Continuously-flowing systems

Other above-ground continuous flow systems have been designed and operated for SCWO processes. A system developed by ModeU Development Corp. (Modec) uses a tubular reactor and can be operated at temperatures above 500°C. It employs a pressure letdown system in which soHd, Hquids, and gases are separated prior to pressure release. This simplifies valve design and material selection on the Hquid leg. 

Nonicosahedral carboranes can be prepared from the icosahedral species by similar degradation procedures or by reactions between boranes such as B H q and B H with acetylenes. The degradative reactions for intermediate C2B H 2 species (n = 6-9) have been described in detail (119). The small closo-Qr Yi 2 species (n = 3-5 are obtained by the direct thermal reaction (500—600°C) of B H using acetylene in a continuous-flow system. The combined yields approach 70% and the product distribution is around 5 5 1 of 2,4-C2B3H2 [20693-69-0] to l,6-C2B Hg [20693-67-8] to 1,5-C2B3H3 [20693-66-7] (120). A similar reaction (eq. 60) employing base catalysts, such as 2 6-dimethylpyridine at ambient temperature gives nido-2 >-(Z, ... 

Reac tors that are nominally CSTRs or PFRs may in practice deviate substantially from ideal mixing or nonmixing. This topic is developed at length in Sec. 23, so only a few summary statements are made here. More information about this topic also may be found in Nauman and Buffham (Mixing in Continuous Flow Systems, Wiley, 1983). 

Figure 2.16 Clirotnatograms of a pentane extract of a water sample containing 200 ppb of a naphtha fraction (a) sample extracted by using a continuous flow system, where a pressurized bottle was employed as the sample-delivery system (b) batch-extracted sample. Reprinted from Journal of Chromatography, A 330, J. Roeraade, Automated monitoring of organic Race components in water. I. Continuous flow exti action together with on-line capillary gas cliro-matography , pp. 263 - 274, copyrigth 1985, with permission from Elsevier Science.

Polysaccharides can also be used to immobilise cells or enzymes, permitting the re-use of the catalyst and continuous flow systems. Alginates have the advantage that gel formation occurs under mild conditions, therefore cells remain viable and enzymes are not denatured but calcium gradually leaches out and the gel dissolves. Gellan or other combinations may prove superior for this application. 

Danckwerts, P. V., Continuous flow systems distribution of residence times, Chem. Eng. ScL, 2, 1-18 (1953). 

Nauman, E. B. and Buffham, B. A., Mixing in Continuous Flow Systems, Wiley, New York, 1983. 

The time that a molecule spends in a reactive system will affect its probability of reacting and the measurement, interpretation, and modeling of residence time distributions are important aspects of chemical reaction engineering. Part of the inspiration for residence time theory came from the black box analysis techniques used by electrical engineers to study circuits. These are stimulus-response or input-output methods where a system is disturbed and its response to the disturbance is measured. The measured response, when properly interpreted, is used to predict the response of the system to other inputs. For residence time measurements, an inert tracer is injected at the inlet to the reactor, and the tracer concentration is measured at the outlet. The injection is carried out in a standardized way to allow easy interpretation of the results, which can then be used to make predictions. Predictions include the dynamic response of the system to arbitrary tracer inputs. More important, however, are the predictions of the steady-state yield of reactions in continuous-flow systems. All this can be done without opening the black box. 

Washout experiments can be used to measure the residence time distribution in continuous-flow systems. A good step change must be made at the reactor inlet. The concentration of tracer molecules leaving the system must be accurately measured at the outlet. If the tracer has a background concentration, it is subtracted from the experimental measurements. The flow properties of the tracer molecules must be similar to those of the reactant molecules. It is usually possible to meet these requirements in practice. The major theoretical requirement is that the inlet and outlet streams have unidirectional flows so that molecules that once enter the system stay in until they exit, never to return. Systems with unidirectional inlet and outlet streams are closed in the sense of the axial dispersion model i.e., Di = D ut = 0- See Sections 9.3.1 and 15.2.2. Most systems of chemical engineering importance are closed to a reasonable approximation. 

Figure 6. Removal of TOC( ) and color(A) during catalytic wet oxidation of a real dyehouse effluent with 10wt% CU/AI2O3 in the continuous flow system.

The combined use of a continuous flow system and a spectrophotometer for sample screening to discriminate between synthetic and natural colorants is also available. With a very simple flow system on a column packed with natural materials, one can discriminate natural and synthetic colorants. The natural (not retained) ones can be determined in the first step and the synthetic (retained) ones in the second step after their elution. For yellow, red, green, blue, and brown, natural or synthetic colorants were chosen as models. The specific maximum wavelength for each color (400,530, and 610 mn, respectively) was selected by a diode array system. A complete discrimination of natural and synthetic colorants was obtained for concentrations of natural colorants (in the absence of synthetic ones) up to 2000 (yellow), 2000 (red), and 10,000 (brown) times that of the detection limits (DLs) of synthetic additives. This method was applied to screen fruit drinks and candies. ... 

Microcosms are laboratory systems generally consisting of tanks such as fish aquaria containing natural sediment and water or soil. In those that have been most extensively evaluated for aquatic systems, continuous flow systems are used. In all of them, continuous measurement of evolved... 

In continuous flow systems, the expenditure in mechanical energy necessary to run a process is directly proportional to the pressure drop over the system. Hence the pressure drop is an important figure determining the operating costs of a device. After having verified the chemical equivalence of the two reactor types introduced above, the question arises of whether using a micro-channel reactor instead of a fixed-bed reactor allows a decrease in the pressure drop. In order to estimate the pressure drop in the fixed-bed reactor, the Carman-Kozeney hydraulic diameter model (see, e.g., [116]) was used ... 

Saurina, J. Hemandez-Cassou, S. Izquierdo-Ridorsa, A. Tauler, R., pH-gradient spectrophotometric data files from flow-injection and continuous flow systems for two- and three-way data analysis, Chem. Intell. Lab. Syst. 50, 263-271 (2000). 

There are a variety of limiting forms of equation 8.0.3 that are appropriate for use with different types of reactors and different modes of operation. For stirred tanks the reactor contents are uniform in temperature and composition throughout, and it is possible to write the energy balance over the entire reactor. In the case of a batch reactor, only the first two terms need be retained. For continuous flow systems operating at steady state, the accumulation term disappears. For adiabatic operation in the absence of shaft work effects the energy transfer term is omitted. For the case of semibatch operation it may be necessary to retain all four terms. For tubular flow reactors neither the composition nor the temperature need be independent of position, and the energy balance must be written on a differential element of reactor volume. The resultant differential equation must then be solved in conjunction with the differential equation describing the material balance on the differential element. 

Figure 7. (a) Flow diagram of the optical fibre continuous-flow system for bioluminescence and chemiluminescence measurements S, sample C, carrier stream PP, peristaltic pump IV, injection valve W, waste FO, optical fibre FC, flow-cell, (b) Details of the optical fibre biosensor/flow-cell interface a, optical fibre b, sensing layer c, light-tight flow-cell d, stirring bar. 

As already mentioned, the scale-up of microwave-assisted reactions is of specific interest in many industrial laboratories. For this purpose, Milestone offers two different continuous-flow systems (Fig. 3.11). 

The process which seems to have the most possibilities for a scale-up development is that using a low amount of graphite, for which the desorption treatment can be totally suppressed in a continuous flow system. We recently proposed the use of such a process to perform FC acylations under the action of MW with FeCl3 as catalyst [76 d]. The replacement of FeCl3 by a graphite bed is quite conceivable in the same continuous flow apparatus. 

G. Jeanty and J.L. Marty, Detection of paraoxon by continuous flow system based enzyme sensor. Biosens. Bioelectron. 13, 213-218 (1998). 

---