Methodology of multiphase reaction kinetics and hydrodynamics identification: Application to catalyzed nitrobenzene hydrogenation

Frikha, Nader; Schaer, Éric; Houzelot, Jean-Léon

doi:10.1016/j.cej.2006.08.012

Cited by 18 publications

(5 citation statements)

References 23 publications

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“…This indicates that the reaction progress is much slower than mass transfer, so that the process is mainly limited by mass transfer. Although this interpretation could be a hasty conclusion given the unverified reaction mechanism, it agrees both with findings in our previous simulations [46] utilizing a verified one-step reaction mechanism and with experimental studies [21,23] where a very long period of time is required to achieve complete conversion of nitrobenzene.…”

Section: Mass Transfer Simulationsupporting

confidence: 91%

“…Although the reaction has long been studied in a wide range of conditions with respect to phase, solvent and catalysts, many studies conclude that its mechanism has not been fully elucidated yet. Thus, simplified global reaction mechanisms such as the Langmuir-Hinshelwood type mechanism have been widely used in the optimization of reaction processes dictated by, for example, liquid-gas or liquid-solid mass transfer, solubility, operating pressure and stirring speed [20][21][22][23]. Recently, models based on the density functional theory enable the reaction path analysis and determination of activation energies for the constituent elementary steps [24,25].…”

Section: Introductionmentioning

confidence: 99%

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A Qualitative Numerical Study on Catalytic Hydrogenation of Nitrobenzene in Gas-Liquid Taylor Flow with Detailed Reaction Mechanism

Woo

Maier

Tischer

et al. 2020

Fluids

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While the number of computational studies considering two-phase flows in microfluidic systems with or without mass transfer is increasing, numerical studies incorporating chemical reactions are still rare. This study aims to simulate the catalytic hydrogenation of nitrobenzene in gas-liquid Taylor flow by combining interface-resolving numerical simulations of two-phase flow and mass transfer by a volume-of-fluid method with detailed modeling of the heterogeneous chemical reaction by software package DETCHEMTM. Practically relevant physical properties are utilized for hydrodynamic and mass transfer simulations in combination with a preliminary reaction mechanism based on density functional theory. Simulations of mass transfer are conducted using a predetermined velocity field and Taylor bubble shape. At the beginning of the simulation when liquid nitrobenzene is not saturated by hydrogen, axial profiles of surface species concentrations and reaction rates show local variations. As hydrogen dissolves in nitrobenzene, the concentration profiles of surface species at the wall become uniform, eventually reaching an equilibrium state. Neglecting the local variation in a short initial period will allow further simplification of modeling surface reactions within a Taylor flow.

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Section: Mass Transfer Simulationsupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

A Qualitative Numerical Study on Catalytic Hydrogenation of Nitrobenzene in Gas-Liquid Taylor Flow with Detailed Reaction Mechanism

Woo

Maier

Tischer

et al. 2020

Fluids

View full text Add to dashboard Cite

show abstract

“…To measure the mass-transfer coefficient, we have followed the variation of pressure as in the work of Laugier, Frikha et al, and Hichri et al The mass-transfer coefficient ( k L a ) is defined by the following equation: …”

Section: Resultsmentioning

confidence: 99%

Carbonation of Vegetable Oils: Influence of Mass Transfer on Reaction Kinetics

Zheng

Burel

Salmi

et al. 2015

Ind. Eng. Chem. Res.

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The carbonation of epoxydized vegetable oil was studied by using tetra-nbutylammonium bromide (TBAB) as catalyst. Thermal stability of TBAB was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and it was demonstrated that the maximum reaction temperature should not exceed 130°C. Reaction conditions were optimum at 130°C, 50 bar, with 3.5% mol of catalyst. The gas-liquid mass transfer coefficient and solubility of CO 2 were determined by taking into account the non-ideality of the gas phase using PengRobinson state equations. At 130°C, the CO 2 solubility was found to be independent from epoxide conversion and equal to 0.57 mol.L -1 , and the gas liquid mass transfer coefficient (k L a) decrease with the epoxide conversion, i.e., at 0 % of conversion k L a = 0.0249 s -1 and at 94 % of conversion k L a = 0.0021 s -1 .

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“…The calculated liquid hydrogen concentration is then used in the rate expressions. The mass transfer coefficient is characterized as a function of the stirring speed rather than relying on a power-to-volume correlation, considering the unavailability of power measurements for the impeller in this particular process. − It is important to note that the correlation in eq is not guaranteed to be independent of flow regimes like a power-to-volume correlation since this simplification assumes a constant gas power number . However, it still accounts for the variation in stirring speed and is, therefore, more descriptive than only considering a constant mass transfer coefficient.…”

Section: Model Construction and Methodology Developmentmentioning

confidence: 99%

Advancing Nitrobenzene Hydrogenation Process Understanding: A Multiscale Modeling Approach using Industrial Pharmaceutical Production Data

Callewaert,

Pessanha,

Lauwaert

et al. 2024

Ind. Eng. Chem. Res.

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The pharmaceutical industry is under increasing pressure to reduce production costs and operate within agile supply chains by leveraging the capabilities that come with integrated data infrastructures and increasing access to various forms of modeling. In contrast to bulk chemical production, pharmaceutical productions typically operate at significantly lower volumes and allow for narrower variability in critical parameters due to tightly defined operating ranges. This makes the data acquired from the process challenging to analyze with statistical methods, but the application of engineering and scientific relations as multiscale models offers a more effective way of leveraging the historical data that are available. In this work, a multiscale reaction model is developed for an exothermic liquid phase hydrogenation of a nitrobenzene functionality in the synthesis of an active pharmaceutical ingredient (API) by using available production data. The developed model successfully described the interplay between reaction kinetics, gas−liquid mass transfer, and heat removal present in the process data, as evident from the simulated versus observed temperature evolution with batch time, which was used as an indirect measurement of the reaction conversion. Moreover, the model was also able to reproduce the temperature profiles in the case of a 30% scale-up. Simulated concentration profiles indicate that the end of the reaction occurs within a much shorter time frame than that prescribed by the process recipe, suggesting that the batch time can be reduced by more than 50%. The results demonstrate the flexibility and predictive power of this type of modeling approach because this model was developed using passive data collection of standard process parameters rather than through a dedicated Design of Experiments (DoE).

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Methodology of multiphase reaction kinetics and hydrodynamics identification: Application to catalyzed nitrobenzene hydrogenation

Cited by 18 publications

References 23 publications

A Qualitative Numerical Study on Catalytic Hydrogenation of Nitrobenzene in Gas-Liquid Taylor Flow with Detailed Reaction Mechanism

A Qualitative Numerical Study on Catalytic Hydrogenation of Nitrobenzene in Gas-Liquid Taylor Flow with Detailed Reaction Mechanism

Carbonation of Vegetable Oils: Influence of Mass Transfer on Reaction Kinetics

Advancing Nitrobenzene Hydrogenation Process Understanding: A Multiscale Modeling Approach using Industrial Pharmaceutical Production Data

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