注册 English

正辛烷热裂化和催化裂化生成甲烷反应机理

李福超 ,  张久顺 ,  袁起民

downloadPDF
引用本文: 李福超, 张久顺, 袁起民. 正辛烷热裂化和催化裂化生成甲烷反应机理[J]. 燃料化学学报, 2014, 42(6): 697-703. shu
Citation:  LI Fu-chao, ZHANG Jiu-shun, YUAN Qi-min. Mechanism of methane formation in thermal and catalytic cracking of n-octane[J]. Journal of Fuel Chemistry and Technology, 2014, 42(6): 697-703. shu

正辛烷热裂化和催化裂化生成甲烷反应机理

    通讯作者: 袁起民,男,高级工程师,博士,从事催化裂化工艺研究与开发,E-mail:yuanqm.ripp@sinopec.com。
  • 基金项目:

    国家科技支撑计划(2012BAE05B01)。 (2012BAE05B01)

摘要: 采用脉冲微反装置,在反应温度为550~650 ℃,低转化率(小于15%)下,研究了正辛烷在石英砂和ZRP分子筛上的热裂化和催化裂化反应,分析了甲烷的生成机理。结果表明,正辛烷热裂化时,乙烯、丙烯和正丁烯是初始产物,甲烷由4种反应路径生成。当反应温度为600 ℃时,甲基自由基攻击碳链端部C-H键生成甲烷。中部C-H键脱氢形成的辛基自由基在端部C-C键断裂的活化能较高,仅在高温下生成甲烷。正辛烷在ZRP分子筛上主要发生质子化裂化反应,正构烷烃占有相当比重,甲烷由质子化裂化步骤生成。热裂化与质子化裂化对甲烷贡献的对比可知,当反应温度低于600 ℃时,甲烷由质子化裂化反应生成;在高温下,热裂化反应决定甲烷选择性。

English

  • 

    1. [1] RICE F O. The thermal decomposition of oganic compounds from the standpoint of free radicals. I. Saturated hydrocarbons[J]. J Am Chem Soc, 1931, 53(5): 1959-1972.[1] RICE F O. The thermal decomposition of oganic compounds from the standpoint of free radicals. I. Saturated hydrocarbons[J]. J Am Chem Soc, 1931, 53(5): 1959-1972.

    2. [2] RICE F O. The thermal decomposition of organic compounds from the standpoint of free radicals. Ⅲ. The calculation of the products formed from paraffin hydrocarbons[J]. J Am Chem Soc, 1933, 55(7): 3035-3040.[2] RICE F O. The thermal decomposition of organic compounds from the standpoint of free radicals. Ⅲ. The calculation of the products formed from paraffin hydrocarbons[J]. J Am Chem Soc, 1933, 55(7): 3035-3040.

    3. [3] RICE F O, DOOLEY M D. The thermal decomposition of organic compounds from the standpoint of free radicals. IV. The dehydrogenation of paraffin hydrocarbons and the strength of the C-C bond[J]. J Am Chem Soc, 1933, 55(10): 4245-4247.[3] RICE F O, DOOLEY M D. The thermal decomposition of organic compounds from the standpoint of free radicals. IV. The dehydrogenation of paraffin hydrocarbons and the strength of the C-C bond[J]. J Am Chem Soc, 1933, 55(10): 4245-4247.

    4. [4] KOSSIAKOFF A, RICE F O. Thermal decomposition of hydrocarbons, resonance stabilization and isomerization of free radicals[J]. J Am Chem Soc, 1943, 65(4): 590-595.[4] KOSSIAKOFF A, RICE F O. Thermal decomposition of hydrocarbons, resonance stabilization and isomerization of free radicals[J]. J Am Chem Soc, 1943, 65(4): 590-595.

    5. [5] GREENSFELDER B, VOGE H, GOOD G. Catalytic cracking of pure hydrocarbons[J]. Ind Eng Chem, 1945, 37(12): 1168-1176.[5] GREENSFELDER B, VOGE H, GOOD G. Catalytic cracking of pure hydrocarbons[J]. Ind Eng Chem, 1945, 37(12): 1168-1176.

    6. [6] HAAG W, DESSAU R. Duality of mechanism for acid-catalyzed paraffin cracking[C]//Proceedings of the 8th International Congress on Catalysis, Berlin, 1984.[6] HAAG W, DESSAU R. Duality of mechanism for acid-catalyzed paraffin cracking[C]//Proceedings of the 8th International Congress on Catalysis, Berlin, 1984.

    7. [7] YALURIS G, REKOSKE J E, APARICIO L M, MADON R J, DUMESIC J A. Isobutane cracking over Y-zeolites: I. Development of a kinetic-model[J]. J Catal, 1995, 153(1): 54-64.[7] YALURIS G, REKOSKE J E, APARICIO L M, MADON R J, DUMESIC J A. Isobutane cracking over Y-zeolites: I. Development of a kinetic-model[J]. J Catal, 1995, 153(1): 54-64.

    8. [8] YALURIS G, REKOSKE J E, APARICIO L M, MADON R J, DUMESIC J A. Isobutane cracking over Y-zeolites: Ⅱ. Catalytic cycles and reaction selectivity[J]. J Catal, 1995, 153(1): 65-75.[8] YALURIS G, REKOSKE J E, APARICIO L M, MADON R J, DUMESIC J A. Isobutane cracking over Y-zeolites: Ⅱ. Catalytic cycles and reaction selectivity[J]. J Catal, 1995, 153(1): 65-75.

    9. [9] 胡晓燕, 李春义, 杨朝合. 正庚烷在HZSM-5催化剂上的催化裂解行为[J]. 物理化学学报, 2010, 26(12): 3291-3298. (HU Xiao-yan, LI Chun-yi, YANG Chao-he. Catalytic cracking behavior of n-heptane over HZSM-5 catalyst[J]. Acta Physico-Chimica Sinica, 2010, 26(12): 3291-3298.)[9] 胡晓燕, 李春义, 杨朝合. 正庚烷在HZSM-5催化剂上的催化裂解行为[J]. 物理化学学报, 2010, 26(12): 3291-3298. (HU Xiao-yan, LI Chun-yi, YANG Chao-he. Catalytic cracking behavior of n-heptane over HZSM-5 catalyst[J]. Acta Physico-Chimica Sinica, 2010, 26(12): 3291-3298.)

    10. [10] LUKYANOV D B, SHTRAL V I, KHADZHIEV S N. A kinetic model for the hexane cracking reaction over H-ZSM-5[J]. J Catal, 1994, 146(1): 87-92.[10] LUKYANOV D B, SHTRAL V I, KHADZHIEV S N. A kinetic model for the hexane cracking reaction over H-ZSM-5[J]. J Catal, 1994, 146(1): 87-92.

    11. [11] JUNG J S, PARK J W, SEO G. Catalytic cracking of n-octane over alkali-treated MFI zeolites[J]. Appl Catal A: Gen, 2005, 288(1/2): 149-157.[11] JUNG J S, PARK J W, SEO G. Catalytic cracking of n-octane over alkali-treated MFI zeolites[J]. Appl Catal A: Gen, 2005, 288(1/2): 149-157.

    12. [12] KISSIN Y V. Relative reactivities of alkanes in catalytic cracking reactions[J]. J Catal, 1990, 126(2): 600-609.[12] KISSIN Y V. Relative reactivities of alkanes in catalytic cracking reactions[J]. J Catal, 1990, 126(2): 600-609.

    13. [13] WIELERS A F H, VAARKAMP M, POST M F M. Relation between properties and performance of zeolites in paraffin cracking[J]. J Catal, 1991, 127(1): 51-66.[13] WIELERS A F H, VAARKAMP M, POST M F M. Relation between properties and performance of zeolites in paraffin cracking[J]. J Catal, 1991, 127(1): 51-66.

    14. [14] ALTWASSER S, WELKER C, TRAA Y, WEITKAMP J. Catalytic cracking of n-octane on small-pore zeolites[J]. Micropor Mesopor Mater, 2005, 83(1/3): 345-356.[14] ALTWASSER S, WELKER C, TRAA Y, WEITKAMP J. Catalytic cracking of n-octane on small-pore zeolites[J]. Micropor Mesopor Mater, 2005, 83(1/3): 345-356.

    15. [15] RICE F O. Thermal decomposition of hydrocarbons and engine detonation[J]. Ind Eng Chem, 1934, 26(3): 259-262.[15] RICE F O. Thermal decomposition of hydrocarbons and engine detonation[J]. Ind Eng Chem, 1934, 26(3): 259-262.

    16. [16] 徐如人, 庞文琴, 于吉红, 霍启升, 陈接胜. 分子筛与多孔材料化学[M]. 北京: 科学出版社, 2004: 63-65. (XU Ru-ren, PANG Wen-qin, YU Ji-hong, HUO Qi-sheng, CHEN Jie-sheng. Zeolite and porous materials[M]. Beijing: Science Press, 2004: 63-65.)[16] 徐如人, 庞文琴, 于吉红, 霍启升, 陈接胜. 分子筛与多孔材料化学[M]. 北京: 科学出版社, 2004: 63-65. (XU Ru-ren, PANG Wen-qin, YU Ji-hong, HUO Qi-sheng, CHEN Jie-sheng. Zeolite and porous materials[M]. Beijing: Science Press, 2004: 63-65.)

    17. [17] JOLLY S, SAUSSEY J, BETTAHAR M M, LAVALLEY J C, BENAZZI E. Reaction mechanisms and kinetics in the n-hexane cracking over zeolites[J]. Appl Catal A: Gen, 1997, 156(1): 71-96.[17] JOLLY S, SAUSSEY J, BETTAHAR M M, LAVALLEY J C, BENAZZI E. Reaction mechanisms and kinetics in the n-hexane cracking over zeolites[J]. Appl Catal A: Gen, 1997, 156(1): 71-96.

    18. [18] CORMA A, PLANELLES J, SÁNCHEZ-MARÍN J, TOMÁS F. The role of different types of acid site in the cracking of alkanes on zeolite catalysts[J]. J Catal, 1985, 93(1): 30-37.[18] CORMA A, PLANELLES J, SÁNCHEZ-MARÍN J, TOMÁS F. The role of different types of acid site in the cracking of alkanes on zeolite catalysts[J]. J Catal, 1985, 93(1): 30-37.

    19. [19] WOJCIECHOWSKI B W. The reaction mechanism of catalytic cracking: Quantifying activity, selectivity, and catalyst decay[J]. Catal Rev, 1998, 40(3): 209-328.[19] WOJCIECHOWSKI B W. The reaction mechanism of catalytic cracking: Quantifying activity, selectivity, and catalyst decay[J]. Catal Rev, 1998, 40(3): 209-328.

    20. [20] SHERTUKDE P V, MARCELIN G, SILL G A, KEITH HALL W. Study of the mechanism of the cracking of small alkane molecules on HY Zeolites[J]. J Catal, 1992, 136(2): 446-462.[20] SHERTUKDE P V, MARCELIN G, SILL G A, KEITH HALL W. Study of the mechanism of the cracking of small alkane molecules on HY Zeolites[J]. J Catal, 1992, 136(2): 446-462.

  • 加载中
WeChat 扫一扫看文章
计量
  • PDF下载量:  0
  • 文章访问数:  894
  • HTML全文浏览量:  90
文章相关
  • 收稿日期:  2013-10-15
  • 网络出版日期:  2014-02-17
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

All Rights Reserved by the Chinese Chemical Society   中国化学会 版权所有 京ICP备05002797号

本系统由北京仁和汇智信息技术有限公司开发    技术支持: info@rhhz.net