Decomposition of ammonia: The effect of syngas components on the activity of zeolite HΒ supported iron catalyst


Sarioglan A. , Durak-Cetin Y., Okutan H., Akgun F.

Chemical Engineering Science, cilt.171, ss.440-450, 2017 (SCI Expanded İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 171
  • Basım Tarihi: 2017
  • Doi Numarası: 10.1016/j.ces.2017.05.045
  • Dergi Adı: Chemical Engineering Science
  • Sayfa Sayıları: ss.440-450

Özet

Zeolite beta (Sio(2)/Al2O3 = 38) supported iron catalyst (Fe/HZ beta) was used to investigate the effects of syngas components on ammonia decomposition reaction at 700 degrees C and 1 atmosphere. While 97.3% of NH3 conversion was achieved over Fe/HZ beta catalyst under nitrogen atmosphere, conversions decreased tremendously upon the addition of syngas components. Conversion loss with H-2 was attributed to the competing reaction steps: N-H bond breaking and N-2 association. The number of active sites filled with N atoms was thought to be decreased under less favorable dehydrogenation atmosphere where minimum N-H bond breaking might take place. In the presence of CO, its inhibition effect was interpreted as competing reactions on the same active sites: one for CO bond dissociation and the other is N-H bond dissociation. On the other hand, neither H-2 nor CO alone did lead to a permanent activity loss. With coexistence of CO and H-2, a dramatic loss of activity to a level of 12.5% and a severe coking were observed. This was attributed to the metal dusting corrosion. This was verified both by XRD measurement and accumulated carbon inside the reactor. Upon CO2 addition to H-2-CO mixture, reverse water gas shift reaction was prominent. Interestingly, NO2 was detected in the product stream as an indication of the oxidation reaction between NH3 and H2O. In the presence of CO2, hematite phase (alpha-Fe2O3) appeared with the loss of polycrystalline a-iron phase. CH4 addition to CO-H-2-CO2 mixture seemed to be effective in further reducing NH3 concentration in syngas. A well-known reaction between CH4 and NH3 to give HCN was seen to be responsible for the unexpected increase in NH3 conversion. Finally, H2S in syngas did not seem to poison the active sites but was exposed to a similar decomposition giving elemental sulfur. (C) 2017 Elsevier Ltd. All rights reserved.