Reaction rate from laboratory reactors

Equation 8.3.4 may also be used in the analysis of kinetic data taken in laboratory scale stirred tank reactors. One may directly determine the reaction rate from a knowledge of the reactor volume, flow rate through the reactor, and stream compositions. The fact that one may determine the rate directly and without integration makes stirred tank reactors particularly attractive for use in studies of reactions with complex rate expressions (e.g., enzymatic or heterogeneous catalytic reactions) or of systems in which multiple reactions take place. 

The choice of experimental reactor is important to the success of the kinetic modeling effort. The short bench-scale reaction tubes sometimes used for studies of this sort give little or no insight into best mathematical form of the kinetic model, conduct the reaction over varying temperatures and partial pressures along the tube, and inevitably operate at velocities that are a small fraction of those to be encountered in the plant-scale reactor. Rate models from laboratory reactors of this sort rarely scale-up well. The laboratory differential reactor suffers from velocity problems but does at least conduct the reaction at known and relatively constant temperature and partial pressures. However, one usually runs into accuracy problems because calculated reaction rates are based upon the small observed differences in concentration between the reactor inlet and outlet. 

When choosing a laboratory reactor for the measurement of reaction rate data, numerous issues must be resolved. The choice of the reactor is based on the characteristics of the reaction and for all practical matters by the availability of resources (i.e., reactors, analytical equipment, money, etc.). A good example of the issues involved in selecting a laboratory reactor and how they influence the ultimate choice is presented by Weekman [AIChE J., 20 (1974) 833]. Methods for obtaining reaction rate data from laboratory reactors that approximate the ideal reactors listed in Table 3.5.1 are now discussed. 

Pilot-plant studies. The reactors used in these studies are significantly larger than those employed in bench-scale laboratory experiments. One uses essentially the reverse of the design procedures developed later in the chapter to determine the effective reaction rate from the pilot-plant data. In analysis of data of this type, one... 

To predict significant transport effects, respective criteria are needed. This is particularly important for kinetic studies in laboratory reactors to minimize the intrusion of diffusion and heat conduction. The concept used to derive such criteria is the following Since gradients of concentration and temperature always exist in and around a particle (although they are sometimes negligibly small), an assumption has to be made about the deviation up to which the reaction can considered to be uninfluenced by mass and heat transport. Commonly, the criterion is that the deviation of the mean reaction rate from the zero-gradient rate should be within 5%. 

The laboratory studies utilized small-scale (1-5-L) reactors. These are satisfactoiy because the reaction rates observed are independent of reac tor size. Several reac tors are operated in parallel on the waste, each at a different BSRT When steady state is reached after several weeks, data on the biomass level (X) in the system and the untreated waste level in the effluent (usually in terms of BOD or COD) are collected. These data can be plotted for equation forms that will yield linear plots on rec tangular coordinates. From the intercepts and the slope or the hnes, it is possible to determine values of the four pseudo constants. Table 25-42 presents some available data from the literature on these pseudo constants. Figure 25-53 illustrates the procedure for their determination from the laboratory studies discussed previously. 

This involves knowledge of chemistry, by the factors distinguishing the micro-kinetics of chemical reactions and macro-kinetics used to describe the physical transport phenomena. The complexity of the chemical system and insufficient knowledge of the details requires that reactions are lumped, and kinetics expressed with the aid of empirical rate constants. Physical effects in chemical reactors are difficult to eliminate from the chemical rate processes. Non-uniformities in the velocity, and temperature profiles, with interphase, intraparticle heat, and mass transfer tend to distort the kinetic data. These make the analyses and scale-up of a reactor more difficult. Reaction rate data obtained from laboratory studies without a proper account of the physical effects can produce erroneous rate expressions. Here, chemical reactor flow models using matliematical expressions show how physical... 

Example 4. Depolymerization under Pressure.62 PET resin was depolymerized at pressures which varied from 101 to 620 kPa and temperatures of 190—240° C in a stirred laboratory reactor having a bomb cylinder of2000 mL (Parr Instrument) for reaction times of 0.5, 1, 2, and 3 h and at various ratios of EG to PET. The rate of depolymerization was found to be directly proportional to the pressure, temperature, and EG—PET ratio. The depolymerization rate was proportional to the square of the EG concentration at constant temperature, which indicates that EG acts as both a catalyst and reactant in the chain scission process. 

Hydrogenation of lactose to lactitol on sponge itickel and mtheitium catalysts was studied experimentally in a laboratory-scale slurry reactor to reveal the true reaction paths. Parameter estimation was carried out with rival and the final results suggest that sorbitol and galactitol are primarily formed from lactitol. The conversion of the reactant (lactose), as well as the yields of the main (lactitol) and by-products were described very well by the kinetic model developed. The model includes the effects of concentrations, hydrogen pressure and temperature on reaction rates and product distribution. The model can be used for optinuzation of the process conditions to obtain highest possible yields of lactitol and suppressing the amounts of by-products. 

Collect together all the kinetic and thermodynamic data on the desired reaction and the side reactions. It is unlikely that much useful information will be gleaned from a literature search, as little is published in the open literature on commercially attractive processes. The kinetic data required for reactor design will normally be obtained from laboratory and pilot plant studies. Values will be needed for the rate of reaction over a range of operating conditions pressure, temperature, flow-rate and catalyst concentration. The design of experimental reactors and scale-up is discussed by Rase (1977). 

Identify the predominant rate-controlling mechanism kinetic, mass or heat transfer. Choose a suitable reactor type, based on experience with similar reactions, or from the laboratory and pilot plant work. 

Diffusivities in liquids are comparatively low, a factor of 10 lower than in gases, so it is probable in most industrial examples that they are diffusion rate controlled. One consequence is that L-L. reactions are not as temperature sensitive as ordinary chemical reactions, although the effect of temperature rise on viscosity and droplet size sometimes can result in substantial rate increase. On the whole, in the presnt state of the art, the design of L-L reactors must depend on scale-up from laboratory or pilot plant work. 

The utilization of a flow circulation system for laboratory experiments was made difficult by the toxicity of all three gases, CO, Cl2, and COCl2. For this reason, in contrast to other reactions, we studied reaction (368) in a closed system. The experimental apparatus was equipped with a circulation pump so that the gas mixture continuously passed through the catalyst bed in the reactor. The reaction rate was determined from the change in total... 

In these types of laboratory reactor, the flow of the liquid is very carefully controlled so that, although the mass transfer step is coupled with the chemical reaction, the mass transfer characteristics can be disentangled from the reaction kinetics. For some reaction systems, absorption of the gas concerned may be studied as a purely physical mass transfer process in circumstances such that no reaction occurs. Thus, the rate of absorption of C02 in water, or in non-reactive electrolyte solutions, can be measured in the same laboratory contactor as that used when the absorption is accompanied by the reaction between C02 and OH ions from an NaOH solution. The experiments with purely physical absorption enable the diffusivity of the gas in the liquid phase DL to be calculated from the average rate of absorption per unit area of gas-liquid interface NA and the contact time te. As shown in Volume 1, Chapter 10, for the case where the incoming liquid contains none of the dissolved gas, the relationship is ... 

Rates of catalytic reactions are obtained by measurement of the conversion of a key component, often the rate limiting reactant, in laboratory reactors and relating this to the amount of catalyst used and the amount or flow rate of reactants used, to obtain an intrinsic quantity, mols-1 amount-1. For practical application the mass or volume of a catalyst is most relevant as the amount but, for comparitive studies the amount of active phase on a supported catalyst, its specific surface area or the number of active sites may be preferred. In the latter case this yields the turnover frequency (TOF) [3], which is quite relevant for fundamental studies. The number of active sites is, however, usually hard to determine and the mass of the catalyst W will be used, resulting in a rate dimensions of mol s 1 kg-1. Other quantities are easily derived from this. 

Catalytic reaction engineering is a scientific discipline which bridges the gap between the fundamentals of catalysis and its industrial application. Starting from insight into reaction mechanisms provided by catalytic chemists and surface scientists, the rate equations are developed which allow a quantitative description of the effects of the reaction conditions on reaction rates and on selectivities for desired products. The study of intrinsic reaction kinetics, i.e. those determined solely by chemical events, belongs to the core of catalytic reaction engineering. Very close to it lies the study of the interaction between physical transport and chemical reaction. Such interactions can have pronounced effects on the rates and selectivities obtained in industrial reactors. They have to be accounted for explicitly when scaling up from laboratory to industrial dimensions. 

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