Microreactor catalytic

To combine the advantages of packed-bed and catalytic wall microreactors, catalytic bed microreactors were proposed recently. In this novel reactor design, the catalyst is applied on metallic filaments or wires which are incorporated in a microreactor, leading to a low pressure drop and a nanow residence time distribution [87-89]. By insertion of metallic wires a uniform gas distribution and a reduced risk of temperature gradients is obtained. However, similarly to catalytic wall microreactors, an increase in the specific surface area of the grid or wire is required. In addition to metallic wires and grids, modified ceramic tapes can also be used as a catalyst support [90]. 

These results demonstrated that for the microreactor, catalytic layers with thicknesses below 20 fxm allowed rjco > 0.8. Above this thickness, the mass transfer limitations decreased the catalytic performance of the microstructured system. Recently, a similar work [183] studied the effect of the catalytic layer thickness in MRs for the PROX reaction, confirming that the catalytic layer must present an optimal thickness in order to improve the catalytic performance of the microreactors through reducing the transport phenomena effects. 

The advantages of microreactors, for example, well-defined control of the gas-liquid distributions, also hold for photocatalytic conversions. Furthermore, the distance between the light source and the catalyst is small, with the catalyst immobilized on the walls of the microchannels. It was demonstrated for the photodegradation of 4-chlorophenol in a microreactor that the reaction was truly kinetically controlled, and performed with high efficiency [32]. The latter was explained by the illuminated area, which exceeds conventional reactor types by a factor of 4-400, depending on the reactor type. Even further reduction of the distance between the light source and the catalytically active site might be possible by the use of electroluminescent materials [19]. The benefits of this concept have still to be proven. 

The authors developed a multi-layered microreactor system with a methanol reforma- to supply hydrogen for a small proton exchange membrane fiiel cell (PEMFC) to be used as a power source for portable electronic devices [6]. The microreactor consists of four units (a methanol reformer with catalytic combustor, a carbon monoxide remover, and two vaporizers), and was designed using thermal simulations to establish the rppropriate temperature distribution for each reaction, as shown in Fig. 3. 

We have studied the steady-state kinetics and selectivity of this reaction on clean, well-characterized sinxle-crystal surfaces of silver by usinx a special apparatus which allows rapid ( 20 s) transfer between a hixh-pressure catalytic microreactor and an ultra-hixh vacuum surface analysis (AES, XPS, LEED, TDS) chamber. The results of some of our recent studies of this reaction will be reviewed. These sinxle-crystal studies have provided considerable new insixht into the reaction pathway throuxh molecularly adsorbed O2 and C2H4, the structural sensitivity of real silver catalysts, and the role of chlorine adatoms in pro-motinx catalyst selectivity via an ensemble effect. 

The catalytic experiments were performed at the stationnary state and at atmospheric pressure, in a gas flow microreactor. The gas composition (NO, CO, O2, C3H, CO2 and H2O diluted with He) is representative of the composition of exhaust gases. The analysis, performed by gas chromatography (TCD detector for CO2, N2O, O2, N2, CO and flame ionisation detector for C3H6) and by on line IR spectrometry (NO and NO2) has been previously described (1). A small amount of the sample (10 mg diluted with 40 mg of inactive a AI2O3 ) was used in order to prevent mass and heat transfer limitations, at least at low conversion. The hourly space velocity varied between 120 000 and 220 000 h T The reaction was studied at increasing and decreasing temperatures (2 K/min) between 423 and 773 K. The redox character of the feedstream is defined by the number "s" equal to 2[02]+[N0] / [C0]+9[C3H6]. ... 

Catalytic activity tests have been performed in a quartz microreactor (I.D.=0.8 cm) filled with 0.45 g of fine catalyst powders (dp=0 1 micron). The reactor has been fed with lean fiiel/air mixtures (1.3% of CO, 1.3% of H2 and 1% of CH4 in air resp ively) and has been operated at atmospheric pressure and with GHSV= 54000 Ncc/gcath The inlet and outlet gas compositions were determined by on-line Gas Chromatography. A 4 m column (I D. =5mm) filled with Porapak QS was used to separate CH4, CO2 and H2O with He as carrier gas. Two molecular sieves (5 A) columns (I D.=5 mm) 3m length, with He and Ar as carrier gases, were used for the separation and analysis of CO, N2, O2, CH4, and H2, N2, O2 respectively... 

Veser G., Experimental and theoretical investigation cf H2 oxidation in a high-temperature catalytic microreactor, Chem. Eng. Sd. 56 (2001) 1265-1273. 

Ehreeld, W., Gebauer, K., Lowe, H., Richter, T., Synthesis of ethylene oxide in a catalytic microreactor system. Stud. 

M., Zengerle, R., a modular microreactor design for high-temperature catalytic oxidation reactions, in Ehreeld,... 

Microreactors Low conversion, catalytic reactions Simple design, transport rates can be increased by external recycling Limited ease of variation of parameters, maldistribution of flow can be prohibitive... 

DRIFT spectroscopy was used to determine Av0h shifts, induced by adsorption of N2 and hexane for zeolite H-ZSM-5 (ZSM-a and ZSM-b, Si/Al=15.5 and 26), H-mordenite (Mor-a and Mor-b, Si/AI— 6.8 and 10) and H-Y (Y-a and Y-b, Si/Al=2.5 and 10.4) samples. Catalysts were activated in 02 flow at 773 K in situ in the DRIFTS cell and contacted than with N2 at pressures up to 9 bar at 298 K or with 6.1% hexane/He mixture at 553 K, i.e., under reaction conditions. Catalytic activities of the solids were measured in a flow-through microreactor and kapp was obtained as slope of -ln(l-X0) vs. W/F plots. The concentration of Bronsted acid sites was determined by measuring the NH4+ ion-exchange capacity of the zeolite. The site specific apparent rate constant, TOFBapp, was obtained as the ratio of kapp and the concentration of Bronsted acid sites. 

Catalytic activity was determined with a fixed bed microreactor which consisted of two coassial quartz tubes (i.d. 35 and 16 mm) to allow feed gas preheating and heated in an electrical oven (Watlow) with a temperature controller. The bed temperature was monitored by A K-type thermocoupling. On-line analysers (ABB) for CO, C02, CH4, ... 

Catalytic tests were conducted in a pulse microreactor coupled to a quadrupole mass spectrometer. Samples were dried in situ in flowing helium at 773 K for four hours and, thereafter, sequential propane pulses were injected at 703 K with mass-spectrometric analysis of the products.The main text can start here. 

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. 

The point is also made [134] that the very high surface areas and the richly interconnected three-dimensional networks of these micron-sized spaces, coupled with periods of desiccation, could together have produced microenvironments rich in cat-alytically produced complex chemicals and possibly membrane-endosed vesides of bacterial size. These processes would provide the proximate concatenation of lipid vesicular precursors with the complex chemicals that would ultimately produce the autocatalytic and self-replicating chiral systems. A 2.5 km2 granite reef is estimated to contain possibly 1018 catalytic microreactors, open by diffusion to the dynamic reservoir of organic molecules. .. but protected from the dispersive effects of flow and convection [134] as well as protected from the high flux of ultraviolet radiation impinging on the early Earth. [123,137]... 

Mixet/vaporizet Catalytic reformer membrane microreactor... 

Yube, K. and Furuta, M. and Mae, K. (2007). Selective oxidation of phenol with hydrogen peroxide using two types of catalytic microreactor, Catalysis Today, 125, 56-63. 

WUes and Watts [48,53] have reported the use of a rather successful heterogenic catalytic system to carry out these reactions. They have tested a borosilicate glass microreactor (dimensions 3.0 x 3.0 x 0.6 cm) consisting of two etched layers with two inlets, mixing channels, a larger etched region and the outlet. A solid-supported catalyst was dry-packed in this structure (Fig. 4). 

The adsorption of NO, under lean conditions was studied by imposing a step change of NO and NO2 feed concentrations in the presence and absence of excess oxygen over the reference catalysts in a fixed-bed flow microreactor operated at 350 ° C and analyzing the transient response in the outlet concentrations of reactants and products [transient response method (TRM)[. The adsorption/desorption sequence was repeated several times in order to condition the catalytic systems fully due to the regeneration procedure adopted (either reduction with 2000 ppm H2 + He or TPD in flowing He), BaO was the most Ba-abundant species present on the catalyst surface. FT-IR spectroscopy was used as a complementary technique to investigate the nature of the stored NO species. 

---