Generation mechanism of NOx and N2O precursors (NH3 and HCN) from aspartic acid pyrolysis: A DFT study
Keywords:
pyrolysis, aspartic acid (Asp), amino acid, DFTAbstract
Abstract: In order to better understand the mechanism of NOx and N2O precursors (NH3 and HCN) from aspartic acid (Asp) pyrolysis, decomposition reaction networks resulting in the generation of NH3 and HCN were investigated by employing density function theory methods. After several pathways were analyzed in detail, two series of pyrolytic reactions containing three possible pathways were proposed. All the reactants, transition states, intermediates and products were optimized, also the electronic properties on these crucial points were discussed, which shows that Cα acts as the most active site to initiate the pyrolysis reaction, where the direct Cα-Cβ bond breakage, due to the atomic charge population of repulsion, led to one key route for the generation of HCN, and the transfer of Hα from Cα to Cβ resulting in another key route for the generation of HCN, while the transfer of Hα from Cα to N atom of Asp resulting in the key route for the generation of HN3. Further, the kinetic analysis based on speed control method in each key reaction pathway was conducted to further compare the generation of HCN and NH3 under various temperatures. The above results are in accordance with the related experimental results. Keywords: pyrolysis, aspartic acid (Asp), amino acid, DFT DOI: 10.3965/j.ijabe.20160905.2559 Citation: Kang P, Qin W, Fu Z Q, Wang T P, Ju L W, Tan Z F. Generation mechanism of NOx and N2O precursors (NH3 and HCN) from aspartic acid pyrolysis: A DFT study. Int J Agric & Biol Eng, 2016; 9(5): 166-176.References
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[3] Tian F J, Yu J L, McKenzie L J, Hayashi J, Li C Z. Formation of NOx precursors during the pyrolysis of coal and biomass. Part IX. Effects of coal ash and externally loaded-Na on fuel-N conversion during the reforming of coal and biomass in steam. Fuel, 2006; 85(10-11): 1411–1417.
[4] Tian F J, Yu J L, McKenzie L J, Hayashi J, Li C Z. Conversion of fuel-N into HCN and NH3 during the pyrolysis and gasification in steam: a comparative study of coal and biomass. Energ. Fuel, 2007; 21(2): 517–521.
[5] Giuntoli J, de Jong W, Verkooijen A H M, Piotrowska P, Zevenhoven M, Hupa M. Combustion characteristics of biomass residues and biowastes: fate of fuel nitrogen. Energ. Fuel, 2010; 24(10): 5309–5319.
[6] Tian Y, Zhang J, Zuo W, Chen L, Cui Y N, Tan T. Nitrogen conversion in relation to NH3 and HCN during microwave pyrolysis of sewage sludge. Environ. Sci. Technol., 2013; 47(7): 3498–3505.
[7] Stubenberger G, Scharler R, Zahirović S, Obernberger I. Experimental investigation of nitrogen species release from different solid biomass fuels as a basis for release models. Fuel, 2008; 87(6): 793–806.
[8] Tian F J, Yu J L, Mckenzie L J, Hayashi J, Li C Z. Conversion of fuel-N into HCN and NH3 during the pyrolysis and gasification in steam: a comparative study of coal and biomass. Energ. Fuel., 2007; 21(2): 517–521.
[9] Darvell L I, Brindley C, Baxter X C, Jones J M, Williams A. Nitrogen in biomass char and its fate during combustion: a model compound approach. Energ. Fuel, 2012; 26(11): 6482–6491.
[10] Yuan S, Zhou Z J, Li J, Wang F C. Nitrogen conversion during rapid pyrolysis of coal and petroleum coke in a high-frequency furnace. Appl. Energ., 2012; 92: 854–859.
[11] Yuan S, Chen X L, Li W F, Liu H F, Wang F C. Nitrogen conversion under rapid pyrolysis of two types of aquatic biomass and corresponding blends with coal. Bioresource Technol., 2011, 102(21): 10124–10130.
[12] Scicchitano P, Carbonara S, Ricci G, Mandurino C, Locorotondo M, Bulzis G, et al. HCN channels and heart rate. Molecules, 2012; 17(4): 4225–4235.
[13] Ren Q Q, Zhao C S. Evolution of fuel-N in gas phase during biomass pyrolysis. Renew. Sust. Energ. Rev., 2015; 50: 408–418.
[14] Becidan M, Skreiberg Ø, Hustad J E. NOx and N2O precursors (NH3 and HCN) in pyrolysis of biomass residues. Energ. Fuel, 2007; 21(2): 1173–1180.
[15] Hansson K M, Samuelsson J, Åmand L E, Tullin C. The temperature’s influence on the selectivity between HNCO and HCN from pyrolysis of 2, 5-diketopiperazine and 2-Pyridone. Fuel, 2003; 82(18): 2163–2172.
[16] Hansson K M, Samuelsson J, Tullin C, Åmand L E. Formation of HNCO, HCN, and NH3 from the pyrolysis of bark and nitrogen-containing model compounds. Combust. Flame, 2004; 137(3): 265–277.
[17] Yuan S, Zhou Z J, Li J, Chen X L, Wang F C. HCN and NH3 released from biomass and soybean cake under rapid pyrolysis. Energ. Fuel, 2010; 24(11): 6166– 6171.
[18] Ren Q Q, Zhao C S. NOx and N2O precursors from biomass pyrolysis: role of cellulose, hemicellulose and lignin. Environ. Sci. Technol., 2013; 47(15): 8955– 8961.
[19] Ren Q Q, Zhao C S, Wu X, Liang C, Chen X P, Shen J Z, et al. Effect of mineral matter on the formation of NOx precursors during biomass pyrolysis. J. Anal. Appl. Pyrol., 2009; 85(1-2): 447–453.
[20] Ren Q Q, Zhao C S. NOx and N2O precursors from biomass pyrolysis: nitrogen transformation from amino acid. Environ. Sci. Technol., 2012; 46(7): 4236–4240.
[21] Ren Q Q, Zhao C S. NOx and N2O precursors (NH3 and HCN) from biomass pyrolysis: interaction between amino acid and mineral matter. Appl. Energ., 2013; 112(4): 170–174.
[22] Perdew J P, Burke K, Wang Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B., 1996; 54(23): 16533–16537.
[23] Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys. Rev. Lett., 1996; 77(18): 3865–3868.
[24] Delley B. An all-electron numerical method for solving the local density functional for polyatomic. molecules. J. Chem. Phys., 1990; 92(1): 508–517.
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[36] Ren Q Q. Nitrogen transfer mechanism during thermal utilization of agricultural straw. Nanjing: Southeast University, 2011.
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2016-09-30
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Peng, K., Wu, Q., Tipeng, W., Zongqiang, F., Liwei, J., & Zhongfu, T. (2016). Generation mechanism of NOx and N2O precursors (NH3 and HCN) from aspartic acid pyrolysis: A DFT study. International Journal of Agricultural and Biological Engineering, 9(5), 166–176. Retrieved from https://ijabe.migration.pkpps03.publicknowledgeproject.org/index.php/ijabe/article/view/2559
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