The butoxylation of dodecylamine: Reaction mechanism and kinetics

Müller, Pia; Krösschell, R.D.E.; Winkenwerder, Wyatt; Schaaf, J. van der

doi:10.1016/j.cej.2019.122939

Cited by 5 publications

(7 citation statements)

References 24 publications

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“…Comparing the new microkinetic model of this work with our previous work is only possible for the initial rate term of BO. Herein, we observe that compared to our previous published work the activation energy is higher (95 kJ/ vs 60 kJ/mol/K) 31 . The confidence intervals of both kinetic model strongly overlap, thus the quality of fit between these two works for this step are similar.…”

Section: Resultssupporting

confidence: 54%

Detailed chemomechanistic sensitivity study on the alkoxylation of fatty amines

Müller

Eeten

Winkenwerder

et al. 2020

Int J of Chemical Kinetics

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The mechanism of the autocatalytic alkoxylation of fatty amines was elucidated using a combined experimental and theoretical approach. The kinetic parameters of the elementary reaction steps are fitted to the experimental data gained in semibatch for propylene and butylene oxides with dodecylamine. A quality-offit sensitivity study was conducted to assess the robustness and accuracy of the model. Herein, we identified the kinetic parameters that are either crucial for a good fit or rate controlling in terms of the overall kinetics. It was found that the critical steps are the activation of the epoxide ring by a hydroxyl group present on either the intermediate or final product, highlighting the autocatalytic nature of the reaction. Furthermore, we introduced a so-called degree of conversion control to characterize the importance of each elementary reaction step toward the epoxide conversion. The degree of conversion control showed that the uncatalyzed route toward the secondary amine is only influential at low conversion. At higher conversion the route via the catalytic intermediate dominates. Alternative mechanisms were investigated as well but did not significantly improve the quality of fitting and were thus discarded.

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Section: Resultssupporting

confidence: 54%

Detailed chemomechanistic sensitivity study on the alkoxylation of fatty amines

Müller

Eeten

Winkenwerder

et al. 2020

Int J of Chemical Kinetics

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“…The most significant finding from the batch experiments is the clear sigmoidal curve, typical for auto‐catalytic reaction. PO follows in batch the same trends as butylene oxide in our previous reported work, but is a factor of 1.5 faster . The findings in batch were used to design the micro tubular flow set‐up.…”

Section: Resultsmentioning

confidence: 55%

“…The experimental set‐up is briefly explained for the comparable experiments in semi‐batch. A complete description is given in Müller et al The fatty amines were preloaded to a heated and vacuumed stirred 100 mL tank reactor. PO was added via a syringe at the top of the reactor.…”

Section: Methodsmentioning

confidence: 99%

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Propoxylation of fatty amines: Switching from batch to flow

Müller

Aguirre

Ljungdahl³

et al. 2020

J Adv Manuf & Process

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The ethoxylation and propoxylation of fatty amines are important industrial reactions commonly performed in de-intensified semi-batch reactors. The present study aims to intensify these reactions by transferring the process to continuous processing. Therefore, the propoxylation of octylamine, as model system, was performed in a batch reactor and in a micro tubular reactor. The micro tubular reactor operated with a single liquid phase at 15 bar pressure.The batch study found valuable kinetic and solubility information in the temperature range of 120 C-160 C. Moreover, a switch-flow method in the micro tubular reactor combined with inline FTIR gave a more detailed understanding of the reaction kinetics. In the micro tubular reactor, all PO was added in the feed according to stoichiometry, which led to a process intensification factor of 3.7 compared to fed-batch gas phase addition at maximum 2 bar.

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“…In our previous work, the butoxylation of dodecylamine was found to be auto‐catalytic, being both the amine and hydroxyl groups in the formed products the active species . It is generally understood that the reaction mechanism proceeds via destabilization of the epoxide ring in the presence of proton donating groups .…”

Section: Figurementioning

confidence: 99%

Polyurethane as Novel Catalyst for the Propoxylation of Fatty Amines

2020

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The propoxylation of fatty amines is a crucial reaction in the industrial production of surfactants. Catalyzing this reaction has so far proven unrewarding due to severe selectivity losses. In this study, rigid foam‐structured polyurethane, i. e., an extremely inexpensive material which has not been used as a catalyst ever before, shows an unprecedented catalytic activity during the in‐flow propoxylation of octylamine. The foam cells contain bound hydroxyl and amine groups that result in a bifunctional catalyst able to destabilize the ring structure of propylene oxide, and thus catalyze further propoxylation of fatty amines. An outstanding 10‐fold reduction of the residence time without any loss of selectivity is achieved with respect to the un‐catalyzed process. Furthermore, the polyurethane foam showed stable time‐on‐stream performance up to 10 bar and 110 °C.

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The butoxylation of dodecylamine: Reaction mechanism and kinetics

Cited by 5 publications

References 24 publications

Detailed chemomechanistic sensitivity study on the alkoxylation of fatty amines

Detailed chemomechanistic sensitivity study on the alkoxylation of fatty amines

Propoxylation of fatty amines: Switching from batch to flow

Polyurethane as Novel Catalyst for the Propoxylation of Fatty Amines

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