氧化钙对胜利褐煤焦水蒸气气化反应性能及微结构的影响

李阳 刘洋 冯伟 赵斌 智科端 滕英跃 宋银敏 何润霞 周晨亮 刘全生

引用本文: 李阳, 刘洋, 冯伟, 赵斌, 智科端, 滕英跃, 宋银敏, 何润霞, 周晨亮, 刘全生. 氧化钙对胜利褐煤焦水蒸气气化反应性能及微结构的影响[J]. 燃料化学学报, 2015, 43(9): 1038-1043. shu
Citation:  LI Yang, LIU Yang, FENG Wei, ZHAO Bin, ZHI Ke-duan, TENG Ying-yue, SONG Yin-min, HE Run-xia, ZHOU Chen-liang, LIU Quan-sheng. Influence of calcium oxide on Shengli lignite char microstructure and steam gasification performance[J]. Journal of Fuel Chemistry and Technology, 2015, 43(9): 1038-1043. shu

氧化钙对胜利褐煤焦水蒸气气化反应性能及微结构的影响

    通讯作者: 刘全生(1966-),教授,Tel:0471-6575945,E-mail:liuqs@imut.edu.cn。
  • 基金项目:

    国家自然科学基金(21566029, 21566028, 21266017) (21566029, 21566028, 21266017)

    高等学校博士学科点专项科研基金(20111514110001) (20111514110001)

    内蒙古自治区重大基础研究开放课题 

    内蒙古自然科学基金(2014MS0220, 2015BS0206) (2014MS0220, 2015BS0206)

    内蒙古自治区研究生科研创新项目(B20141012809) (B20141012809)

    内蒙古自治区科技创新引导奖励资金项目。 

摘要: 研究了CaO对胜利褐煤焦水蒸气气化反应性能及微结构的影响。脱除矿物质的胜利褐煤混合不同含量的CaO后在1 100 ℃下进行热解得到相应的煤焦,采用BET、XRD和Raman技术对其进行表征,同时在微型固定床反应器上对所制得煤焦进行水蒸气气化实验。比较添加CaO不同含量煤焦的反应性表明,添加2%(质量分数)的CaO对煤焦水蒸气气化的催化作用很小,而CaO添加量增大到5%时,煤焦的气化反应性能明显提高。煤焦比表面积随CaO添加量的提高而增大。XRD结果表明,在热解过程中,CaO能有效地抑制煤焦向石墨化方向发展趋势。煤焦002和100峰的峰强度随CaO添加量的增加而降低,且煤焦芳香度从66.8%降至39.9%。Raman光谱结果表明,随着CaO添加量的增加,ID/IG由1.363增加至1.541,IG/Iall由0.423减少到0.394。意味着由于Ca的催化作用,煤中大芳香环结构的裂解速率明显增加,且随CaO添加量的增多,煤焦的无序化程度和晶格缺陷均增大。

English

  • 
    1. [1] 边岳, 徐宝山, 王本水, 曹景沛, 赵小燕, 魏贤勇. 胜利褐煤负载镍生物质气化催化剂实验研究[J]. 洁净煤技术, 2014, 20(6): 13-18. (BIAN Yue, XU Bao-shan, WANG Ben-shui, CAO Jing-pei, ZHAO Xiao-yan, WEI Xian-yong. Preparation of nickel-loaded on Shengli lignite catalysts for catalytic gasification of biomass[J]. Clean Coal Technol, 2014, 20(6): 13-18.)[1] 边岳, 徐宝山, 王本水, 曹景沛, 赵小燕, 魏贤勇. 胜利褐煤负载镍生物质气化催化剂实验研究[J]. 洁净煤技术, 2014, 20(6): 13-18. (BIAN Yue, XU Bao-shan, WANG Ben-shui, CAO Jing-pei, ZHAO Xiao-yan, WEI Xian-yong. Preparation of nickel-loaded on Shengli lignite catalysts for catalytic gasification of biomass[J]. Clean Coal Technol, 2014, 20(6): 13-18.)

    2. [2] 许修强, 王永刚, 陈宗定, 白磊, 张锟俊, 杨萨莎, 张书. 水蒸气对褐煤原位气化半焦反应性能及微观结构的影响[J]. 燃料化学学报, 2015, 43(1): 1-8. (XU Xiu-qiang,WANG Yong-gang,CHEN Zong-ding,BAI Lei,ZHANG Kun-jun,YANG Sa-sha,ZHANG Shu. Influence of cooling treatments on char microstructure and reactivity of Shengli brown coal[J]. J Fuel Chem Technol, 2015, 43(1): 1-8.)[2] 许修强, 王永刚, 陈宗定, 白磊, 张锟俊, 杨萨莎, 张书. 水蒸气对褐煤原位气化半焦反应性能及微观结构的影响[J]. 燃料化学学报, 2015, 43(1): 1-8. (XU Xiu-qiang,WANG Yong-gang,CHEN Zong-ding,BAI Lei,ZHANG Kun-jun,YANG Sa-sha,ZHANG Shu. Influence of cooling treatments on char microstructure and reactivity of Shengli brown coal[J]. J Fuel Chem Technol, 2015, 43(1): 1-8.)

    3. [3] 许修强, 王永刚, 张书, 陈宗定, 陈绪军, 贺欣. 褐煤原位气化半焦的反应性及微观结构的演化行为[J]. 燃料化学学报, 2015, 43(3): 273-280. (XU Xiu-qiang,WANG Yong-gang,ZHANG Shu,CHEN Zong-ding,CHEN Xu-jun,HE Xin. Evolution behavior of reactivity and microstructure of lignite char during in-situ gasification with steam[J]. J Fuel Chem Technol, 2015, 43(3): 273-280.)[3] 许修强, 王永刚, 张书, 陈宗定, 陈绪军, 贺欣. 褐煤原位气化半焦的反应性及微观结构的演化行为[J]. 燃料化学学报, 2015, 43(3): 273-280. (XU Xiu-qiang,WANG Yong-gang,ZHANG Shu,CHEN Zong-ding,CHEN Xu-jun,HE Xin. Evolution behavior of reactivity and microstructure of lignite char during in-situ gasification with steam[J]. J Fuel Chem Technol, 2015, 43(3): 273-280.)

    4. [4] 周晨亮, 刘全生, 李阳, 智科端, 滕英跃, 宋银敏. 胜利褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用[J]. 化工学报, 2013, 64(6): 2092-2102. (ZHOU Chen-liang, LIU Quan-sheng, LI Yang, ZHI Ke-duan, TENG Ying-yue, SONG Yin-min. Production of hydrogen-rich syngas by steam gasification of Shengli lignite and catalytic effect of inherent minerals[J]. CIESC J, 2013, 64(6): 2092-2102.)[4] 周晨亮, 刘全生, 李阳, 智科端, 滕英跃, 宋银敏. 胜利褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用[J]. 化工学报, 2013, 64(6): 2092-2102. (ZHOU Chen-liang, LIU Quan-sheng, LI Yang, ZHI Ke-duan, TENG Ying-yue, SONG Yin-min. Production of hydrogen-rich syngas by steam gasification of Shengli lignite and catalytic effect of inherent minerals[J]. CIESC J, 2013, 64(6): 2092-2102.)

    5. [5] ZHUANG X G, QUEROL X, ALASTUEY A, JUAN R, PLANA F, LOPEZ-SOLER A, DU G, MARTYNOV V V. Geochemistry and mineralogy of the Cretaceous Wulantuga high-germanium coal deposit in Shengli coal field, Inner Mongolia, Northeastern China[J]. Int J Coal Geol, 2006, 66(1): 119-136.[5] ZHUANG X G, QUEROL X, ALASTUEY A, JUAN R, PLANA F, LOPEZ-SOLER A, DU G, MARTYNOV V V. Geochemistry and mineralogy of the Cretaceous Wulantuga high-germanium coal deposit in Shengli coal field, Inner Mongolia, Northeastern China[J]. Int J Coal Geol, 2006, 66(1): 119-136.

    6. [6] HUANG W H, WAN H, DU G, SUN L, MA Y Y, TANG X Y, WU W, QIN S L. Research on element geochemical characteristics of coal-ge deposit in Shengli coalfield, Inner Mongolia, China[J]. Earth Sci Front, 2008, 15(4): 56-64.[6] HUANG W H, WAN H, DU G, SUN L, MA Y Y, TANG X Y, WU W, QIN S L. Research on element geochemical characteristics of coal-ge deposit in Shengli coalfield, Inner Mongolia, China[J]. Earth Sci Front, 2008, 15(4): 56-64.

    7. [7] LIN S Y, WANG Y, SUZUKI Y. Effect of coal rank on steam gasification of coal/CaO mixtures[J]. Energy Fuels, 2007, 21(5): 2763-2768.[7] LIN S Y, WANG Y, SUZUKI Y. Effect of coal rank on steam gasification of coal/CaO mixtures[J]. Energy Fuels, 2007, 21(5): 2763-2768.

    8. [8] WANG J, YAO Y H, CAO J Q, JIANG M Q. Enhanced catalysis of K2CO3 for steam gasification of coal char by using Ca(OH)2 in char preparation[J]. Fuel, 2010, 89(2): 310-317.[8] WANG J, YAO Y H, CAO J Q, JIANG M Q. Enhanced catalysis of K2CO3 for steam gasification of coal char by using Ca(OH)2 in char preparation[J]. Fuel, 2010, 89(2): 310-317.

    9. [9] 朱廷钰, 张守玉, 黄戒介, 王洋. 氧化钙对流化床煤温和气化半焦性质的影响[J]. 燃料化学学报, 2000, 28(1): 40-43. (ZHU Ting-yu, ZHANG Shou-yu, HUANG Jie-jie, WANG Yang. Effect of calcium oxide on properties of char from fluidized bed coal mild gasification[J]. J Fuel Chem Technol, 2000, 28(1): 40-43.)[9] 朱廷钰, 张守玉, 黄戒介, 王洋. 氧化钙对流化床煤温和气化半焦性质的影响[J]. 燃料化学学报, 2000, 28(1): 40-43. (ZHU Ting-yu, ZHANG Shou-yu, HUANG Jie-jie, WANG Yang. Effect of calcium oxide on properties of char from fluidized bed coal mild gasification[J]. J Fuel Chem Technol, 2000, 28(1): 40-43.)

    10. [10] FELDMANN H F, CREAMER K S. Coal catalyzation to simplify the conversion of coal to SNG. Final report, March 1988-May 1990. Battelle Memorial Inst., Columbus, OH (USA), 1990.[10] FELDMANN H F, CREAMER K S. Coal catalyzation to simplify the conversion of coal to SNG. Final report, March 1988-May 1990. Battelle Memorial Inst., Columbus, OH (USA), 1990.

    11. [11] 李绍锋, 吴诗勇. 高温下煤焦的碳微晶及孔结构的演变行为[J]. 燃料化学学报, 2010, 38(5): 513-517. (LI Shao-feng, WU Shi-yong. Evolvement behavior of carbonm inicrystal and pore structure of coal chars at high temperatures[J]. J Fuel Chem Technol, 2010, 38(5): 513-517.)[11] 李绍锋, 吴诗勇. 高温下煤焦的碳微晶及孔结构的演变行为[J]. 燃料化学学报, 2010, 38(5): 513-517. (LI Shao-feng, WU Shi-yong. Evolvement behavior of carbonm inicrystal and pore structure of coal chars at high temperatures[J]. J Fuel Chem Technol, 2010, 38(5): 513-517.)

    12. [12] 杨景标, 蔡宁生. 催化剂对褐煤焦孔隙结构和表面形态的影响[J]. 中国电机工程学报, 2008, 28(11): 24-29. (YANG Jing-biao, CAI Ning-sheng. Effects of catalysts on the pore structure and morphology of a lignite char[J]. Proc CSEE, 2008, 28(11): 24-29.)[12] 杨景标, 蔡宁生. 催化剂对褐煤焦孔隙结构和表面形态的影响[J]. 中国电机工程学报, 2008, 28(11): 24-29. (YANG Jing-biao, CAI Ning-sheng. Effects of catalysts on the pore structure and morphology of a lignite char[J]. Proc CSEE, 2008, 28(11): 24-29.)

    13. [13] ROUZAUD J N, OBERLIN A. Structure, microtexture, and optical properties of anthracene and saccharose-based carbons[J]. Carbon, 1989, 27(4): 517-529.[13] ROUZAUD J N, OBERLIN A. Structure, microtexture, and optical properties of anthracene and saccharose-based carbons[J]. Carbon, 1989, 27(4): 517-529.

    14. [14] JIAO Y, TIAN W J, CHEN H L, SHI H G, YANG B B, LI C, SHAO Z P, ZHU Z P, LI S D. In situ catalyzed Boudouard reaction of coal char for solid oxide-based carbon fuel cells with improved performance[J]. Appl Energy, 2015, 141: 200-208.[14] JIAO Y, TIAN W J, CHEN H L, SHI H G, YANG B B, LI C, SHAO Z P, ZHU Z P, LI S D. In situ catalyzed Boudouard reaction of coal char for solid oxide-based carbon fuel cells with improved performance[J]. Appl Energy, 2015, 141: 200-208.

    15. [15] LU L M, KONG C H, SAHAJWALLA V, HARRIS D. Char structural ordering during pyrolysis and combustion and its influence on char reactivity[J]. Fuel, 2002, 81(9): 1215-1225.[15] LU L M, KONG C H, SAHAJWALLA V, HARRIS D. Char structural ordering during pyrolysis and combustion and its influence on char reactivity[J]. Fuel, 2002, 81(9): 1215-1225.

    16. [16] SONIBARE O O, HAEGER T, FOLEY S F. Structural characterization of Nigerian coals by X-ray diffraction, Raman and FT-IR spectroscopy[J]. Energy, 2010, 35(12): 5347-5353.[16] SONIBARE O O, HAEGER T, FOLEY S F. Structural characterization of Nigerian coals by X-ray diffraction, Raman and FT-IR spectroscopy[J]. Energy, 2010, 35(12): 5347-5353.

    17. [17] TREJO F, ANCHEYTA J, MORGAN T J, HEROD A A, KANDIYOTI R. Characterization of asphaltenes from hydrotreated products by SEC, LDMS, MALDI, NMR, and XRD[J]. Energy Fuels, 2007, 21(4): 2121-2128.[17] TREJO F, ANCHEYTA J, MORGAN T J, HEROD A A, KANDIYOTI R. Characterization of asphaltenes from hydrotreated products by SEC, LDMS, MALDI, NMR, and XRD[J]. Energy Fuels, 2007, 21(4): 2121-2128.

    18. [18] 齐学军, 郭欣, 罗重奎, 郑楚光. 热解过程中铁对神府褐煤焦结构的影响[J]. 工程热物理学报, 2014, 35(4): 796-800. (QI Xue-Jun, GUO Xin, LUO Zhong-kui, ZHENG Chu-guang. Effect of Iron on the structure of Shenfu Brown coal char during pyrolysis[J]. J Eng Thermophys, 2014, 35(4): 796-800.)[18] 齐学军, 郭欣, 罗重奎, 郑楚光. 热解过程中铁对神府褐煤焦结构的影响[J]. 工程热物理学报, 2014, 35(4): 796-800. (QI Xue-Jun, GUO Xin, LUO Zhong-kui, ZHENG Chu-guang. Effect of Iron on the structure of Shenfu Brown coal char during pyrolysis[J]. J Eng Thermophys, 2014, 35(4): 796-800.)

    19. [19] QI X J, GUO X, XUE L C, ZHENG C G. Effect of iron on Shenfu coal char structure and its influence on gasification reactivity[J]. J Anal Appl Pyrol, 2014, 110: 401-407.[19] QI X J, GUO X, XUE L C, ZHENG C G. Effect of iron on Shenfu coal char structure and its influence on gasification reactivity[J]. J Anal Appl Pyrol, 2014, 110: 401-407.

    20. [20] LI X J, LI C Z. FT-Raman spectroscopic characterisation of chars from the pyrolysis of coals of varying rank[J]. J Fuel Chem Technol, 2005, 33(4): 385-390.[20] LI X J, LI C Z. FT-Raman spectroscopic characterisation of chars from the pyrolysis of coals of varying rank[J]. J Fuel Chem Technol, 2005, 33(4): 385-390.

    21. [21] LI X J, HAYASHI J I, LI C Z. FT-Raman spectroscopic study of the evolution of char structure during the pyrolysis of a Victorian brown coal[J]. Fuel, 2006, 85(12): 1700-1707.[21] LI X J, HAYASHI J I, LI C Z. FT-Raman spectroscopic study of the evolution of char structure during the pyrolysis of a Victorian brown coal[J]. Fuel, 2006, 85(12): 1700-1707.

    22. [22] 齐学军, 宋文武, 刘亮. Fe对胜利褐煤焦结构和气化反应性能的影响[J]. 燃料化学学报, 2015, 43(5): 554-559. (QI Xue-jun, SONG Wen-wu, LIU Liang. Effect of iron on Shengli brown coal char structure and its influence on gasification reactivity[J]. J Fuel Chem Technol, 2015, 43(5): 554-559.)[22] 齐学军, 宋文武, 刘亮. Fe对胜利褐煤焦结构和气化反应性能的影响[J]. 燃料化学学报, 2015, 43(5): 554-559. (QI Xue-jun, SONG Wen-wu, LIU Liang. Effect of iron on Shengli brown coal char structure and its influence on gasification reactivity[J]. J Fuel Chem Technol, 2015, 43(5): 554-559.)

    23. [23] 柳晓飞, 尤静林, 王媛媛, LU Li-ming, 解迎芳, 余立旺, 伏清. 澳大利亚烟煤热解的拉曼光谱研究[J]. 燃料化学学报, 2014, 42(3): 270-276. (LIU Xiao-fei, YOU Jing-lin, WANG Yuan-yuan, LU Li-ming, XIE Ying-fang, YU Li-wang, FU Qing. Raman spectroscopic study on the pyrolysis of Australian bituminous coal[J]. J Fuel Chem Technol, 2014, 42(3): 270-276.)[23] 柳晓飞, 尤静林, 王媛媛, LU Li-ming, 解迎芳, 余立旺, 伏清. 澳大利亚烟煤热解的拉曼光谱研究[J]. 燃料化学学报, 2014, 42(3): 270-276. (LIU Xiao-fei, YOU Jing-lin, WANG Yuan-yuan, LU Li-ming, XIE Ying-fang, YU Li-wang, FU Qing. Raman spectroscopic study on the pyrolysis of Australian bituminous coal[J]. J Fuel Chem Technol, 2014, 42(3): 270-276.)

    24. [24] FERRARI A C. Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects[J]. Solid State Commun, 2007, 143(1): 47-57.[24] FERRARI A C. Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling, doping and nonadiabatic effects[J]. Solid State Commun, 2007, 143(1): 47-57.

    25. [25] WANG F J, ZHANG S, CHEN Z D, LIU C, WANG Y G. Tar reforming using char as catalyst during pyrolysis and gasification of Shengli brown coal[J]. J Anal Appl Pyrolysis, 2014, 105: 269-275.[25] WANG F J, ZHANG S, CHEN Z D, LIU C, WANG Y G. Tar reforming using char as catalyst during pyrolysis and gasification of Shengli brown coal[J]. J Anal Appl Pyrolysis, 2014, 105: 269-275.

    26. [26] ZAIDA A, BAR-ZIV E, RADOVIC L R, LEE Y J. Further development of Raman microprobe spectroscopy for characterization of char reactivity[J]. Proc Combust Inst, 2007, 31(2): 1881-1887.[26] ZAIDA A, BAR-ZIV E, RADOVIC L R, LEE Y J. Further development of Raman microprobe spectroscopy for characterization of char reactivity[J]. Proc Combust Inst, 2007, 31(2): 1881-1887.

  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  647
  • HTML全文浏览量:  54
文章相关
  • 收稿日期:  2015-05-04
  • 网络出版日期:  2015-06-21
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章