Flow reactor techniques description

Several different methods exist for measuring HN03, most commonly FTIR and TDLS, which were described earlier. Other techniques commonly used include filters, denuders, transition flow reactors, and scrubbers, followed by analysis of the collected material for nitrate, e.g., by ion chromatography. A modification of the luminol method has also been used. Finally, mass spectrometric methods look very promising as a sensitive and specific method of detection and measurement. A brief description of each of these methods that have not yet been treated follows. 

The active site responsible for the aerobic oxidation of alcohols over Pd/AljO, catalysts has long been debated [96-lOOj. Many reports claim that the active site for this catalyst material is the metallic palladium based on electrochemical studies of these catalysts [100, 101]. On the contrary, there are reports that claim that palladium oxide is the active site for the oxidation reaction and the metalhc palladium has a lesser catalytic activity [96,97). In this section, we present examples on how in situ XAS combined with other analytical techniques such as ATR-IR, DRIFTS, and mass spectroscopic methods have been used to study the nature of the actual active site for the supported palladium catalysts for the selective aerobic oxidation of benzylic alcohols. Initially, we present examples that claim that palladium in its metallic state is the active site for this selective aerobic oxidation, followed by some recent examples where researchers have reported that ojddic palladium is the active site for this reaction. Examples where in situ spectroscopic methods have been utilized to arrive at the conclusion are presented here. For this purpose, a spectroscopic reaction cell, acting as a continuous flow reactor, has been equipped with X-ray transparent windows and then charged with the catalyst material. A liquid pump is used to feed the reactants and solvent mixture into the reaction cell, which can be heated by an oven. The reaction was monitored by a transmission flow-through IR cell. A detailed description of the experimental setup and procedure can be found elsewhere [100]. Figure 12.10 shows the obtained XAS results as well as the online product analysis by FTIR for a Pd/AljOj catalyst during the aerobic oxidation of benzyl alcohol. 

In this section, we present a description of the MAFBS apparatus, an account of challenges encountered during its development, a brief description of the materials characterization techniques used in this research, and an explanation of the flow reactor used to test the catalytic activity of the prepared carbides and nitrides. 

The study of reaction kinetics in flow reactors to derive microkinetic expressions also rehes on an adequate description of the flow field and well-defined inlet and boundary conditions. The stagnation flow on a catalytic plate represents such a simple flow system, in which the catalytic surface is zero dimensional and the species and temperature profiles of the estabhshed boundary layer depend only on the distance from the catalytic plate. This configuration consequently allows the application of simple measurement and modehng approaches (Sidwell et al., 2002 Wamatz et al., 1994a). SFRs are also of significant technical importance because they have extensively been used for CVD to produce homogeneous deposits. In this deposition technique, the disk is often additionally forced to spin to achieve a thick and uniform deposition across the substrate (Houtman et al., 1986a Oh et al., 1991). 

Since no detailed description of the experimental techniques used in the cited works will be given in the main text, we would like to note that most experiments in the 1930s, as well as experiments at very high (thousands of atmospheres) pressures [46—48] were performed in static reactors. In later studies, predominantly flow reactors have been used, which are more suited to the conditions of the practical implementation of the process. Experiments in flow reactors have been carried out over a wide pressure range (1—300 bar) and initial temperatures of 300—600 °C and above, with the reaction time ranging from a second to tens of minutes. In addition, more exotic reactors, such a cylinder of a high-compression internal combustion engine [49] or a rapid compression machine [50] were used. 

A variety of experimental techniques have been used for the determination of uptake coefficients and especially Knudsen cells and flow tubes have found most application [42]. Knudsen cells are low-pressure reactors in which the rate of interaction with the surface (solid or liquid) is measured relative to the escape through an aperture, which can readily be calibrated, thus putting the gas-surface rate measurement on an absolute basis. Usually, a mass spectrometer detection system monitors the disappearance of reactant species, as well as the appearance of gas-phase products. The timescale of Knudsen cell experiments ranges from a few seconds to h lindens of seconds. A description of Knudsen cell applied to low temperature studies is given [66,67]. 

Such a simplification is possible through the introduction of a continuum mathematical description of the gas-solid flow processes where this continuum description is based upon spatial averaging techniques. With this methodology, point variables, describing thermohydrodynamic processes on the scale of the particle size, are replaced by averaged variables which describe these processes on a scale large compared to the particle size but small compared to the size of the reactor. There is an extensive literature of such derivations of continuum equations for multiphase systems (17, 18, 19). In the present study, we have developed (17, ) a system of equations for... 

Detailed reviews of the CARPT technique have been given by Devanathan et al. [51, 52], Moslemian et al. [142] and Sannaes [175] including the principles of operation, calibration and discussions of problems/difficulties related to this technique. A brief description of the set-up can also be found in the thesis by Sannaes [175]. Duducovic [55] presented a survey on the use of nuclear techniques to characterize opaque multiphase reactor flows, and Chaouki et al. [36] reviewed the non-invasive Tomographic and velocimetric techniques for monitoring multiphase flows. 

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