The selective oxidation of ammonia over alumina supported catalysts: Experiments and modelling

J. M. Jones (Corresponding Author), M. Pourkashanian, A. Williams, R.I. Backreedy, L.I. Darvell, Pekka Simell, Katja Heiskanen, P. Kilpinen

Research output: Contribution to journalArticleScientificpeer-review

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Abstract

Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on γ-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H2O, H2, CO2, CH4, H2S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H2S; Cu/Al2O3 was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al2O3 was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723–906 K. Excellent conversion and selectivity to N2 was found in the temperature window 973–1173 K and 2.6 vol% O2. However, it also catalyses a rapid H2O2 reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or ‘tar’). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism Kilpinen 97. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723–906 K temperature range using a gas mixture containing 0.4 vol% ammonia and 0.01 vol% H2S in the presence of O2 (0–2.6 vol%).
Original languageEnglish
Pages (from-to)139 - 146
Number of pages8
JournalApplied Catalysis B: Environmental
Volume60
Issue number1-2
DOIs
Publication statusPublished - 2005
MoE publication typeA1 Journal article-refereed

Fingerprint

Aluminum Oxide
Ammonia
Catalyst supports
aluminum oxide
Catalytic oxidation
Alumina
ammonia
catalyst
oxidation
Oxidation
Gases
Tars
modeling
Tar
Gasification
Gas mixtures
experiment
Experiments
tar
Catalysts

Keywords

  • Ammonia (selective catalytic oxidation)
  • Gasification (biomass)
  • Modelling (kinetics, ammonia oxidation)

Cite this

Jones, J. M., Pourkashanian, M., Williams, A., Backreedy, R. I., Darvell, L. I., Simell, P., ... Kilpinen, P. (2005). The selective oxidation of ammonia over alumina supported catalysts: Experiments and modelling. Applied Catalysis B: Environmental, 60(1-2), 139 - 146. https://doi.org/10.1016/j.apcatb.2004.11.013
Jones, J. M. ; Pourkashanian, M. ; Williams, A. ; Backreedy, R.I. ; Darvell, L.I. ; Simell, Pekka ; Heiskanen, Katja ; Kilpinen, P. / The selective oxidation of ammonia over alumina supported catalysts : Experiments and modelling. In: Applied Catalysis B: Environmental. 2005 ; Vol. 60, No. 1-2. pp. 139 - 146.
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The selective oxidation of ammonia over alumina supported catalysts : Experiments and modelling. / Jones, J. M. (Corresponding Author); Pourkashanian, M.; Williams, A.; Backreedy, R.I.; Darvell, L.I.; Simell, Pekka; Heiskanen, Katja; Kilpinen, P.

In: Applied Catalysis B: Environmental, Vol. 60, No. 1-2, 2005, p. 139 - 146.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - The selective oxidation of ammonia over alumina supported catalysts

T2 - Experiments and modelling

AU - Jones, J. M.

AU - Pourkashanian, M.

AU - Williams, A.

AU - Backreedy, R.I.

AU - Darvell, L.I.

AU - Simell, Pekka

AU - Heiskanen, Katja

AU - Kilpinen, P.

PY - 2005

Y1 - 2005

N2 - Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on γ-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H2O, H2, CO2, CH4, H2S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H2S; Cu/Al2O3 was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al2O3 was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723–906 K. Excellent conversion and selectivity to N2 was found in the temperature window 973–1173 K and 2.6 vol% O2. However, it also catalyses a rapid H2O2 reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or ‘tar’). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism Kilpinen 97. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723–906 K temperature range using a gas mixture containing 0.4 vol% ammonia and 0.01 vol% H2S in the presence of O2 (0–2.6 vol%).

AB - Hot gas-clean up will improve the efficiency of emerging gasification technologies. Selective catalytic oxidation (SCO) of ammonia is a promising approach for dealing with the main fixed nitrogen species. The work presented here comprises both laboratory scale experimental measurements of potential SCO catalysts, as well as the development of a simple four-step reaction model to describe the behaviour of one of the more promising catalysts. A range of transition metal oxides supported on γ-alumina were studied for their activity in the SCO of ammonia in a simulated gasification gas mixture containing CO, H2O, H2, CO2, CH4, H2S and toluene as model tar species. Both copper and chromium based catalysts demonstrated a window of operating temperature over which they were resistant to poisoning by H2S; Cu/Al2O3 was in fact promoted by this gas for the SCO reaction. The ammonia conversion over 7% Cu/Al2O3 was studied in more detail, and this data was further used to develop a kinetic model for the reactions taking place over the temperature range 723–906 K. Excellent conversion and selectivity to N2 was found in the temperature window 973–1173 K and 2.6 vol% O2. However, it also catalyses a rapid H2O2 reaction. This reaction consumes all remaining available oxygen so that no other oxidation reactions take place (e.g. of methane or ‘tar’). The four-step reaction model was developed using the PLUG application of Chemkin and Surface Chemkin software coupled with the gas-phase mechanism Kilpinen 97. Rates for the heterogeneous oxidation of ammonia and hydrogen are included as well as forward and reverse reactions of the water gas shift. Over the temperature range in question, the surface reaction rates are much faster than the gas-phase reactions. The model is applicable for the 723–906 K temperature range using a gas mixture containing 0.4 vol% ammonia and 0.01 vol% H2S in the presence of O2 (0–2.6 vol%).

KW - Ammonia (selective catalytic oxidation)

KW - Gasification (biomass)

KW - Modelling (kinetics, ammonia oxidation)

U2 - 10.1016/j.apcatb.2004.11.013

DO - 10.1016/j.apcatb.2004.11.013

M3 - Article

VL - 60

SP - 139

EP - 146

JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

SN - 0926-3373

IS - 1-2

ER -