Reactor residence time

Cyclohexane, produced from the partial hydrogenation of benzene [71-43-2] also can be used as the feedstock for A manufacture. Such a process involves selective hydrogenation of benzene to cyclohexene, separation of the cyclohexene from unreacted benzene and cyclohexane (produced from over-hydrogenation of the benzene), and hydration of the cyclohexane to A. Asahi has obtained numerous patents on such a process and is in the process of commercialization (85,86). Indicated reaction conditions for the partial hydrogenation are 100—200°C and 1—10 kPa (0.1—1.5 psi) with a Ru or zinc-promoted Ru catalyst (87—90). The hydration reaction uses zeotites as catalyst in a two-phase system. Cyclohexene diffuses into an aqueous phase containing the zeotites and there is hydrated to A. The A then is extracted back into the organic phase. Reaction temperature is 90—150°C and reactor residence time is 30 min (91—94). 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Anionic polymerization offers fast polymerization rates on account of the long life-time of polystyryl carbanions. Early studies have focused on this attribute, most of which were conducted at short reactor residence times (< 1 h), at relatively low temperatures (10—50°C), and in low chain-transfer solvents (typically benzene) to ensure that premature termination did not take place. Also, relatively low degrees of polymerization (DP) were typically studied. Continuous commercial free-radical solution polymerization processes to make PS, on the other hand, operate at relatively high temperatures (>100° C), at long residence times (>1.5 h), utilize a chain-transfer solvent (ethylbenzene), and produce polymer in the range of 1000—1500 DP. 

The production rate is 2—4 t/h, depending on the feed rate, monomer concentration in the feed, and conversion. The conversion of isobutylene and isoprene typically ranges from 75—95% and 45—85%, respectively, depending on the grade of butyl mbber being produced. The composition and mol wt of the polymer formed depend on the concentration of the monomers in the reactor Hquid phase and the amount of chain transfer and terminating species present. The Hquid-phase composition is a function of the feed composition and the extent of monomer conversion. In practice, the principal operating variable is the flow rate of the initiator/coinitiator solution to the reactor residence time is normally 30—60 minutes. 

In Fig. 28, the abscissa kt is the product of the reaction rate constant and the reactor residence time, which is proportional to the reciprocal of the space velocity. The parameter k co is the product of the CO inhibition parameter and inlet concentration. Since k is approximately 5 at 600°F these three curves represent c = 1, 2, and 4%. The conversion for a first-order kinetics is independent of the inlet concentration, but the conversion for the kinetics of Eq. (48) is highly dependent on inlet concentration. As the space velocity increases, kt decreases in a reciprocal manner and the conversion for a first-order reaction gradually declines. For the kinetics of Eq. (48), the conversion is 100% at low space velocities, and does not vary as the space velocity is increased until a threshold is reached with precipitous conversion decline. The conversion for the same kinetics in a stirred tank reactor is shown in Fig. 29. For the kinetics of Eq. (48), multiple solutions may be encountered when the inlet concentration is sufficiently high. Given two reactors of the same volume, and given the same kinetics and inlet concentrations, the conversions are compared in Fig. 30. The piston flow reactor has an advantage over the stirred tank... 

Figure 1. Typical reactor temperature profile for continuous addition polymerization a plug-flow tubular reactor. Kinetic parameters for the initiator 1 = 10 ppm Ea = 32.921 kcal/mol In = 26.492 In sec f = 0.5. Reactor parameter [(4hT r)/ (DpCp)] = 5148.2. [(Cp) = heat capacity of the reaction mixture (p) = density of the reaction mixture (h) = overall heat-transfer coefficient (Tf) = reactor jacket temperature (r) = reactor residence time (D) = reactor diameter].

T = reactor residence time Z = dimensionless axial distance... 

Tanks-in-series reactor configurations provide a means of approaching the conversion of a tubular reactor. In modelling, they are employed for describing axial mixing in non-ideal tubular reactors. Residence time distributions, as measured by tracers, can be used to characterise reactors, to establish models and to calculate conversions for first-order reactions. 

The reactor residence time is about 45 minutes, a 95 per cent approach to equilibrium being achieved in this time. The ammonia is fed directly to the reactor, but the carbon dioxide is fed to the reactor upwardly through a stripper, down which flows the product stream from the reactor. The carbon dioxide decomposes some of the carbamate in the product stream, and takes ammonia and water to a high-pressure condenser. The stripper is steam heated and operates at 180°C, whilst the high-pressure condenser is at 170°C and the heat released in it by recombination of ammonia and carbon dioxide to carbamate is used to raise steam. Additional recycled carbamate solution is added to the stream in the high-pressure condenser, and the combined flow goes to the reactor. 

At this stage, type (1) is more apparent than type (2), and we provide some preliminary discussion of (2) here. Flow characteristics include relative times taken by elements of fluid to pass through the reactor (residence-time distribution), and mixing character-... 

Consequently, in the early 1990s, interest in the direct processes decreased markedly, and the emphasis in research on CH4 conversion returned to the indirect processes giving synthesis gas (13). In 1990, Ashcroft et al. (13) reported some effective noble metal catalysts for the reaction about 90% conversion of methane and more than 90% selectivity to CO and H2 were achieved with a lanthanide ruthenium oxide catalyst (L2Ru207, where L = Pr, Eu, Gd, Dy, Yb or Lu) at a temperature of about 1048 K, atmospheric pressure, and a GHSV of 4 X 104 mL (mL catalyst)-1 h-1. This space velocity is much higher than that employed by Prettre et al. (3). Schmidt et al. (14-16) and Choudhary et al. (17) used even higher space velocities (with reactor residence times close to 10-3 s). 

The reactor residence time is defined by the volume of the reactor divided by the volumetric influent flow rate ... 

By using graphical methods, Ng and Vermeulen [20] showed that predictions could be made from data obtained in experiments in which a single starting composition was used. Reactor residence time needed to be varied. The reaction schemes they considered were... 

These problems are easy Note that the reactor residence time (proportional to reactor size) increases markedly as the required conversion increases. Note also that for this example (first-order kinetics) we did not need even to specify Cao because the equation involves only the ratio Cao/Ca-... 

Kinetic data are frequently acquired in continuous reactors rather than batch reactors. These data permit one to determine whether a process has come to steady state and to examine activation and deactivation processes. These data are analyzed in a similar fashion to that discussed previously for the batch reactor, but now the process variables such as reactant flow rate (mean reactor residence time) are varied, and the composition will not be a function of time after the reactor has come to steady state. Steady-state reactors can be used to obtain rates in a differential mode by maintaining conversions small. In this configuration it is particularly straightforward to vary parameters individually to find rates. One must of course wait until the reactor has come to steady state after any changes in feed or process conditions. 

We call the volume divided by the volumetric flow rate the reactor residence time... 

Whenever the density of the fluid in the reactor varies as the reaction proceeds, the reactor residence time r is not a simple independent variable to describe reactor performance. Typically, we stiU know the inlet variables such as Uq, Tq, Fjo, and Co, and these are independent of conversion. 

Since the volumetric flow rate is a function of X, T, and P, the residence time V/v depends on these variables. Instead of using the reactor residence time T to describe performance, an analogous quantity called the space time ST, defined as... 

Figure 3-7 Plot of nominal space times (or reactor residence times) required for several important industrial reactors versus the nominal reactor temperatiwes. Times go from days (for fermentation) down to milliseconds (for ammonia oxidation to form nihic acid). The low-temperature, long-time processes involve liquids, while the high-temperature, short-time processes involve gases, usually at high pressures.

Note carefully here the difference between Ca (initial concentration within the tank) and Cao (feed concentration into the tank). Note also the difference between the reactor residence time t and the time t after the switch in the feed is initiated.]... 

---