Miniplant-Scale Evaluation of a Semibatch-Continuous Tandem Reactor System for the Hydroformylation of Long-Chain Olefins

Abstract

Innovative reactor concepts show evidence to significantly improve the reaction performance in comparison to conventional reactor systems. To evaluate the reactor concepts, experimental investigation of the process behavior is indispensable. In this contribution, a reactor tandem comprising a repeatedly operated semibatch reactor (RSBR) followed by a continuously stirred tank reactor (CSTR) is analyzed for the hydroformylation of 1-dodecene. This reactor tandem was suggested by N. M. Kaiser et al. [Ind. Eng. Chem. Res. 2017, 56, 11507–11518] to increase the selectivity toward the linear aldehyde at high conversion levels of 1-dodecene. An additional degree of freedom is gained because of the combined utilization of a batchwise and continuously operated reactor. By using a dynamic process model for planning of the experiments, comparability is ensured with studies of a single CSTR from literature. The experiments confirm an increase in conversion and target product yield applying the RSBR + CSTR tandem, so that up to 90% selectivity is achieved with closed byproduct recycle.

Effect of Liquid–Liquid Interfacial Area on Biphasic Catalysis Exemplified by Hydroformylation

“…Among these are the use of additives that allow for an increased degree of mixing by enlarging the interfacial area through emulsions, − by increasing the solubility in the catalyst phase using cosolvents ,− such as alcohols, or by utilizing transport agents such as modified cyclodextrins − or pillararenes . Other strategies revolve around removing the phase boundary during the reaction using thermomorphic solvent systems , or, for the reductive hydroformylation, CO 2 -switchable solvent systems . Further, some strategies target the ligand design to move the catalyst species closer to the interface, such as catalyst-binding ligands or surface-active amphiphilic ligands, ,,− or to create a more active and selective complex. , However, these strategies introduce other challenges such as the use of additives, increased catalyst costs, metal leaching, and low separability .…”

Systematic Green Solvent Selection for the Hydroformylation of Long-Chain Alkenes

“…Recently, the hydroformylation of long-chain olefins, which can be produced from renewable feedstocks, was carefully investigated in order to design an efficient process using homogeneous catalysis. − The process is based on a temperature-controlled switchable solvent system called a thermomorphic multicomponent system (TMS) enabling the reaction and the separation of the product from the catalyst. N , N -Dimethylformamide (DMF) was proposed initially as a promising solvent candidate by chemical intuition and was later identified as one of the best performing solvents from a thermodynamic point of view. , However, DMF is a developmental toxic substance, and is included in the REACH list of components of very high concern.…”

“…The ligand steers the selectivity to the desired terminal aldehyde by suppressing the hydroformylation to the branched aldehyde and hydrogenation to the alkane . The left-hand side of Figure shows the desired hydroformylation reaction of 1-decene to 1-undecanal, the example reaction considered in this work. , Typical reaction conditions are in a temperature range of 105–115 °C and a pressure of 20 bar at an equimolar composition of hydrogen and carbon monoxide …”