Multiphase microreactors

Multiphase catalytic reactors are employed in nearly 80% of industrial processes with annual global sales of about 1.5 trillion, contributing around 35% of the world s GDP [17]. Microreactors for multiphase reactions are classified based on the contact principles of gas and liquid phases continuous-phase contacting and dispersed-phase contacting [18]. In the former type, the two phases are kept in continuous contact with each other by creating an interface. In the latter case, one fluid phase is dispersed into another fluid phase. In addition, micro trickle bed operation is reported following the path of classical chemical engineering. The study of mass and heat transfer in two-phase flow in micro trickle bed reactors still remains as a less 

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This chapter provides an overview of the mass transfer characteristics of multiphase microreactors. Basic concepts are explained and related to mass transfer in sequented (drop/bubble) flow, annular flow, and to multiphase flow through packed microchannels. In multiphase microreactors, a chemical reaction can either involve two immiscible fluid phases (e.g. for gas-liquid reactions) or two fluid phases in the presence of a solid catalyst or the reaction is exclusively confined to one of the fluid phases that are present in the system. 

In many multiphase microreactor applications, stable fluid interfaces have been particularly important for performing gas-liquid reactions in the annular flow... 

J. R. Burns, C. Ramshaw, A multiphase microreactor for organic nitration, in Proceedings of the 4th International Conference on Process Intensification for the Chemical Industry Better Processes for Better Products, Bruges, 2001. 

For catalytic reactions many multiphase microreactors contain catalysts coated on walls, incorporated in thin nonporous films or in packed beds... 

WangX, Nie Y, Lee JLC, Jaenicke S. Evaluation of multiphase microreactors for the direct formation of hydrogen peroxide. Applied Catalysis A General 2007 317 258-265. 

Nitrite reduction in water is tested as a model reaction. It is shown that nitrite reduction proceeds by both catalytic reduction (with Pd and H2) and by the reactor material itself (i.e., by Fe on CNFs). Eventually, the latter effect will exhaust in time and the reaction will still proceed with the immobilized Pd-catalyst on the CN Fs and the membrane-assisted supply of hydrogen. Results proved that the porous metallic membrane microreactors with carbon nanofibers are suitable materials for the reduction of nitrite and the reactor design is very promising for the multiphase microreactor technologies [lOOj. 

Quite new ideas for the reactor design of aqueous multiphase fluid/fluid reactions have been reported by researchers from Oxeno. In packed tubular reactors and under unconventional reaction conditions they observed very high space-time yields which increased the rate compared with conventional operation by a factor of 10 due to a combination of mass transfer area and kinetics [29]. Thus the old question of aqueous-biphase hydroformylation "Where does the reaction takes place " - i.e., at the interphase or the bulk of the liquid phase [23,56h] - is again questionable, at least under the conditions (packed tubular reactors, other hydrodynamic conditions, in mini plants, and in the unusual,and costly presence of ethylene glycol) and not in harsh industrial operation. The considerable reduction of the laminar boundary layer in highly loaded packed tubular reactors increases the mass transfer coefficients, thus Oxeno claim the successful hydroformylation of 1-octene [25a,26,29c,49a,49e,58d,58f], The search for a new reactor design may also include operation in microreactors [59]. 

Multiphase catalytic reactions, such as catalytic hydrogenations and oxidations are important in academic research laboratories and chemical and pharmaceutical industries alike. The reaction times are often long because of poor mixing and interactions between the different phases. The use of gaseous reagents itself may cause various additional problems (see above). As mentioned previously, continuous-flow microreactors ensure higher reaction rates due to an increased surface-to-volume ratio and allow for the careful control of temperature and residence time. 

Doku GN, Haswell SJ, McCreedy T, Greenway GM (2001) Electric Field-Induced Mobilisation of Multiphase Solution Systems Based on the Nitration of Benzene in a Microreactor. Analyst 126 14-20... 

In addition to absolute pressure measurements, pressure sensors can be used to determine flow rates when combined with a well-defined pressure drop over a microfluidic channel. Integration of optical waveguide structures provides opportunities for monitoring of segmented gas-liquid or liquid-liquid flows in multichannel microreactors for multiphase reactions, including channels inside the device not accessible by conventional microscopy imaging (Fig. 2c) (de Mas et al. 2005). Temperature sensors are readily incorporated in the form of thin film resistors or simply by attaching thin thermocouples (Losey et al. 2001). 

Hessel V, Hofmann C, Lob P, Lohndorf J, Lowe H, Ziogas A (2005) Aqueous Kolbe-Schmitt synthesis using resorcinol in a microreactor laboratory rig under high-P,T conditions. Org Process Res Dev 9 479-489 Inoue T, Schmidt MA, Jensen KF (2007) Microfabricated multiphase reactors for the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Ind Eng Chem Res 46 1153-1160... 

Ruy et al. have performed a similar reaction under microreactor conditions in a multiphase solvent system containing an ionic liquid as the catalyst carrier and reaction promoter [35]. Their system consisted of two T-shaped micromixers (i.d. 1,000 and 400 pm) and a capillary stainless steel tube as an RTU (1,000 pm i.d. and 18 m length, giving a 14.1 ml volume), equipped with pumps and control valves. Under the optimized conditions, Pd-catalysed carbonylation of aromatic iodides in the presence of a secondary amine provided only the double carbonylated product, ot-ketoamide, while the amide obtained by the single carbonylation was observed in high quantities only when the reaction was performed in batch (Scheme 13). 

A further improvement of the multiphase reactor concept using lipase for enantioselective transformation has been recently reported, that is, an emulsion enzyme membrane reactor. Here, the organic/water interface within the pores at the enzyme level is achieved by stable oil-in-water emulsion, prepared by membrane emulsification. In this way, each pore forms a microreactor containing immobilized... 

The issues to be solved for direct fluorinations are heat release and mass transfer via the gas-liquid interface. Multiphase microstructured reactors enable process intensification [230,248-250,304—306]. Often geometrically well-defined interfaces are formed with large specific values, for example, up to 20 000 m2/m3 and even more. These areas can be easily accessible, as flow conditions are often highly periodic and transparent microreactors are available. For the nondispersing... 

Doku, G.N. Verboom, W. Reinhoudt, D.N. van den Berg, A. On-microchip multiphase chemistry— a review of microreactor design principles and reagent contacting modes. Tetrahedron. 2004, 61 (11), 2733-2742. 

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