Century of Technology Trends in Methanol Synthesis: Any Need for Kinetics Refitting?

Abstract

Recently, methanol has gained increasing attention thanks to the variety of feedstocks suitable for its production and its low environmental impact granting the molecule a key role in future economic roadmaps as in Olah’s development model. Nowadays, fossil sources are not the exclusive sources to produce syngas: biogas is a promising alternative, leading to less severe operating conditions and smaller plant scales. The most widespread kinetic models for methanol synthesis, namely, the Graaf and the Vanden Bussche–Froment models, will be proven not to be fully adequate in characterizing these conditions. A robust refit is shown to outperform predictions from conventional models and follow recent trends in process operations. The refitted Graaf model is more flexible on the operating conditions and feed compositions, removing also some infeasible discontinuities present in conventional models. The final result is a more generalized and accurate Graaf’s model for methanol synthesis on CZA catalysts.

Impact of Kinetic Models on Methanol Synthesis Reactor Predictions: In Silico Assessment and Comparison with Industrial Data

“…Concerning the kinetic models, the kinetic parameters are taken from the corresponding references: or-GR, 51 ref-GR, 13 and VBF. 55 Table 6 reports the original expression for the considered kinetics, while Table 7 reports the corresponding values for the kinetic parameters, adsorption, and equilibrium constants.…”

“…In the case that the outliers or influential observation are uniformly distributed within the subsets, it is impossible to detect and remove them. 60 In the recent publication, Bisotti et al 13 proposed an effective way to robustly refit the or-GR model obtaining a more flexible kinetic model for the prediction of methanol production over CZA catalyst in a wider operating range. We Recycling ratio is defined as recycled gas to fresh make-up on volume flow.…”

“…The usage of industrial data for validation is the topic of this paper since ref-GR with lab-scale reactor experimental datasets has already been validated in a previous study. 13 Here, 78 or-GR both papers describe the same MegaMethanol plant in Shiraz; these papers deal with the same industrial plant and data; Keramat provides stream temperatures, while Rahmatmand includes the composition and reactors features Rahmatmand et al 83…”

Computer‐aided process intensification of natural gas to methanol process

“…The WGS kinetics is represented by the Amadeo and Laborde 41 model. Several kinetic models (e.g., Graaf et al, 42 Slotboom et al, 43 Lacerda et al, 44 Bisotti et al, 45 among others) are available for the MeOH reaction. We employ the Bussche and Froment model 46 as it shows good agreement with industrial reactor data 47,48 .…”

Economic Evaluation of Renewable Hydrogen Integration into Steelworks for the Production of Methanol and Methane

“…Methanol can be produced from syngas that is derived from a variety of sources, such as process off-gases [7,39], biogas [40], biomass [41,42], coal [22], and natural gas [43,44]. Methanol synthesis is based on the CO and CO 2 hydrogenation reactions that can be combined to form the reverse water-gas shift (RWGS) reaction [7]:…”