperature test.The results showed that:sodium mainly affected the ignition temperatureand the stage of char combustion of the synthetic coal.The increasing of sodium would rise the Ti.When the mass fraction of Na_2O increased from 5%to8%,the rate of char combustion decreased first and then accelerated.Sodium could improve the burnout characteristics of coal and would decrease ash fusion temperature which was more obviously when5%.The fluxing effect of sodium to mullite in the ternary phase diagram was the important reason of the decreasing ash fusion temperature.XRD analysis showed that quartz,which acts as a framework in ash,can react with refractory minerals(such as xonotlite and MgO)to generate low-melting feldspar minerals under the fluxing action of sodium.These feldspar minerals would promote ash melting under high temperature and decrease ash fusion temperature.At the same time,the generated nepheline could intensify ash fusion.
引文
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[2]陈川,张守玉,刘大海,等.新疆高钠煤中钠的赋存形态及其对燃烧过程的影响[J].燃料化学学报, 2013, 41(7):832-838.CHEN C, ZHANG S Y, LIU D H, et al. Existence form of sodiumin high sodium coals from Xinjiang and its effect on combustionprocess[J]. Journal of Fuel Chemistry and Technology, 2013, 41(7):832-838.
[3]陈新蔚,庄新国,周继兵,等.准东煤田煤质特征及分布规律[J].新疆地质, 2013(1):89-93.CHEN X W, ZHUANG X G, ZHOU J B, et al. Coal qualityfeatures and distribution of Zhundong coalfield[J]. XinjiangGeology, 2013(1):89-93.
[4]陶玉洁.高碱金属准东煤燃烧特性及灰渣行为的基础研究[D].杭州:浙江大学, 2015.TAO Y J. Basic research on combustion characteristics and ashbehaviors of high-alkali Zhundong coal[D]. Hangzhou:ZhejiangUniversity, 2015.
[5] SONG G L, QI X B, SONG W J, et al. Slagging behaviors of highalkali Zhundong coal during circulating fluidized bed gasification[J]. Fuel, 2016, 186:140-149.
[6]白向飞,王越,丁华,等.准东煤中钠的赋存状态[J].煤炭学报,2015, 40(12):2909-2915.BAI X F, WANG Y, DING H, et al. Modes of occurrence ofsodium in Zhundong coal[J]. Journal of China Coal Society, 2015,40(12):2909-2915.
[7] QI X B, SONG G L, SONG W J, et al. Combustion performanceand slagging characteristics during co-combustion of Zhundongcoal and sludge[J]. Journal of the Energy Institute, 2018, 91(3):397-410.
[8]高姗姗,金晶,刘敦禹,等.蛭石复合添加剂对准东煤灰特性影响[J].化工进展, 2017, 36(9):3280-3286.GAO S S, JIN J, LIU D Y, et al. Effect of vermiculite compositeadditives on the anti-slagging behavior during combustion ofZhundong coal[J]. Chemical Industry and Engineering Progress,2017, 36(9):3280-3286.
[9] CHEN X D, KONG L X, JIN B, et al. Effect of Na2O on mineraltransformation of coal ash under high temperature gasification condition[J]. Journal of Fuel Chemistry&Technology, 2016, 44(3):263-272.
[10] NIU Y Q, WANG Z Z, ZHU Y M, et al. Experimental evaluation ofadditives and K2O–SiO2–Al2O3diagrams on high-temperaturesilicate melt-induced slagging during biomass combustion[J].Fuel, 2016, 179:52-59.
[11] SONG W J, SONG G L, QI X B, et al. Speciation and distributionof sodium during Zhundong coal gasification in a circulatingfluidized bed[J]. Energy&Fuels, 2017, 31(2):1889-1895.
[12] NANOU P, MURILLO H E G, SWAAIJ W P M V, et al. Intrinsicreactivity of biomass-derived char under steam gasificationconditions-potential of wood ash as catalyst[J]. ChemicalEngineering Journal, 2013, 217(2):289-299.
[13]翁青松,王长安,车得福,等.准东煤碱金属赋存形态及对燃烧特性的影响[J].燃烧科学与技术, 2014, 20(3):216-221.WENG Q S, WANG C A, CHE D F, et al. Alkali metal occurrencemode and its influence on combustion characteristics in Zhundongcoals[J]. Journal of Combustion Science and Technology, 2014, 20(3):216-221.
[14]刘辉,许连飞,朱书骏,等.水溶钠对准东煤快速热解煤焦燃烧特性的影响[J].煤炭学报, 2016, 41(5):1259-1265.LIU H, XU L F, ZHU S J, et al. Effect of water-soluble sodium oncombustion characteristics of Zhundong rapidly pyrolyzed coalchar[J]. Journal of China Coal Society, 2016, 41(5):1259-1265.
[15] ZHANG H X, GUO X W, ZHU Z P. Effect of temperature ongasification performance and sodium transformation of Zhundongcoal[J]. Fuel, 2017, 189:301-311.
[16]肖劲,王炳杰,李发闯,等.酸碱法制备超纯煤[J].煤炭技术,2016, 35(1):290-292.XIAO J, WANG B J, LI F C, et al. Preparation of ultra-clean coalby acid-alkali method[J]. Coal Technology, 2016, 35(1):290-292.
[17]曾凡.常规酸碱化学脱灰法:超纯煤的选制工艺专题之三[J].煤炭加工与综合利用, 1995(1):32-36.ZENG F. Conventional acid-alkali chemical deliming method:thethird of the selection process of ultra-pure coal[J]. CoalProcessing and Comprehensive Utilization, 1995(1):32-36.
[18] WANG C P, WANG F Y, YANG Q R, et al. Thermogravimetricstudies of the behavior of wheat straw with added coal duringcombustion[J]. Biomass and Bioenergy, 2009, 33(1):50-56.
[19]聂其红,孙绍增,李争起,等.褐煤混煤燃烧特性的热重分析法研究[J].燃烧科学与技术, 2001, 7(1):72-76.NIE Q H, SUN S Z, LI Z Q, et al. Thermogravimetric analysis onthe combustion characteristics of brown coal blends[J]. Journal ofCombustion Science and Technology, 2001, 7(1):72-76.
[20]鄢晓忠,邱靖,尹艳山,等.褐煤中官能团对其燃烧特性的影响[J].煤炭科学技术, 2016, 44(4):169-174.YAN X Z, QIU J, YIN Y S, et al. Effects of functional groups inlignite on its combustion characteristics[J]. Coal Science andTechnology, 2016, 44(4):169-174.
[21]刘建忠,刘明强,赵卫东,等.褐煤半焦燃烧特性的热重试验研究[J].热力发电, 2013, 42(11):86-92.LIU J Z, LIU M Q, ZHAO W D, et al. Thermogravimetric study oncombustion characteristics of lignite semicoke[J]. Thermal PowerGeneration, 2013, 42(11):86-92.
[22]侯康,武建军,尚晓玲,等.热重法研究逐级脱矿对褐煤燃烧特性的影响[J].化工进展, 2017, 36(3):900-908.HOU K, WU J J, SHANG X L, et al. Experimental study on effects of stepwise removal of minerals on the combustion characteristicsof lignites by TG/DTG[J]. Chemical Industry and EngineeringProgress, 2017, 36(3):900-908.
[23]张洪,蒲文秀,哈斯,等.化学脱灰对低灰煤粉性质的影响[J].工程热物理学报, 2009, 30(4):699-702.ZHANG H, PU W X, HA S, et al. Influence of acid treatment onthe properties of pulverized coals with low ash content[J]. Journalof Engineering Thermophysics, 2009, 30(4):699-702.
[24]肖劲,李发闯,邓松云,等.酸碱脱灰对煤结构及其热解特性的影响[J].中南大学学报(自然科学版), 2016, 47(1):14-19.XIAO J, LI F C, DENG S Y, et al. Influence of demineralization onstructure and pyrolysis characteristics of coal with acid-alkalimethod[J]. Journal of Central South University(Science andTechnology), 2016, 47(1):14-19.
[25] CHENG J, ZHOU F, XUAN X X, et al. Comparison of thecatalytic effects of eight industrial wastes rich in Na, Fe, Ca andAl on anthracite coal combustion[J]. Fuel, 2017, 187:398-402.
[26]刘永新,张波波,王福先,等.碱金属对焦炭热性能的影响[J].煤炭转化, 2008, 31(3):43-47.LIU Y X, ZHANG B B, WANG F X, et al. Effect of alkali metal onthe thermal properties of coke[J]. Coal Conversion, 2008, 31(3):43-47.
[27]蔡雪贞,孙章,王杰平,等.焦炭气化反应性对抚顺气煤容惰能力的评价[J].化工进展, 2018, 37(3):976-983.CAI X Z, SHUN Z, WANG J P, et al. Study on the inert-tolerantcapacity of Fushun gas coal by the characteristics of coke-CO2gasification[J]. Chemical Industry and Engineering Progress,2018, 37(3):976-983.
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