Flow reactors CSTRs

The titration of an acid with a base, or vice versa, and the precipitation of an ion in an insoluble compound are examples of chemical methods of analysis used to determine the concentration of a species in a liquid sample removed from a reactor. Such methods are often suitable for relatively slow reactions. This is because of the length of time that may be required for the analysis the mere collection of a sample does not stop further reaction from taking place, and a method of quenching the reaction may be required. For a BR, there is the associated difficulty of establishing the time t at which the concentration is actually measured. This is not a problem for steady-state operation of a flow reactor (CSTR or PFR). 

In chapters 2-5 two models of oscillatory reaction in closed vessels were considered one based on chemical feedback (autocatalysis), the other on thermal coupling under non-isothermal reaction conditions. To begin this chapter, we again return to non-isothermal systems, now in a well-stirred flow reactor (CSTR) such as that considered in chapter 6. 

Kinetics can also be studied at surface science conditions. Feed can be leaked at a constant rate into the chamber containing the crystal face, and the gas is removed at a constant rate by the pumps. The composition of the chamber gas can be continuously monitored by mass spectrometry. The pressure in the reaction chamber is low enough to ensure Knudsen flow The gaseous molecules collide almost exclusively with the exposed solid surfaces, and the system behaves as a perfectly mixed flow reactor (CSTR). Experiments in the transient regime with various forcing functions can be performed, and response times can be orders of magnitude smaller than those at atmospheric pressure. The catalytic oxidation of CO on Pt(llO) was one of the first studies of this type (33). 

Batch reactor Plug flow reactor CSTR... 

In an open system, such as a well mixed flow reactor (CSTR), the convective transport of reactants and products must be allowed for the analogue of equation (2) is ... 

For the simple steady-state, mixed-flow reactor (CSTR), da Jdt = 0, F = I, Q — and Equation 4.71 (Chapter 4) is recovered. Written in terms of conversion, this equation becomes... 

Fig. U7 Definition sketch showing e amm modes of operation for reactors, (a) Simple batch reactor, (b) Single-pass reactor, (c) tetcb-mlfEylatioii reactor, (d) Cascade of n identical reactors, PFR, plug flow reactor CSTR. oootuiiowl r stirred tank reactor.

By studying appropriately perturbed autocatalytic reactions in a flow reactor (cSTR), we have produced a family of some 20 new oscillators containing chlorite ion. In addition, several new bromate oscillators (e.g., BrOs -Mn -Br " and BrOs - ), which are simpler in composition and mechanism than the classic Belous ov-Zhabotinskii system, have been discovered. Mechanistic considerations have given rise to a tentative classification of oxyhalogen based oscillators which shows the linkage and differences between the various classes. 

Fig. 7. Schematic diagram of the apparatus LFR, laminar flow reactor CSTR, continuous-flow stirred tank reactor. Reprinted from [36].

Another important reaction supporting nonlinear behaviour is the so-called FIS system, which involves a modification of the iodate-sulfite (Landolt) system by addition of ferrocyanide ion. The Landolt system alone supports bistability in a CSTR the addition of an extra feedback chaimel leads to an oscillatory system in a flow reactor. (This is a general and powerfiil technique, exploiting a feature known as the cross-shaped diagram , that has led to the design of the majority of known solution-phase oscillatory systems in flow... 

Continuous-Flow Stirred-Tank Reactor. In a continuous-flow stirred-tank reactor (CSTR), reactants and products are continuously added and withdrawn. In practice, mechanical or hydrauHc agitation is required to achieve uniform composition and temperature, a choice strongly influenced by process considerations, ie, multiple specialty product requirements and mechanical seal pressure limitations. The CSTR is the idealized opposite of the weU-stirred batch and tubular plug-flow reactors. Analysis of selected combinations of these reactor types can be useful in quantitatively evaluating more complex gas-, Hquid-, and soHd-flow behaviors. 

Copolymers are typically manufactured using weU-mixed continuous-stirred tank reactor (cstr) processes, where the lack of composition drift does not cause loss of transparency. SAN copolymers prepared in batch or continuous plug-flow processes, on the other hand, are typically hazy on account of composition drift. SAN copolymers with as Httle as 4% by wt difference in acrylonitrile composition are immiscible (44). SAN is extremely incompatible with PS as Httle as 50 ppm of PS contamination in SAN causes haze. Copolymers with over 30 wt % acrylonitrile are available and have good barrier properties. If the acrylonitrile content of the copolymer is increased to >40 wt %, the copolymer becomes ductile. These copolymers also constitute the rigid matrix phase of the ABS engineering plastics. 

Over 25 years ago the coking factor of the radiant coil was empirically correlated to operating conditions (48). It has been assumed that the mass transfer of coke precursors from the bulk of the gas to the walls was controlling the rate of deposition (39). Kinetic models (24,49,50) were developed based on the chemical reaction at the wall as a controlling step. Bench-scale data (51—53) appear to indicate that a chemical reaction controls. However, flow regimes of bench-scale reactors are so different from the commercial furnaces that scale-up of bench-scale results caimot be confidently appHed to commercial furnaces. For example. Figure 3 shows the coke deposited on a controlled cylindrical specimen in a continuous stirred tank reactor (CSTR) and the rate of coke deposition. The deposition rate decreases with time and attains a pseudo steady value. Though this is achieved in a matter of rninutes in bench-scale reactors, it takes a few days in a commercial furnace. 

Flow reactors are used for greater production rates when the reaction time is comparatively short, when uniform temperature is desired, when labor costs are high. CSTRs are used singly or in multiple units in series, in either separate vessels or single, compartmented shells. 

Plug flow reactors with recycle exhibit some of the characteristics of CSTRs, including the possibility of multiple steady states. This topic is explored by Penmutter Stah dity of (%emical Reactors, Prentice-Hall, 1972). 

Analysts should review the technical basis for uncertainties in the measurements. They should develop judgments for the uncertainties based on the plant experience and statistical interpretation of plant measurements. The most difficult aspect of establishing the measurement errors is estabhshing that the measurements are representative of what they purport to oe. Internal reactor CSTR conditions are rarely the same as the effluent flow. Thermocouples in catalyst beds may be representative of near-waU instead of bulk conditions. Heat leakage around thermowells results in lower than actual temperature measurements. 

Continuous-flow Stirred Tank Reactor (CSTR) A reaction vessel in which the feed is continuously added, and the products continuously removed. The vessel (tank) is continuously stirred to maintain a uniform concentration within the vessel. 

Various experimental methods to evaluate the kinetics of flow processes existed even in the last centuty. They developed gradually with the expansion of the petrochemical industry. In the 1940s, conversion versus residence time measurement in tubular reactors was the basic tool for rate evaluations. In the 1950s, differential reactor experiments became popular. Only in the 1960s did the use of Continuous-flow Stirred Tank Reactors (CSTRs) start to spread for kinetic studies. A large variety of CSTRs was used to study heterogeneous (contact) catalytic reactions. These included spinning basket CSTRs as well as many kinds of fixed bed reactors with external or internal recycle pumps (Jankowski 1978, Berty 1984.)... 

We wish to compare the performance of two reactor types plug flow versus CSTR with a substrate concentration of Csf = 60g-m 3 and a biomass yield of Y = 0.1. In a plug flow bioreactor with volume of 1 m3 and volumetric flow rate of 2.5 m -li what would be the recycle ratio for maximum qx compared with corresponding results and rate models proposed for the chemostat ... 

The performance data for plug versus mix reactor were obtained. The data were collected as the inverse of qx vs inverse of substrate concentration. Table E.1.1 shows the data based on obtained kinetic data. From the data plotted in Figure E.1.1, we can minimise the volume of the chemostat. A CSTR works better than a plug flow reactor for the production of biomass. Maximum qx is obtained with a substrate concentration in the leaving stream of 12g m 3. 

---