褐煤模型化合物中含氧官能团脱出反应的理论研究

doi:10.7503/cjcu20140612

摘要/Abstract

摘要：

选取苯甲酸和苯酚作为褐煤含氧官能团模型化合物, 采用密度泛函理论(DFT)中的B3LYP泛函和6-311+G(d,p)基组, 研究了羧基和羟基可能的脱出反应机理. 结果表明, 不同含氧官能团脱出方式不同, 脱出所需的能量也有差异; 含有羧基物质的自催化交联脱羧是相对容易发生的反应; 考虑到水分子对含氧官能团脱出的影响, 选取甲酸和丙三醇作为褐煤含氧官能团模型, 研究了水分子参与反应的过渡态结构及其反应活化能的变化, 结果表明, 反应中水分子作为质子传递介质能降低反应活化能, 加快反应速率, 一般1~2个水分子的催化效果较佳; 同时研究了Na⁺, K⁺及其羧酸盐对丙三醇中羟基脱出反应过渡态结构和反应活化能的影响, 表明Na⁺和K⁺均能与模型化合物形成络合物, 稳定过渡态结构, 降低活化能, 其中Na⁺的催化效果更佳; 与单纯的离子相比, K⁺羧酸盐催化效果变化不大, Na⁺羧酸盐催化能力降低幅度较大.

关键词: 密度泛函理论, 含氧官能团, 反应机理, 活化能, 褐煤模型化合物

Abstract:

The removal reaction mechanism of different kinds of oxygen-containing functional groups in lignite was investigated, benzoic and phenol were chosen as model compounds. Density function theory(DFT) and DFT-based B3LYP method along with mixed basis sets 6-311+G(d,p) were applied in all calculations. The results suggest that removal approaches are different from different kinds of oxygen-containing functional groups and the taking off energy is also different. According to the reaction activation energy of different kinds of reactions, autocatalysis reaction of structure unit containing carboxyl is the easiest. Taking account of the influence of water molecular to the reaction, formic acid and glycerin were studied as model compounds. The results show that water molecular can reduce the reaction activation energy and accelerate the reaction process, the best catalytic effect is achieved with one or two water molecular. The effects of Na⁺, K⁺ and their carboxylates to the reaction were studied on glycerin as well. The results suggest that Na⁺ and K⁺ can reduce the reaction activation energy by forming complexes with glycerin, which stabilizes the transition state structure. Na⁺ has a better catalytic effect to the reaction. Comparing with sheer ions, the catalytic effects of carboxylate can’t reach that good. However, potassium carboxylate’s catalytic effect doesn’t change a lot, while the catalytic effect of sodium carvoxylate has a significant decrease.

Key words: Density functional theory, Oxygen-containing functional group, Reaction mechanism, Activation energy, Lignite model compound

中图分类号:

O641

TrendMD:

汤海燕, 赵茂爽, 冯莉, 曹泽星. 褐煤模型化合物中含氧官能团脱出反应的理论研究. 高等学校化学学报, 2014, 35(11): 2370.

TANG Haiyan, ZHAO Maoshuang, FENG Li, CAO Zexing. Theoretical Studies on the Taking off of Oxygen-containing Functional Groups in Lignite Model Compounds^†. Chem. J. Chinese Universities, 2014, 35(11): 2370.

图/表 7

Fig.1 Potential energy profiles of the cross-linking reaction of benzoic acid(Paths A1—A3) Bond lengths are in nm; energies are in kJ/mol.

Fig.2 Potential energy profiles of the cross-linking reaction of benzoic acid and phenol(Paths B1—B3) Bond lengths are in nm; energies are in kJ/mol.

Fig.3 Potential energy profiles of the cross-linking reaction of phenol(Path C) Bond lengths are in nm; energies are in kJ/mol.

Fig.4 Reaction mechanism of the two reaction paths of formic acid involves the different number of water molecules (A) HCOOH=CO2+H2; (B) HCOOH=H2O+CO2. The reaction activation energies are in kJ/mol.

Fig.5 Reaction mechanism of the three reaction paths of glycerol involves the different number of water molecules The reaction activation energies are in kJ/mol.

Fig.6 Reaction mechanism of the initial reaction of glycerol with metal ion The reaction activation energies are in kJ/mol.

Fig.7 Transition-state structure parameters for the dehydration of glycerol without Na+(A) and with Na+(B) Bond lengths are in nm.

参考文献 37

[1]	Feng L., Liu X. C., Song L. L., Wang X. H., Zhang Y., Cui T. W., Tang H. Y., Powder Technology,2013, 247, 19—23
[2]	Wang Y. G., Zhou J. L., Lin X. C., Coal Science and Technology,2013, 41(9), 182—184
	(王永刚, 周剑林, 林雄超. 煤炭科学技术,2013, 41(9), 182—184)
[3]	Zhao N., Lv Y. Z., Li G. J., Chem. Res. Chinese Universities,2013, 29(6), 1180—1184
[4]	Solomon P. R., Coal Structure: Advances in Chemistry Series, 1981, 192, 184—195
[5]	Li A. R., Wu D. H., Wang Q. C., Zhang K., Coal Conversion,2013, 36(1), 9—13
	(李爱蓉, 吴道洪, 王其成, 张锴. 煤炭转化,2013, 36(1), 9—13)
[6]	Zhu X. D., Zhu Z. B., Journal of East China University of Science and Tecnology,2000, 26(1), 14—17
	(朱学栋, 朱子彬. 华东理工大学学报,2000, 26(1), 14—17)
[7]	Wang S. R., Liang T., Ru B., Guo X. J., Chem. Res. Chinese Universities,2013, 29(4), 782—787
[8]	Bradley L. C., Miller S. F., Miller B. G., Tillman D. A., Energy & Fuels, 2011, 25, 1989—1995
[9]	Qian C. M., Zhou M., Wei J. H., Ye P. H., Yang X., International Journal of Mining Science and Technology,2014, 24, 137—141
[10]	Kuznetsov P. N., Kamenskii E. S., Kolesnikova S. M., Kuznetsova L. I., Solid Fuel Chemistry,2014, 48, 51—57
[11]	Liu L. J., Fei J. X., Cui M. Q., Hu Y. F., Wang J., Fuel Processing Technology,2014, 121, 56—62
[12]	Abbasi A. E., Yozgatligil A., Fuel,2014, 115, 841—849
[13]	Zhao G. W., Journal of Thermal Science, 2014, 23, 275—278
[14]	Wang N., Yu J. L., Tahmasebi A., Han Y.N., Lucas J., Wall T., Jiang Y., Energy & Fuels,2014, 28, 254—263
[15]	Xu Y., Zhang Y. F., Wang Y., Zhang G. J., Chen L., Journal of Analytical and Applied Pyrolysis,2013, 104, 625—631
[16]	Yang X. J., Zhang C., Tan P., Yang T., Fang Q. Y., Chen G., Energy & Fuels,2014, 28, 264—274
[17]	Zhao L. J., Ling L. X., Zhang R. G., Liu X. F., Wang B. J., Journal of Chemical Industry and Engineering,2008, 59(8), 2095—2102
	(赵俐娟, 凌丽霞, 章日光, 柳学芳, 王宝俊. 化工学报,2008, 59(8), 2095—2102)
[18]	Ling L. X., Zhao L. J., Zhang R. G., Wang B. J., Journal of Chemical Industry and Engineering,2009, 60(5), 1224—1230
	(凌丽霞, 赵俐娟, 章日光, 王宝俊. 化工学报,2009, 60(5), 1224—1230)
[19]	Wang B. J., Ling L. X., Zhang R. G., Xie K. C., Journal of China Coal Society,2009, 34(9), 1239—1248
	(王宝俊, 凌丽霞, 章日光, 谢克昌. 煤炭学报,2009, 34(9), 1239—1248)
[20]	Zeng F. G., Jia J. B., Acta Physico-Chimica Sinica,2009, 25(6), 1117—1124
	(曾凡桂, 贾建波. 物理化学学报,2009, 25(6), 1117—1124)
[21]	Zhou S. Q., Gu Y. X., Gu X., Chinese Journal of Inorganic Chemistry,2011, 27(6), 1202—1206
	(周素芹, 谷亚昕, 固旭. 无机化学学报,2011, 27(6), 1202—1206)
[22]	Wang X. H., Feng L., Cao Z. X., Liu X. C., Tang H. Y., Zhang M., Acta Chimica Sinica,2013, 71(7), 1047—1052
	(王新华, 冯莉, 曹泽星, 刘祥春, 汤海燕, 张曼. 化学学报,2013, 71(7), 1047—1052)
[23]	Jüntgen H., Fuel, 1984, 63, 731—737
[24]	Mae K., Maki T., Miura K., Journal of Chemical Engineering of Japan,2002, 35, 778—785
[25]	Xu W. C., Tomita., Fuel,1987, 66, 632—636
[26]	Berkovitz N., Hertog W., Fuel,1962, 41, 507—520
[27]	Eskay T. P., Britt P. F., Energy & Fuels,1996, 10, 1257—1261
[28]	Ibarra J. V., Moliner R., Gavilin M. P., Fuel,1991, 70, 408—413
[29]	Mae K., Maki T., Okutsu H., Minra K., Fuel,2000, 79, 417—425
[30]	Li C. Z., Yu J. L., Chang L. P., Advances in the Science of Victorian Brown Coal, Chemical Idustry Press, Beijing, 2009, 184—187
	(李春柱, 余江龙, 常丽萍. 维多利亚褐煤科学进展, 北京: 化学工业出版社, 2009, 184—187)
[31]	Zhang D. J., Xian X. F., Chem. J. Chinese Universities,1990, 11(7), 912—914
	(张代钧, 鲜学福. 高等学校化学学报, 1990, 11(7), 912—914)
[32]	Liu S. Y., Zhang Z. Q., Wang H. F., Journal of Molecular Modeling,2012, 18, 359—365
[33]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.02, Gau-ssian Inc., Wallingford CT, 2009
[34]	Ruelle P., Kesselring U. W., Nam-Tran H., J. Am. Chem. Soc., 1986, 108, 371—375
[35]	Gao C. G., Long Z. W., Tan X. F., Long B., Long C. Y., Qin S. J., Zhang W. J., Acta Chimica Sinica,2013, 71(5), 849—856
	(高成贵, 隆正文, 谭兴凤, 龙波, 龙超云, 秦水介, 张为俊. 化学学报,2013, 71(5), 849—856)
[36]	Murakami K., Shirato H., Ozaki J., Fuel Processing Technology,1996, 46, 183—194
[37]	Tang Q., Yu F. W., Lü H. Y., Ji B. J., Chemical Industry and Engineering Progress,2010, 29(1), 48—51
	(唐强, 于凤文, 吕红云, 计建炳. 化工进展,2010, 29(1), 48—51)

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