Hydroformylation of 1-Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior–Reaction Performance–Catalyst Recycling

Schäfer, Elisabeth; Brunsch, Yvonne; Sadowski, Gabriele; Behr, Arno

doi:10.1021/ie300484q

Cited by 110 publications

(134 citation statements)

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“…In this work, we consider the separation of a mixture of the closely boiling isomers n-dodecanal and 2-methylundecanal resulting from hydroformylation of long-chain olefines based on renewable resources in a new type of process [31,32] into its single components with a predefined purity. This mixture is exemplary for a large class of binary isomeric mixtures.…”

mentioning

confidence: 99%

Deterministic global optimization in conceptual process design of distillation and melt crystallization

Kunde

Michaels

Mićović

et al. 2016

Chemical Engineering and Processing: Process Intensification

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mentioning

confidence: 99%

Deterministic global optimization in conceptual process design of distillation and melt crystallization

Kunde

Michaels

Mićović

et al. 2016

Chemical Engineering and Processing: Process Intensification

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“…In reality this is not the case and different compositions of the TMS can greatly affect reactor performance and catalyst leaching amounts. 18,23,24 These works also reveal that higher molecular weight alkanes and lower temperature phase separation in the decanter have a beneficial effect by reducing catalyst leaching. This data is, regrettably, relatively sparse to use in a process model within the complete allowable design space of solvent selection.…”

Section: ■ Introductionmentioning

confidence: 98%

“…The solid lines represent the predicted LLE, and the points represent the experimental data collected by Schafer et al24 …”

mentioning

confidence: 99%

Data Driven Conceptual Process Design for the Hydroformylation of 1-Dodecene in a Thermomorphic Solvent System

McBride

Sundmacher

2015

Ind. Eng. Chem. Res.

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The purpose of this work is to investigate the effect that a solvent mixture has on the process-wide performance of the hydroformylation of 1-dodecene. A thermomorphic solvent mixture consisting of dimethylformamide and decane is used as a tunable solvent that ensures monophasic conditions during the reaction and that is also used to separate the homogeneous catalyst from the product through temperature controlled phase splitting in a decantation unit. So far reactor and process design for this reaction has been primarily based on a specific composition of the solvent mixture and without considering the economic impact of catalyst leaching. In order to reduce the complexity of the conceptual process design problem, linear regression models were used to accurately estimate the partition coefficients of the multicomponent mixture in the decanter. Using limited available experimental data from the literature, correlations were derived for catalyst loss based on the composition of the thermomorphic solvent system. Optimization results show that the catalyst loss has a significant effect on the total annualized cost of the process and that the frequently studied solvent composition should be altered to increase catalyst retention. ■ INTRODUCTIONIn the past decade, interest in homogeneous catalysis has increased substantially with the recovery or retention of expensive transition metal catalysts being the object of much study. This is especially true in the hydroformylation of longchain olefins where, due to the high cost of the catalyst complex composed quite often of rhodium and expensive ligands, industrial realization has been problematic. 1 Many different methods have been investigated primarily for the hydroformylation of 1-octene, which is extensively discussed in the review by Cole-Hamilton. 2 One effective method for hydroformylation has been done using supported ionic liquid phase catalysis, where the catalyst is supported in a thin film formed by an ionic liquid. 3 Other attempts at restricting catalyst loss involve tethering the catalyst complex to mesoporous materials, effectively creating semiheterogeneous catalysts. 4 Membrane filtration methods were also effectively developed for the continuous hydroformylation of 1-octene using specially designed polymer catalysts, whose bulky nature reduces the permeability of the catalyst through the membrane. 5 A CO 2 -expanded liquid (CXL) enhanced version of this process has also been implemented and operated economically with reasonably low and stable levels of catalyst loss. 6 A similar principle has been investigated using molecular weight enhanced ligands with polyhedral oligomeric silsesquioxanes (POSS) to increase retention in nanofilters. 7 Various hydrogenation reactions also utilizing a rhodium-based homogeneous catalyst in aqueous micellar solutions were investigated for catalyst performance and recovery. 8 Similar procedures have been used to recover the rhodium-based catalyst complex in the hydroformylation of 1-dodecene by using surfactants 9,10 or by...

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“…By choice of appropriate conditions, the formation of undesired side products can be suppressed and thus an increase of yield or selectivity can be obtained. 7 Long chain olefins from sustainable resources are a versatile alternative to substrates from petrochemicals. 8,9 Their use poses challenges to an appropriate process design in terms of the solubility of substrates and the separation of products and catalyst.…”

Section: Introductionmentioning

confidence: 99%

The thermochemistry of long chain olefin isomers during hydroformylation

Kohls

Stein

2017

New J. Chem.

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Rhodium-catalysed hydroformylation is the major industrial process to obtain aldehyde products from olefins. The isomerization of the olefin at the catalyst is the most prominent side reaction and lowers the overall yield of the process. We here investigate whether the olefin isomer distribution obtained from batch experiments using Rh(BiPhePhos) as a catalyst and n-decene as the olefin reaches the thermodynamic equilibrium and computational quantum chemical approaches are able to accurately reproduce the experimental olefin isomer distribution. The relative energies of cis/trans configurational and double bond positional isomers of long chain n-decene were calculated using Hartree-Fock, DFT and correlated ab initio methods. Results were compared to experimental data. Electron correlation was found to be critical for the description of cis-isomer relative energies. Dispersion corrections in the DFT calculations partially compensate for deficiencies and generally improve the agreement with experiment. Adding thermodynamic corrections suffers from the neglect of certain contributions to the entropy of flexible molecules. Accounting for the entropy of mixing of multiple conformers significantly reduces the deviation from experiment. The equilibrium distribution of long chain olefins is reasonably described by correlated QM and also some density functional methods. Computational thermochemistry has thus reached a state where it provides reliable parameters for complex reaction network models and process engineering.

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Hydroformylation of 1-Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior–Reaction Performance–Catalyst Recycling

Cited by 110 publications

References 45 publications

Deterministic global optimization in conceptual process design of distillation and melt crystallization

Deterministic global optimization in conceptual process design of distillation and melt crystallization

Data Driven Conceptual Process Design for the Hydroformylation of 1-Dodecene in a Thermomorphic Solvent System

The thermochemistry of long chain olefin isomers during hydroformylation

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