(439h) Autothermal (CO2 and O2) Di-Reforming of Methane with the Ni-UGSO Catalyst: Lab-Scale Results and Kg-Lab Scale Tests at Industrial H2 Production Conditions

This work belongs to a larger endeavor aimed at studying the performance and the stability of a patent pending hydrocarbons reforming spinellized nickel catalyst prepared from an ilmenite metallurgical residue. Said residue is a negative value upgraded slag oxide (UGSO) coming from a TiO₂ slag production unit, operated by Rio Tinto Iron & Titanium, Quebec, Canada. Recently published results from experiments carried out with this catalyst exhibited high hydrogen production selectivity during methane steam, dry (CO₂) and autothermal (CO₂ and O₂) reforming and stability over time-on-stream (TOS).

At the lab-sale barometric conditions the best results are registered at T=850°C, molar ratios of CH₄/O₂=2 and CH₄/CO₂=3 and space velocity of GHSV=4500+/-100ml_STP/(h.g_cat). In these conditions, the catalyst remained stable without any deactivation and nil carbon formation during the entire 2 days of operation. The CH₄ conversion (98%) and the H₂ and CO yields (respectively 98.8% and 95.5% were equally stable and near-thermodynamic equilibrium. The steady state operation is characterized by the coexistence of multiple phases in the catalyst structure, including metallic, oxides and spinels.

Based on these results, a new project is funded by the Quebec and Canada Governments as well as our industrial partner (Rio Tinto Iron and Titane). Said project focuses on scaling up the process by a factor of 1000 (from g-lab to kg-lab scale); it aims at proving that both the catalyst (Ni-UGSO) and the autothermal direforming process can compete with the prevailing catalysts and processes for the production of H₂ from natural gas steam reforming. The main challenges are to prove that:

• this much cheaper catalytic formulation has at least the same efficiency, robustness and life cycle characteristics with the best commercially available catalysts;
• the autothermal direforming proposed is at least equally effective as the presently only commercially available process for H₂ production, that is ‘steam reforming’.

In this publication, we will present (a) the lab-scale results and the mechanistic explanation of the catalyst efficiency and robustness; (b) the scale-up calculations and criteria used; (c) the kg-lab set-up and operation protocol and (d) the first results at kg-lab scale towards answering the above challenges.