This thesis presents new kinetic models that have been validated over a wider range of conditions for methanol and ammonia synthesis, as well as a more accurate model for describing catalyst deactivation and a new reactor design for methanol synthesis that enables cheaper production from CO2 and H2 as renewable raw materials.
The transition to renewable energy requires sustainable production of key chemicals such as methanol and ammonia. These molecules serve dual roles as industrial feedstocks and as energy carriers for storing and transporting renewable hydrogen and carbon. However, the intermittency of renewable energy sources demands robust kinetic models that remain valid under dynamic operating conditions, which existing models lack.
This dissertation develops comprehensive kinetic frameworks for methanol and ammonia synthesis, validated against extensive experimental datasets totaling over 17,000 datapoints. For methanol synthesis on Cu/ZnO/Al2O3 catalysts, a simplified 7-parameter model is first developed, followed by an extended 40-parameter framework that incorporates methanol autocatalysis and byproduct formation across five industrial catalysts. This represents the first unified model capable of predicting dimethyl ether, methyl formate, methane, and higher alcohol formation kinetics. For ammonia synthesis, unified Langmuir-Hinshelwood models are developed for both iron-based and ruthenium-based catalysts, integrating over a century of literature data with improved thermodynamic descriptions validated up to 1000 bar.
Catalyst deactivation under CO2-rich conditions is quantified through symbolic regression, yielding models that outperform traditional approaches by factors of 2-4. A novel “Infinity Reactor” design is proposed, achieving 20% cost reduction in the methanol synthesis loop through internal heat integration between countercurrent catalyst beds. Dynamic modeling demonstrates flexible operation under fluctuating renewable energy availability. These contributions provide predictive and design tools that reduce technical and economic risks in the transition to renewable chemicals production.
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