Thermodynamics of metal reactants for ammonia synthesis from steam, nitrogen and biomass at atmospheric pressure

Abstract

Catalytic ammonia synthesis at approximately 30 MPa and 800 K consumes about 5% of the global annual natural gas production causing significant CO₂ emissions. A conceptual solar thermochemical reaction cycle to produce NH₃ at near atmospheric pressure without natural gas is explored here and compared to solar thermochemical steam/air reforming to provide H₂ used in the Haber-Bosch process for NH₃ synthesis. Mapping of Gibbs free energy planes quantifies the tradeoff between the yield of N₂ reduction via metal nitridation, and NH₃ liberation via steam hydrolysis vs. the temperatures required for reactant recovery from undesirably stable metal oxides. Equilibrium composition simulations suggest that reactants combining an ionic nitride-forming element (e.g., Mg or Ce) with a transition metal (e.g., MgCr₂O₄, MgFe₂O₄, or MgMoO₄) may enable the concept near 0.1 MPa (at maximum 64 mol % yield of Mg₃N₂ through nitridation of MgFe₂O₄ at 1,300 K, and 72 mol % of the nitrogen in Mg₃N₂ as NH₃ during hydrolysis at 500 K). © 2011 American Institute of Chemical Engineers AIChE J, 58: 3203–3213, 2012