钙化合物在煤热解过程中的作用

刘振宇;王仁醒;纪雷鸣;蒋卷涛;承小杰;石磊

北京化工大学学报(自然科学版) ›› 2015, Vol. 42 ›› Issue (4) : 1-9.

PDF(791 KB)
欢迎访问北京化工大学学报(自然科学版),今天是 2025年5月14日 星期三
Email Alert  RSS
PDF(791 KB)
北京化工大学学报(自然科学版) ›› 2015, Vol. 42 ›› Issue (4) : 1-9.
专题综述

钙化合物在煤热解过程中的作用

  • 刘振宇;王仁醒;纪雷鸣;蒋卷涛;承小杰;石磊
作者信息 +

Effect of calcium compounds on pyrolysis of coals

  • LIU ZhenYu;WANG RenXing;JI LeiMing;JIANG JuanTao;CHENG XiaoJie;SHI Lei
Author information +
文章历史 +

摘要

煤热解联产焦炭、焦油和煤气,是煤化工的重要分支。为了提高焦油和煤气的品质及产率,国内外研究了多种催化剂对煤热解过程的影响,大量文献表明,含钙化合物可以催化焦油裂解、提高焦油品质和煤气中高附加值组分(如H2和CO)的产率。本文基于近30年来的文献数据,从钙化合物对煤热解产物的收率、组成以及性质的影响方面展开评述,分析了钙化合物对煤热解过程的作用机理、对S和N迁移的影响,最后提出了需要进一步解决的问题。

Abstract

Coal pyrolysis has been employed for more than a century to produce coke, tar and coal gas. To enhance the quality of the tar and gas and to increase their yields many researches were carried out on catalysis of coal pyrolysis. A notable trend among these studies is the role of calcium compounds, which were found to catalyze tar into lighter fractions and gases of higher market value, reduce S and N contents in the products,and overcome operation problems. This article reviews the developments made and knowledge gained in past decades on the subject, analyzes the mechanisms involved, and attempts to show the researches needed in the future.

引用本文

导出引用
刘振宇;王仁醒;纪雷鸣;蒋卷涛;承小杰;石磊. 钙化合物在煤热解过程中的作用[J]. 北京化工大学学报(自然科学版), 2015, 42(4): 1-9
LIU ZhenYu;WANG RenXing;JI LeiMing;JIANG JuanTao;CHENG XiaoJie;SHI Lei. Effect of calcium compounds on pyrolysis of coals[J]. Journal of Beijing University of Chemical Technology, 2015, 42(4): 1-9

参考文献

[1]中华人民共和国国家统计局. 中国统计年鉴2014[EB/OL]. [2015-06-20]. http: www.stats.gov.cn/tjsj/ndsj/2014/indexch.htm.
National
Bureau of Statistics of the People’s Republic of China. China Statistical Yearbook 2014[EB/OL].[2015-06-20]. http: www.stats.gov.cn/tjsj/ndsj/2014/indexch.htm. (in Chinese)
[2]高晋生. 煤的热解、炼焦和煤焦油加工[M]. 北京: 化学工业出版社, 2010.
Gao J S. Coal pyrolysis, coking and coal tar processing[M].Beijing: Chemical Industry Press, 2010. (in Chinese)
[3]杨景标, 蔡宁生, 李振山. 几种金属催化褐煤焦水蒸气气化的实验研究[J]. 中国电机工程学报, 2007, 27(26): 7-12.
Yang J B, Cai N S, Li Z S. Experimental study on steam gasification of lignite char catalyzed by several metals[J]. Proceedings of the CSEE, 2007, 27(26): 7-12. (in Chinese)
[4]郝丽芳, 李松庚, 崔丽杰, 等. 煤催化热解技术研究进展[J]. 煤炭科学技术, 2012, 40(10): 108-112.
Hao L F, Li S G, Cui L J, et al. Research progress of coal catalytic pyrolysis technology[J]. Coal Science and Technology, 2012, 40(10): 108-112. (in Chinese)
[5]Zou X W, Yao J Z, Yang X M, et al. Catalytic effects of metal chlorides on the pyrolysis of lignite[J]. Energy & Fuels, 2007, 21(2): 619-624.
[6]Li C Z, Sathe C, Kershaw J R, et al. Fates and roles of alkali and alkaline earth metals during the pyrolysis of a Victorian brown coal[J]. Fuel, 2000, 79(3): 427-438. 
[7]Lin S Y, Harada M, Suzuki Y, et al. Comparison of pyrolysis products between coal, coal/CaO, and coal/Ca(OH)2 materials[J]. Energy & Fuels, 2003, 17(3): 602-607.
[8]Lin S Y, Suzuki Y, Hatano H, et al. Developing an innovative method, HyPr-RING, to produce hydrogen from hydrocarbons[J]. Energy Conversion and Management, 2002, 43(9): 1283-1290.
[9]Liu L J, Liu H J, Cui M Q, et al. Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char: Transformations of sulfur[J]. Fuel, 2013, 112: 687-694.
[10]Li G D, Liu Q Y, Liu Z Y, et al. Production of calcium carbide from fine biochars[J]. Angewandte Chemie International Edition, 2010, 49(45): 8480-8483.
[11]刘振宇, 刘清雅, 王仁醒, 等. 一种联产电石、煤气和焦油的复合床反应器及方法:中国,103272536 A[P]. 2013-0904. 
Liu Z Y, Liu Q Y, Wang R X, et al. Hybrid reactor and method of coproduction of calcium carbide, CO gas and tar: CN, 103272536 A[P]. 2013-09-04. (in Chinese)
[12]Yamashita H, Nomura M, Tomita A. Local structures of metals dispersed on coal. 4. Local structure of calcium species on coal after heat treatment and carbon dioxide gasification[J]. Energy & Fuels, 1992, 6(5): 656-661.
[13]Khan M R. Production of high quality liquid fuels from coal by mild pyrolysis of coal-lime mixtures[J]. Fuel Science & Technology International, 1987, 5(2): 185-231.
[14]刘慧君, 周锦文, 王杰. 钙基添加剂对煤慢速和快速热解行为的影响[J]. 现代化工, 2011, 31(3): 70-72.
Liu H J, Zhou J W, Wang J. Effects of Ca-based additves on behaviors of slow and fast coal pyrolysis[J]. Modern Chemical Industry, 2011, 31(3): 70-72. (in Chinese
[15]刘慧君. 钙基添加剂作用下煤热解和气化行为及其硫迁移[D]. 上海: 华东理工大学, 2011.
Liu H J. The coal pyrolytic and gasification behaviors and sulfur transformation under the effect of Ca-based additives[D]. Shanghai: East China University of Science and Technology, 2011. (in Chinese)
[16]刘振宇. 煤化学的前沿与挑战: 结构与反应[J]. 中国科学: 化学, 2014, 44(9): 1431-1438.
Liu Z Y. Advancement in coal chemistry: structure and reactivity[J]. SCIENTIA SINICA Chimica, 2014, 44(9): 1431-1438. (in Chinese)
[17]贾永斌, 黄戒介, 程中虎, 等. 煤快速热解过程中氧化钙对焦油裂解的影响[J]. 煤炭转化, 2011, 24(2): 53-57.
Jia Y B, Huang J J, Cheng Z H, et al. Effect of CaO on tar cracking in a rapid-pyrolysis fixed bed reactor[J]. Coal Conversion, 2011, 24(2): 53-57. (in Chinese)
[18]贾永斌, 黄戒介, 王洋. 氧化钙在流化床稀相段对焦油裂解的影响[J]. 中国矿业大学学报, 2004, 33(5): 552-556.
Jia Y B, Huang J J, Wang Y. Influence of calcium oxide ontar cracking in freeboard of fluidized bed[J]. Journal of China University of Mining & Technology, 2004, 33(5): 552-556. (in Chinese)
[19]Zhu T Y, Zhang S Y, Huang J J, et al. Effect of calcium oxide on pyrolysis of coal in a fluidized bed[J]. Fuel Processing Technology, 2000, 64(1): 271-284.
[20]Wornat M J, Nelson P F. Effects of ion-exchanged calcium on brown coal tar composition as determined by Fourier transform infrared spectroscopy[J]. Energy & Fuels, 1992, 6(2): 136-142. 
[21]Zhang L X, Kudo S J, Tsubouchi N, et al. Catalytic effects of Na and Ca from inexpensive materials on in-situ steam gasification of char from rapid pyrolysis of low rank coal in a drop-tube reactor[J]. Fuel Processing Technology, 2013, 113: 1-7.
[22]贾永斌, 黄戒介, 王洋. 停留时间对氧化钙催化裂解焦油的影响[J]. 燃烧科学与技术, 2004, 10(6): 549-553.
Jia Y B, Huang J J, Wang Y. Effect of residence time on tar catalytic cracking behavior with calcium oxide[J]. Journal of Combustion Science and Technology, 2004, 10(6): 549-553. (in Chinese)
[23]Franklin H D, Cosway R G, Peters W A, et al. Effects of cations on the rapid pyrolysis of a Wyodak subbituminous coal[J]. Industrial & Engineering Chemistry Process Design and Development, 1983, 22(1): 39-42.
[24]韩艳娜, 王磊, 余江龙, 等. 钙对褐煤热解和煤焦水蒸气气化反应性的影响[J]. 太原理工大学学报, 2013, 44(3): 264-267.
Han Y N, Wang L, Yu J L, et al. Effects of calcium on pyrolysis of lignite and reactivity of char in steam gasification[J]. Journal of Taiyuan University of Technology, 2013, 44(3): 264-267. (in Chinese)
[25]Gavalas G R. Coal Pyrolysis[M].Amsterdam: Elsevier, 1982.
[26]Liu Z Y, Guo X J, Shi L, et al. Reaction of volatiles—A crucial step in pyrolysis of coals[J]. Fuel, 2015, 154: 361-369.
[27]杨会民, 王美君, 张玉龙, 等. 添加物对宁夏热解气相产物生成的影响[J]. 煤炭学报, 2010, 35(8): 1364-1368.
Yang H M, Wang M J, Zhang Y L, et al. Effects of additives on Ningxia coal pyrolysis behavior[J]. Journal of Coal Society, 2010, 35(8): 1364-1368. (in Chinese)
[28]Jia Y, Huang J, Wang Y. Effects of calcium oxide on the cracking of coal tar in the freeboard of a fluidized bed[J]. Energy & Fuels, 2004, 18(6): 1625-1632.
[29]殷宏彦, 王美君, 王俊宏, 等. 钙、钠添加剂对平朔煤热解特性的影响[J]. 洁净煤技术, 2010, 16(3): 31-35.
Yin H Y,Wang M J,Wang J H,et al. Effect of calcium and sodium additives on the pyrolysis characteristic of Pingshuo demineralized coal[J]. Clean Coal Technology, 2010, 16(3): 31-35. (in Chinese)
[30]Reichel D, Klinger M, Krzack S, et al. Effect of ash components on devolatilization behavior of coal in comparison with biomass—Product yields, composition, and heating values[J]. Fuel, 2013, 114: 64-70.
[31]Feng B, Liu W Q, Li X, et al. Overcoming the problem of loss-in-capacity of calcium oxide in CO2 capture[J]. Energy & Fuels, 2006, 20(6): 2417-2420.
[32]Liu Q R, Hu H Q, Zhou Q, et al. Effect of inorganic matter on reactivity and kinetics of coal pyrolysis[J]. Fuel, 2004, 83(6): 713-718.
[33]郭崇涛. 煤化学[M]. 北京: 化学工业出版社, 1999.
Guo C T. Coal Chemistry[M].Beijing: Chemical Industry Press, 1999. (in Chinese)
[34]杜娟, 王俊宏, 崔银萍, 等. 西部煤热解过程中气相产物的生成与释放规律[J]. 中国矿业大学学报, 2008, 37(5): 694-698.
Du J, Wang J H, Cui Y P, et al. Forming and releasing of gaseous products of coal during pyrolysis in western China[J]. Journal of China University of Mining & Technology, 2008, 37(5): 694-698. (in Chinese) 
[35]白向飞. 中国褐煤及低阶烟煤利用与提质技术开发[J]. 煤质技术, 2010, 6:9-11.
Bai X F. Discussion on utilization and development of improving quality technology of lignite and low rank bituminous coal inChina[J]. Coal Quality Technology, 2010, 6: 9-11. (in Chinese)
[36]Doolan K R, Mackie J C. Products from the rapid pyrolysis of a brown coal in inert and reducing atmospheres[J]. Fuel, 1985, 64(3): 400-405.
[37]Doolan K R, Mackie J C. Kinetics of rapid pyrolysis of a calcium-exchanged brown coal and of a calcium model compound[C]∥Symposium(International) on Combustion, 1985, 20(1): 1463-1469.
[38]吕俊复, 岳光溪. 氧化钙条件下焦油主要组分的催化裂解[J]. 清华大学学报:自然科学版, 1997, 37(2): 6-10.
Lv J F, Yue G X. Catalytic cracking reactions of tar components over CaO[J]. Journal of Tsinghua University:Sci & Tech, 1997, 37(2): 6-10. (in Chinese)
[39]Guan R G, Li W, Li B Q. Effects of Ca-based additives on desulfurization during coal pyrolysis[J]. Fuel, 2003, 82(15): 1961-1966.
[40]Chang C C-S. Thermal reactions of freshly generated coal tar over calcium oxide[D].Cambridge, USA: Massachusetts Institute of Technology, 1986.
[41]Wu Z H, Sugimoto Y, Kawashima H. Effect of calcium catalyst on coal nitrogen removal during pyrolysis[J]. Energy & Fuels, 2000, 14(5): 1119-1120.
[42]Tsubouchi N, Ohtsuka Y. Formation of N2 during pyrolysis of Ca-loaded coals[J]. Fuel, 2002, 81(11): 1423-1431.
[43]Tsubouchi N, Ohtsuka Y. Nitrogen release during high temperature pyrolysis of coals and catalytic role of calcium in N2 formation[J]. Fuel,2002, 81(18): 2335-2342.
[44]Radovic L a R, Walker P L, Jenkins R G. Effect of lignite pyrolysis conditions on calcium oxide dispersion and subsequent char reactivity[J]. Fuel, 1983, 62(2): 209-212.
[45]Tsubouchi N, Xu C B, Ohtsuka Y. Carbon crystallization during high-temperature pyrolysis of coals and the enhancement by calcium[J].Energy & Fuels, 2003, 17(5): 1119-1125. 
[46]Khan M R, Seshadri K. Compositional changes in the mild gasification liquids produced in the presence of calcium compounds[J]. Fuel Processing Technology, 1991, 27(1): 83-94.
[47]Ellig D L, Lai C K, Mead D W, et al. Pyrolysis of volatile aromatic hydrocarbons and n-heptane over calcium oxide and quartz[J]. Industrial & Engineering Chemistry Process Design and Development, 1985, 24(4): 1080-1087.
[48]Lai C-K S, Chen P, Longwell J P, et al. Thermal reactions of m-cresol over calcium oxide between 350 and 600℃[J]. Fuel, 1987, 66(4): 525-531.
[49]Case P A, Truong C, Wheeler M C, et al. Calcium-catalyzed pyrolysis of lignocellulosic biomass components[J]. Bioresource Technology,2015, 192: 247-252.
[50]Khan M R, Jenkins R G. Influence of added calcium compounds on swelling, plastic, and pyrolysis behaviour of coal devolatilized at elevated pressures[J]. Fuel, 1986, 65(9): 1203-1208.
[51]李世光. 煤热解和煤与生物质共热解过程中硫的变迁[D]. 大连: 大连理工大学, 2006.
Li S G. Desulufrization of coal during pyrolysis and copyrolysis with biomass[D]. Dalian: Dalian University of Technology, 2006. (in Chinese)
[52]管仁贵, 李文, 李保庆. 钙基添加剂在大同煤热解中的作用[J]. 中国矿业大学学报, 2002, 31(4): 396-401.
Guan R G, Li W, Li B Q. Effect of Ca-based additives on pyrolysis ofDatong coal[J]. Journal of China University of Mining & Technology, 2002, 31(4): 396-401. (in Chinese)
[53]Zhou S F, Yang J L, Liu Z Y, et al. Effect of temperature on the reaction of H2S with a coke[J]. Fuel Processing Technology, 2011, 92(9): 1671-1674.
[54]Burchill P, Welch L S. Variation of nitrogen content and functionality with rank for some UK bituminous coals[J]. Fuel, 1989, 68(1): 100-104.
[55]Ohtsuka Y, Zhiheng W, Furimsky E. Effect of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal[J]. Fuel, 1997, 76(14): 1361-1367.
[56]顾颖. 氧/燃料燃烧方式下钙与铁对煤中氮释放特性的影响[D]. 武汉: 华中科技大学, 2013.
Gu Y. Effects of Ca and Fe on coal nitrogen release in oxyfuel combustion[D]. Wuhan: Huazhong University of Science and Technology, 2013.(in Chinese)

PDF(791 KB)

2488

Accesses

0

Citation

Detail

段落导航
相关文章

/