生物柴油替代混合物化学动力学模型构建及路径分析

引用本文: 裴毅强, 郑朝蕾, 张博. 生物柴油替代混合物化学动力学模型构建及路径分析[J]. 物理化学学报, 2014, 30(2): 217-226. doi: 10.3866/PKU.WHXB201312102 shu

Citation: PEI Yi-Qiang, ZHENG Zhao-Lei, ZHANG Bo. Chemical Kinetic Model Development of Biodiesel Surrogate Fuel and Reaction Path Analysis[J]. Acta Physico-Chimica Sinica, 2014, 30(2): 217-226. doi: 10.3866/PKU.WHXB201312102 shu

生物柴油替代混合物化学动力学模型构建及路径分析

基金项目:
国家自然科学基金(51006128)资助项目 (51006128)

摘要:

以癸酸甲酯(C₁₁H₂₂O₂)和正庚烷(nC₇H₁₆)作为生物柴油替代混合物，通过相对分子质量、低热值以及含氧量与实际生物柴油对比确定两种组分按摩尔比1：1混合，并在此基础上构建了一个由691种组分、3226个基元反应组成的生物柴油替代混合物的化学动力学机理. 在激波管条件下该机理计算的着火延迟与实验数据吻合很好；在发动机条件下该机理计算的缸内压力与实验值吻合很好，CO、未燃碳氢和NOx与实验结果趋势一致.此外，本文还对替代混合物的低温反应动力学过程进行了分析，结果表明癸酸甲酯脱氢产物主要为MD2J和MDMJ. MD2J在低温阶段的主要消耗途径除了加氧之外,还有与正庚烷基(C₇H₁₅-1)第一次加氧产物(C₇H₁₅O₂-3)进行交叉反应；发生分解反应生成MP2D及与氧发生脱氢反应生成MD2D. 另一种主要脱氢产物MDMJ在低温阶段的主要消耗途径为通过同分异构转化为MD2J和MD3J.

关键词:

English

Chemical Kinetic Model Development of Biodiesel Surrogate Fuel and Reaction Path Analysis

1.
1 State Key Laboratory of Engines, Tianjin University, Tianjin 300072, P. R. China;
2 Key Laboratory of Low-Grade Energy Utilization Technologies and Systems of Ministry of Education, Chongqing University, Chongqing 400044, P. R. China
Received Date: 18 September 2013
Available Online: 23 January 2014
Fund Project:
国家自然科学基金(51006128)资助项目

Abstract:

In the present study, methyl decanoate (C₁₁H₂₂O₂) and n-heptane (nC₇H₁₆) were selected as a surrogate of biodiesel fuel. The molar ratio of the two constituents was determined to be 1:1, based on a comparison of the relative molecular weights, low heat values, and oxygen contents of the surrogate fuel and real biodiesel fuel. Furthermore, a chemical kinetic model including 691 species and 3226 elementary reactions of this biodiesel surrogate fuel was developed. The ignition delay times from experiments and calculations, under shock tube conditions, were compared; the computational results agree well with the experimental results. Comparisons of the in-cylinder pressure and main emissions under the engine conditions showed that the in-cylinder pressure calculated using this model agrees very well with the experimental result, and the trends in variations in the amounts of CO, unburned hydrocarbons, and NO_x emissions calculated using this model are also close to the experimental results. In addition, the lowtemperature reaction kinetics was analyzed in this study. The results show that the main products of methyl decanoate H- abstraction are MD2J and MDMJ. Besides the oxygen addition reaction, the main consumption paths of MD2J include reaction with C₇H₁₅O₂-3 (the product of the first oxygen addition of C₇H₁₅-1), decomposition to MP2D, and H-abstraction by O₂ forming MD2D. The main consumption paths of MDMJ are conversion to its isomers, MD2J and MD3J.

Key words:

1. [1]
  
  (1) Yao, G. X.; Wang, J. M. Sino-Global Energy 2010, 15 (9), 23.[姚国欣,王建明.中外能源, 2010, 15 (9), 23.]
  (1) Yao, G. X.; Wang, J. M. Sino-Global Energy 2010, 15 (9), 23.[姚国欣,王建明.中外能源, 2010, 15 (9), 23.]
2. [2]
  (2) Zhang, S. W. Chemical Industry 2007, 25 (9), 5. [张泗文. 化学工业, 2007, 25 (9), 5.](2) Zhang, S. W. Chemical Industry 2007, 25 (9), 5. [张泗文. 化学工业, 2007, 25 (9), 5.]
3. [3]
  (3) Szybist, J. P.; Song, J. H.; Alam, M. Fuel Process. Technol.2007, 88 (7), 679. doi: 10.1016/j.fuproc.2006.12.008(3) Szybist, J. P.; Song, J. H.; Alam, M. Fuel Process. Technol.2007, 88 (7), 679. doi: 10.1016/j.fuproc.2006.12.008
4. [4]
  (4) Lee, C. S.; Park, S. W.; Kwon, S. L. Energy Fuels 2005, 19 (5),2201. doi: 10.1021/ef050026h(4) Lee, C. S.; Park, S. W.; Kwon, S. L. Energy Fuels 2005, 19 (5),2201. doi: 10.1021/ef050026h
5. [5]
  (5) Gaurav, K.; Srivastava, R.; Singh, R. Int. J. Green Energy 2013,10 (8), 775. doi: 10.1080/15435075.2012.726673(5) Gaurav, K.; Srivastava, R.; Singh, R. Int. J. Green Energy 2013,10 (8), 775. doi: 10.1080/15435075.2012.726673
6. [6]
  (6) Lü, X. C.; Ma, J. J.; Ji, L. B.; Huang, Z. Combust. Sci. Technol.2009, 15 (3), 203. [吕兴才,马骏骏, 吉丽斌,黄震.燃烧科学与技术, 2009, 15 (3), 203.](6) Lü, X. C.; Ma, J. J.; Ji, L. B.; Huang, Z. Combust. Sci. Technol.2009, 15 (3), 203. [吕兴才,马骏骏, 吉丽斌,黄震.燃烧科学与技术, 2009, 15 (3), 203.]
7. [7]
  (7) Komninos, N. P.; Rakopoulos, C. D. Renew. Sust. Energ. Rev.2012, 16 (3), 1588. doi: 10.1016/j.rser.2011.11.026(7) Komninos, N. P.; Rakopoulos, C. D. Renew. Sust. Energ. Rev.2012, 16 (3), 1588. doi: 10.1016/j.rser.2011.11.026
8. [8]
  (8) Mancaruso, E.; Vaglieco, B. M. Exp. Therm. Fluid Sci. 2010, 34 (3), 346. doi: 10.1016/j.expthermflusci.2009.10.010(8) Mancaruso, E.; Vaglieco, B. M. Exp. Therm. Fluid Sci. 2010, 34 (3), 346. doi: 10.1016/j.expthermflusci.2009.10.010
9. [9]
  (9) Zhang, Q. F.; Zheng, Z. L.; He, Z. W.; Wang, Y. Acta Phys. -Chim. Sin. 2011, 27 (3), 530. [张庆峰, 郑朝蕾, 何祖威,王迎.物理化学学报, 2011, 27 (3), 530.] doi: 10.3866/PKU.WHXB20110334(9) Zhang, Q. F.; Zheng, Z. L.; He, Z. W.; Wang, Y. Acta Phys. -Chim. Sin. 2011, 27 (3), 530. [张庆峰, 郑朝蕾, 何祖威,王迎.物理化学学报, 2011, 27 (3), 530.] doi: 10.3866/PKU.WHXB20110334
10. [10]
  (10) Szybist, J. P.; McFarlane, J.; Bunting, B. G. SAE Tech. Pap. Ser.2007, 2007-01-4010.(10) Szybist, J. P.; McFarlane, J.; Bunting, B. G. SAE Tech. Pap. Ser.2007, 2007-01-4010.
11. [11]
  (11) Valeri, I. G.; Yang, J. F. Biotechnol. Adv. 2009, 27 (5), 641. doi: 10.1016/j.biotechadv.2009.04.024(11) Valeri, I. G.; Yang, J. F. Biotechnol. Adv. 2009, 27 (5), 641. doi: 10.1016/j.biotechadv.2009.04.024
12. [12]
  (12) Fisher, E. M.; Pitz, W. J.; Curran, H. J.; Westbrook, C. K. Proc. Combust. Inst. 2000, 2 (28), 1579.(12) Fisher, E. M.; Pitz, W. J.; Curran, H. J.; Westbrook, C. K. Proc. Combust. Inst. 2000, 2 (28), 1579.
13. [13]
  (13) Herbinet, O.; William, J. P.; Charles, K. W. Combust. Flame2008, 154 (3), 507. doi: 10.1016/j.combustflame.2008.03.003(13) Herbinet, O.; William, J. P.; Charles, K. W. Combust. Flame2008, 154 (3), 507. doi: 10.1016/j.combustflame.2008.03.003
14. [14]
  (14) Diévart, P.; Won, S. H.; Dooley, S.; Dryer, F. L.; Ju, Y. G.Combust. Flame 2012, 159, 1793. doi: 10.1016/j.combustflame.2012.01.002(14) Diévart, P.; Won, S. H.; Dooley, S.; Dryer, F. L.; Ju, Y. G.Combust. Flame 2012, 159, 1793. doi: 10.1016/j.combustflame.2012.01.002
15. [15]
  (15) Hakka, M. H.; Glaude, P. A.; Herbinet, O.; Battin-Leclerc, F.Combust. Flame 2009, 156, 2129. doi: 10.1016/j.combustflame.2009.06.003(15) Hakka, M. H.; Glaude, P. A.; Herbinet, O.; Battin-Leclerc, F.Combust. Flame 2009, 156, 2129. doi: 10.1016/j.combustflame.2009.06.003
16. [16]
  (16) Brakora, J. L.; Ra, Y.; Reitz, R. D.; McFarlane, J.; Daw, C. S.SAE Tech. Pap. Ser. 2008, 2008-01-1378.(16) Brakora, J. L.; Ra, Y.; Reitz, R. D.; McFarlane, J.; Daw, C. S.SAE Tech. Pap. Ser. 2008, 2008-01-1378.
17. [17]
  (17) Herbinet, O.; Pitz, W. J.; Westbrook, C. K. Combust. Flame2010, 157, 893. doi: 10.1016/j.combustflame.2009.10.013(17) Herbinet, O.; Pitz, W. J.; Westbrook, C. K. Combust. Flame2010, 157, 893. doi: 10.1016/j.combustflame.2009.10.013
18. [18]
  (18) Sarathy, S. M.; Thomson, M. J.; Pitz, W. J.; Lu, T. Proc. Combust. Inst. 2011, 33, 399. doi: 10.1016/j.proci.2010.06.058(18) Sarathy, S. M.; Thomson, M. J.; Pitz, W. J.; Lu, T. Proc. Combust. Inst. 2011, 33, 399. doi: 10.1016/j.proci.2010.06.058
19. [19]
  (19) Patel, A.; Kong, S. C.; Reitz, R. D. SAE Tech. Pap. Ser. 2004,2004-01-0558.(19) Patel, A.; Kong, S. C.; Reitz, R. D. SAE Tech. Pap. Ser. 2004,2004-01-0558.
20. [20]
  (20) Hori, M.; Matsunaga, N.; Marinov, N. M.; Pitz, W.; Westbrook,C. Proc. Combust. Inst. 1998, 27, 389.(20) Hori, M.; Matsunaga, N.; Marinov, N. M.; Pitz, W.; Westbrook,C. Proc. Combust. Inst. 1998, 27, 389.
21. [21]
  (21) Kee, R. J.; Rupley, F. M.; Miller, J. A.; Coltrin, M. E.; Grcar, J.F.; Meeks, E.; Moffat, H. K.; Lutz, A. E.; Dixon-Lewis, G.;Smooke, M. D.; Warnatz, J.; Evans, G. H.; Larson, R. S.;Mitchell, R. E.; Petzold, L. R.; Reynolds, W. C.; Caracotsios,M.; Stewart, W. E.; Glarborg, P.; Wang, C.; McLellan, C. L.;Adigun, O.; Houf, W. G.; Chou, C. P.; Miller, S. F.; Ho, P.;Young, P. D.; Young, D. J.; Hodgson, D. W.; Petrova, M. V.;Puduppakkam, K. V. CHEMKIN Release 4.1; Reaction Design:San Die , CA. 2006(21) Kee, R. J.; Rupley, F. M.; Miller, J. A.; Coltrin, M. E.; Grcar, J.F.; Meeks, E.; Moffat, H. K.; Lutz, A. E.; Dixon-Lewis, G.;Smooke, M. D.; Warnatz, J.; Evans, G. H.; Larson, R. S.;Mitchell, R. E.; Petzold, L. R.; Reynolds, W. C.; Caracotsios,M.; Stewart, W. E.; Glarborg, P.; Wang, C.; McLellan, C. L.;Adigun, O.; Houf, W. G.; Chou, C. P.; Miller, S. F.; Ho, P.;Young, P. D.; Young, D. J.; Hodgson, D. W.; Petrova, M. V.;Puduppakkam, K. V. CHEMKIN Release 4.1; Reaction Design:San Die , CA. 2006
22. [22]
  (22) Hernandez, J. J.; Serrano, C.; Perez, J. Energ Fuel 2006, 20,532. doi: 10.1021/ef058025c(22) Hernandez, J. J.; Serrano, C.; Perez, J. Energ Fuel 2006, 20,532. doi: 10.1021/ef058025c
23. [23]
  (23) Nicolas, G. J. The Rate-controlled Constrained-EquilibriumModeling of C1-C2/O2/diluent Mixtures. Ph. D. Dissertation,Northeastern University, Boston, 2012.(23) Nicolas, G. J. The Rate-controlled Constrained-EquilibriumModeling of C1-C2/O2/diluent Mixtures. Ph. D. Dissertation,Northeastern University, Boston, 2012.
24. [24]
  (24) Hernandez, J. J.; Sanz-Argent, J.; Carot, J. M.; Jabaloyes, J. M.Int. J. Engine Res. 2010, 11, 199. doi: 10.1243/14680874JER06209(24) Hernandez, J. J.; Sanz-Argent, J.; Carot, J. M.; Jabaloyes, J. M.Int. J. Engine Res. 2010, 11, 199. doi: 10.1243/14680874JER06209
25. [25]
  (25) Andrae, J. C. G.; Brinck, T.; Kalghatgi, G. T. Combust. Flame2008, 155, 696. doi: 10.1016/j.combustflame.2008.05.010(25) Andrae, J. C. G.; Brinck, T.; Kalghatgi, G. T. Combust. Flame2008, 155, 696. doi: 10.1016/j.combustflame.2008.05.010
26. [26]
  (26) Andrae, J. C. G. Fuel 2013, 107, 740. doi: 10.1016/j.fuel.2013.01.070(26) Andrae, J. C. G. Fuel 2013, 107, 740. doi: 10.1016/j.fuel.2013.01.070
27. [27]
  (27) Gustavsson, J.; lovitchev, V. I. SAE Tech. Pap. Ser. 2003,2003-01-1848.(27) Gustavsson, J.; lovitchev, V. I. SAE Tech. Pap. Ser. 2003,2003-01-1848.
28. [28]
  (28) Ciezki, H. K.; Adomeit, G. Combust. Flame 1993, 93 (4), 421.doi: 10.1016/0010-2180(93)90142-P(28) Ciezki, H. K.; Adomeit, G. Combust. Flame 1993, 93 (4), 421.doi: 10.1016/0010-2180(93)90142-P
29. [29]
  (29) Wang, W. J.; Oehlschlaeger, M. A. Combust. Flame 2012, 159,476. doi: 10.1016/j.combustflame.2011.07.019(29) Wang, W. J.; Oehlschlaeger, M. A. Combust. Flame 2012, 159,476. doi: 10.1016/j.combustflame.2011.07.019
30. [30]
  (30) Cheng, X. B.; Chen, D. L.; Ju, H. L. Automobile Technology2008, No. 1, 46. [成晓北,陈德良, 鞠洪玲.汽车技术, 2008,No. 1, 46.](30) Cheng, X. B.; Chen, D. L.; Ju, H. L. Automobile Technology2008, No. 1, 46. [成晓北,陈德良, 鞠洪玲.汽车技术, 2008,No. 1, 46.]
31. [31]
  (31) Zheng, Z. L.; Yao, M. F. Fuel 2006, 85 (17-18), 2605. doi: 10.1016/j.fuel.2006.05.005
  (31) Zheng, Z. L.; Yao, M. F. Fuel 2006, 85 (17-18), 2605. doi: 10.1016/j.fuel.2006.05.005

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

生物柴油替代混合物化学动力学模型构建及路径分析

English

Chemical Kinetic Model Development of Biodiesel Surrogate Fuel and Reaction Path Analysis

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

生物柴油替代混合物化学动力学模型构建及路径分析

English

Chemical Kinetic Model Development of Biodiesel Surrogate Fuel and Reaction Path Analysis

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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