Plasma (catalyst) assisted nitrogen fixation reactor development for nitric oxide and ammonia production
Year: 2017

This chapter focuses on the production of NOx from air and air+O2 is investigated in a pulsed powered milli scale gliding arc (GA) reactor, aiming at a containerized process for fertilizer production. First, the electrical parameters of the gliding arc reactor, such as frequency, pulse width, and amplitude of input voltage are investigated. Influence of process parameters such as feed mixture, flowrate, feed preheating, and effect of Ar and O2 content in feed are also investigated at varying specific energy input. The findings are correlated with high speed imaging of the GA dynamics. Increase in frequency, pulse width and input voltage amplitude resulted in an increased specific energy input, which lead to increase in NOx production. An O2 content of 40 48% was optimum, with an enhancement of ~20% in NOx production. Addition of Ar and preheating of the feed resulted in lower NOx production. The volume covered by GA depends strongly on the gas flowrate, emphasizing that the gas flowrate has a major impact on the GA dynamics and the reaction kinetics. For 0.5 L/min, 1.4 vol% of NOx concentration was realized. Chapter 1 Introduction Page 20 Processing, Wiley, 2005.  S. L. Miller, Science 1953, 117, 528 529.  S. L. Miller, H. C. Urey,   R. Hippler, Low Temperature Plasma Physics: Fundamental Aspects and Applications, Wiley VCH, 2001.  A. P. Napartovich, Plasmas Polym. 2001, 6, 1 14.  M. Thiemann, E. Scheibler, K. W. Wiegand, in Ullmann's Encycl. Ind. Chem. Wiley VCH Verlag GmbH Co. KGaA, 2000.  D. C. Frost, C. A. McDowell,  A, 278 284.  F. Coudert J, Contribution D L'ktude de La Synthese Des Oxydes D'azote Par Chalumeau D Plasma, Universitt de Limoges, 1978.  P. R. Ammann, R. S. Timmins,  1966, 12, 956 963.  G. Schaub, T. Turek, Energy Flows, Material Cycles and Global Development: A Process Engineering Approach to the Earth System, 2011.  S. Samukawa, M. Hori, S. Rauf, K. Tachibana, P. Bruggeman, G. Kroesen, J. C. Whitehead, A. B. Murphy, A. F. Gutsol, S. Starikovskaia, et al.  2012, 45, 253001.  P. Fauchais, J. Rakowitz,   J. C. Whitehead,  2016, 49, 243001.  J. C. Whitehead,  2010, 82, 1329 1336.  H. Kim, Y. Teramoto, N. Negishi, A. Ogata, Catal. Today 2015, 256, 13 22.  E. C. Neyts, K. (Ken) Ostrikov, M. K. Sunkara, A. Bogaerts,  2015, 115, 13408 13446.  E. C. Neyts, a Bogaerts,  2014, 47, 224010.  C. E. Stere, W. Adress, R. Burch, S. Chansai, A. Goguet, W. G. Graham, F. De Rosa, V. Palma, C. Hardacre, ACS Catal. 2014, 4, 666 673.  A. Gomez Ramirez, V. J. Rico, J. Cotrino, A. R. Gonzalez Elipe, R. M. Lambert, ACS Catal. 2014, 4, 402 408.  L. Wang, Y. Yi, Y. Zhao, R. Zhang,  Guo, ACS Catal. 2015, 4167 4174.  X. Duan, Z. Hu, Y. Li, B. Wang,  2014, DOI 10.1002/aic.  Q. Wang, B. H. Yan, Y. Jin, Y. Cheng, Plasma Chem. Plasma Process. 2009, 29, 217 228.  X. Tu, H. J. Gallon, M. V Twigg, P. a Gorry, J. C. Whitehead,  2011, 44, 274007.  H. L. Chen, H. M. Lee, S. H. Chen, M. B. Chang, S. J. Yu, S. N. Li,  2009, 43, 2216 27.  A. M. Vandenbroucke, R. Morent, N. De Geyter, C. Leys,  2011, 195, 30 54.  J. Van Durme, J. Dewulf, C. Leys, H. Van Langenhove,  2008, 78, 324 333.  F. Thevenet, L. Sivachandiran, O. Guaitella, C. Barakat, a Rousseau,  2014, 47, 224011.  M. B. Kizling, S. G. Jaras,  21.  A. Fridman, S. Nester, L. A. Kennedy, A. Saveliev, O. Mutaf yardimci, 1999, 25, 211 231.  A. Czemichowski, 1994, 66, 1301 1310.  S. Kolev, a Bogaerts, Plasma Sources Sci. Technol. 2015, 24, 15025.  A. Indarto, D. R. Yang, J. W. Choi, H. Lee, H. K. Song,  2007, 146, 309 315.  Pornmai, A. Jindanin, H. Sekiguchi, 2012, 2 12.  B. Spasova, D. Tiemann, M. O'Connell, A. Ziogas, G. Kolb, V. Hessel,  Energy 2014, 39, 12657 12666.  X. Tu, J. C. Whitehead,  Energy 2014, 39, 9658 9669.  K. Krawczyk, B. Ulejczyk, Plasma Chem. Plasma Process. 2003, 23, 265 281.  V. Dalaine, J. M. Cormier, P. Lefaucheux,  1998, 83, 2435 2441.  K. Krawczyk, M. Mlotek,  2001, 30, 233 245.  V. Hessel, a. Anastasopoulou, Q. Wang, G. Kolb, J. Lang, Catal. Today 2013, 211, 9 28.  V. Hessel, Q. Wang, J. Lang, Chim. Oggi/Chemistry Today 2016, 34, 78 81.  A. Anastasopoulou, Q. Wang, V. Hessel, J. Lang, Processes 2014, 2, 694 710.  A. Anastasopoulou, S. Butala, B. S. Patil, J. Lang, V. Hessel, Q. Wang, Submitt. to Process. 2016. CHAPTER 2 PLASMA ASSISTED NITROGEN OXIDE PRODUCTION FROM AIR IN A GLIDING ARC REACTOR: CHARACTERIZATION FOR ELECTRICAL AND PROCESS PARAMETERS This chapter has been adapted from: Patil, B. S. F. J. J. Peeters, Medrano J. A. Gerard van Rooij, Gallucci F. Lang, J. Wang, Q. Hessel, V. (2016) Plasma nitrogen oxide production from air at atmospheric pressure using a pulse powered milli scale gliding arc reactor.  Patil, B. S. Rovira Palau, Joan, Hessel, V. Lang, J. Wang, Q. (2016) Plasma nitrogen oxides synthesis in a milli scale gliding arc reactor: investigating the electrical and process parameters. Plasma Chem. Plasma Proc. 36(1) 241 257.  This chapter focuses on the production of NOx from air and air+O2 is investigated in a pulsed powered milli scale gliding arc (GA) reactor, aiming at a containerized process for fertilizer production. First, the electrical parameters of the gliding arc reactor, such as frequency, pulse width, and amplitude of input voltage are investigated. Influence of process parameters such as feed mixture, flowrate, feed preheating, and effect of Ar and O2 content in feed are also investigated at varying specific energy input. The findings are correlated with high speed imaging of the GA dynamics. Increase in frequency, pulse width and input voltage amplitude resulted in an increased specific energy input, which lead to increase in NOx production. An O2 content of 40 48% was optimum, with an enhancement of ~20% in NOx production. Addition of Ar and preheating of the feed resulted in lower NOx production. The volume covered by GA depends strongly on the gas flowrate, emphasizing that the gas flowrate has a major impact on the GA dynamics and the reaction kinetics. For 0.5 L/min, 1.4 vol% of NOx concentration was realized.This chapter focuses on the production of NOx from air and air+O2 is investigated in a pulsed powered milli scale gliding arc (GA) reactor, aiming at a containerized process for fertilizer production. First, the electrical parameters of the gliding arc reactor, such as frequency, pulse width, and amplitude of input voltage are investigated. Influence of process parameters such as feed mixture, flowrate, feed preheating, and effect of Ar and O2 content in feed are also investigated at varying specific energy input. The findings are correlated with high speed imaging of the GA dynamics. Increase in frequency, pulse width and input voltage amplitude resulted in an increased specific energy input, which lead to increase in NOx production. An O2 content of 40 48% was optimum, with an enhancement of ~20% in NOx production. Addition of Ar and preheating of the feed resulted in lower NOx production. The volume covered by GA depends strongly on the gas flowrate, emphasizing that the gas flowrate has a major impact on the GA dynamics and the reaction kinetics. For 0.5 L/min, 1.4 vol% of NOx concentration was realized. 2 Chapter 2 NOx Production in Milli scale Gliding Arc Reactor Page 22 2.1 Introduction Among several alternatives, electricity driven non equilibrium plasma processes are considered to be very attractive contenders for energy efficient nitrogen fixation[9,10] It is worth noting that nitrogen fixation via nonthermal plasma (NTP) offers an opportunity to produce fossil free nitrogen oxides due its 3.5 times lower theoretical energy requirement[11,12] In NTP, highly energetic electrons collide with bulk gas molecules, yielding a mixture of highly reactive species which enable thermodynamically unfavorable reactions like nitrogen fixation at low temperatures and atmospheric pressures[13,14] Plasma processes are more attractive on smaller scales like in containers or modular plants[15] Plasma assisted nitrogen fixation offers an interesting opportunity as atmospheric pressure and ambient temperature processing will substantially improve plant safety and decrease the operational and capital costs compared to the high pressure HaberBosch process[16] The mild operating conditions and relatively small scale could also encourage development of localized nitrogen fertilizer production plants. The approach of decentralized chemical production has been undertaken in the EU funded MAPSYN project for plasma assisted nitrogen fixation process[11,12] which would eventually benefit remote places to produce their own fertilizer and fuels, using only renewable energy sources such as solar or wind[17] along similar lines, N2 applied, a Norwegian company, is commercializing the plasma assisted nitrogen fixation process on smaller scale for use by farmers[18] The overall reactions representing nitrogen fixation with oxygen to give NOx (NO NO2) which further absorbed in water to yield nitric acid are depicted by reaction R1 and R2. The ratio of NO and NO2 is determined by thermodynamic equilibrium and the reaction kinetics[29] The reaction enthalpy of the process (DH) is fairly high, therefore high energy is needed to carry out this reaction. DHf= 90.4 kJ mol 1 (R1) DHf= 33.2 kJ mol