Effect of Conversion, Temperature and Feed Ratio on In₂O₃/In(OH)₃ Phase Transitions in Methanol Synthesis Catalysts: A Combined Experimental and Computational Study

Abstract

Catalytic hydrogenation of CO2 to methanol has attracted lots of attention as it makes CO2 useable as a sustainable carbon source. This study combines theoretical calculations based on the dummy catalytic cycle model with experimental studies on the performance and degradation of Indium‐based methanol synthesis catalysts. In detail, the reversibility of phase transitions in the In2O3/In(OH)3 system under industrial methanol synthesis conditions are investigated depending on conversion, temperature and feed ratio. The dummy catalytic cycle model predicts a peculiar degradation behavior of In(OH)3 at 275°C depending on the water formed either by methanol synthesis or the competing reverse water‐gas‐shift reaction. These results were validated by dedicated experimental studies confirming the predicted trends. Moreover, X‐ray diffraction and thermogravimetric analysis analysis proved the ensuing phase transition between the indium species. Finally, the validated model is used to predict how hydrogen drop out will affect the stability of the catalyst and derive practical strategies to prevent irreversible catalyst degradation.

Effect of Ni content on Cu–Mn/ZrO2 catalysts for methanol synthesis from CO2 hydrogenation

“…This was due to the stronger desorption ability of Ni for H 2 compared to that of Cu. 41 Combining this with findings from the literature, H 2 spilled over from Ni to Cu, [42][43][44] thereby providing more desorbed H 2 , which further contributed to the increase in hydrogenation ability.…”

Catalyst and Parameter Optimization Study for Slurry-Phase Methanol Synthesis Using Ni-Doped Indium-Based Catalysts

“…Under methanol synthesis conditions, In(OH) 3 dehydrates into In 2 O 3 and therefore the activity was in the range of M-In 2 O 3 /ZrO 2 . 30 However, a slightly lower STY was observed, which could be attributed to the surface reduction taking place before, subsequently initiating oxygen vacancies (Table 1). The experiment of the best-performing M-In 2 O 3 / ZrO 2 catalyst was repeated three times showing a very low standard deviation of ±0.0025 g MeOH g cat −1 h −1 (Table S2 and Figure S4).…”

Spatially Resolved Reaction Profiles of CO2 Hydrogenation to Methanol Using In-Based Catalysts in a Compact Profile Reactor

“…Indium-based catalysts have recently been studied extensively as alternative methanol synthesis catalysts by CO 2 hydrogenation. − The ZrO 2 supported In 2 O 3 catalyst also showed high stability, selectivity, and activity for CO 2 hydrogenation to methanol. ,,− In previous studies by Wesner and Kampe et al, the effects of the catalyst support, synthesis method, and metal promoter were identified to be key factors to increase the catalytic performance in the CO 2 hydrogenation to methanol …”