Tracer residence time distribution

Equation (7) has been used traditionally in medicine as the Stewart-Hamilton indicator-dilution technique (23-25) to measure the unknown flow rate through isolated organs. In this method a known bolus, mr, of tracer is injected into an artery and the tracer dilution curve, Cp(t), is measured at the outflow in a major vein. In chemical engineering systems eq. (7) should be used as a basic mass balance consistency check on the accuracy of the tracer experiment. Failure to satisfy eq. (7) indicates errors and nonidealities, and requires repeats of the experiment at different mij, s to establish linearity. On occasion, only a response R(t), which is linearly proportional to tracer concentration, is measured and the mass injected m,j, is unknown. Then the experiment should be repeated to establish linearity of R(t) with respect to HLp. The obtained age density function R(t)// R(t)dt should be invariant to the mass injected. Although the above simple rules are rather evident, they are all too often neglected by practitioners. Unfortunately, not all tracers at concentrations used behave ideally, and erroneous conclusions result when the nonideal tracer residence time distribution is accepted as the F curve of the system. The tracer tests needed to determine E(t), F(t) and W(t) functions are schematically represented in Figure 1. 

Fig. 7. Residence time distributions where U = velocity, V = reactor volume, t = time, = UtjV, Cj = tracer concentration to initial concentration and Q = reactor volume (a) output responses to step changes (b) output responses to pulse inputs.

Residence Time Distribution (RTD) This is established by injecting a known amount of tracer into the feed stream and monitor-... 

To measure a residence-time distribution, a pulse of tagged feed is inserted into a continuous mill and the effluent is sampled on a schedule. If it is a dry miU, a soluble tracer such as salt or dye may be used and the samples analyzed conductimetricaUy or colorimetricaUy. If it is a wet mill, the tracer must be a solid of similar density to the ore. Materials hke copper concentrate, chrome brick, or barites have been used as tracers and analyzed by X-ray fluorescence. To plot results in log-normal coordinates, the concentration data must first be normalized from the form of Fig. 20-15 to the form of cumulative percent discharged, as in Fig. 20-16. For this, one must either know the total amount of pulse fed or determine it by a simple numerical integration... 

Nonreacdive substances that can be used in small concentrations and that can easily be detected by analysis are the most useful tracers. When making a test, tracer is injected at the inlet of the vessel along with the normal charge of process or carrier fluid, according to some definite time sequence. The progress of both the inlet and outlet concentrations with time is noted. Those data are converted to a residence time distribution (RTD) that tells how much time each fracdion of the charge spends in the vessel. 

A distinc tion is to be drawn between situations in which (1) the flow pattern is known in detail, and (2) only the residence time distribution is known or can be calculated from tracer response data. Different networks of reactor elements can have similar RTDs, but fixing the network also fixes the RTD. Accordingly, reaction conversions in a known network will be unique for any form of rate equation, whereas conversions figured when only the RTD is known proceed uniquely only for hnear kinetics, although they can be bracketed in the general case. 

Axial Dispersion and the Peclet Number Peclet numbers are measures or deviation from phig flow. They may be calculated from residence time distributions found by tracer tests. Their values in trickle beds are fA to Ve, those of flow of liquid alone at the same Reynolds numbers. A correlation by Michell and Furzer (Chem. Eng. /., 4, 53 [1972]) is... 

A practical method of predicting the molecular behavior within the flow system involves the RTD. A common experiment to test nonuniformities is the stimulus response experiment. A typical stimulus is a step-change in the concentration of some tracer material. The step-response is an instantaneous jump of a concentration to some new value, which is then maintained for an indefinite period. The tracer should be detectable and must not change or decompose as it passes through the mixer. Studies have shown that the flow characteristics of static mixers approach those of an ideal plug flow system. Figures 8-41 and 8-42, respectively, indicate the exit residence time distributions of the Kenics static mixer in comparison with other flow systems. 

Tracer A substance that is used for measuring the residence time distribution in a vessel. Usually, it is inert and used in small concentrations so as not to change the physical properties of the process fluid appreciably, and analyzable for accuracy. 

As we have said, the key to the analysis of asystemlike this one is tohave a function that approximates to the actual residence time distribution. The tracer experiment is used to find that distribution function,butwewillworkfroman assumed function to the tracer concentration-timecurvetoseewhattheexperimentaloutcomemightlooklike. 

Glaser and Lichtenstein (G3) measured the liquid residence-time distribution for cocurrent downward flow of gas and liquid in columns of -in., 2-in., and 1-ft diameter packed with porous or nonporous -pg-in. or -in. cylindrical packings. The fluid media were an aqueous calcium chloride solution and air in one series of experiments and kerosene and hydrogen in another. Pulses of radioactive tracer (carbon-12, phosphorous-32, or rubi-dium-86) were injected outside the column, and the effluent concentration measured by Geiger counter. Axial dispersion was characterized by variability (defined as the standard deviation of residence time divided by the average residence time), and corrections for end effects were included in the analysis. The experiments indicate no effect of bed diameter upon variability. For a packed bed of porous particles, variability was found to consist of three components (1) Variability due to bulk flow through the bed... 

Ross (R2) measured liquid-phase holdup and residence-time distribution by a tracer-pulse technique. Experiments were carried out for cocurrent flow in model columns of 2- and 4-in. diameter with air and water as fluid media, as well as in pilot-scale and industrial-scale reactors of 2-in. and 6.5-ft diameters used for the catalytic hydrogenation of petroleum fractions. The columns were packed with commercial cylindrical catalyst pellets of -in. diameter and length. The liquid holdup was from 40 to 50% of total bed volume for nominal liquid velocities from 8 to 200 ft/hr in the model reactors, from 26 to 32% of volume for nominal liquid velocities from 6 to 10.5 ft/hr in the pilot unit, and from 20 to 27 % for nominal liquid velocities from 27.9 to 68.6 ft/hr in the industrial unit. In that work, a few sets of results of residence-time distribution experiments are reported in graphical form, as tracer-response curves. 

Hoogendoorn and Lips (H10) carried out residence-time distribution experiments for countercurrent trickle flow in a column of 1.33-ft diameter and 5- and 10-ft height packed with -in. porcelain Raschig rings. The fluid media were air and water, and ammonium chloride was used as tracer. The total liquid holdup was calculated from the mean residence time as found... 

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. 

Transient experiments with inert tracers are used to determine residence time distributions. In real systems, they will be actual experiments. In theoretical studies, the experiments are mathematical and are applied to a d5mamic model of the system. 

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. 

The use of inert tracer experiments to measure residence time distributions can be extended to systems with multiple inlets and outlets, multiple phases within the reactor, and species-dependent residence times. This discussion ignores these complications, but see Suggestions for Further Reading. ... 

Given k fit) for nny reactor, you automatically have an expression for the fraction unreacted for a first-order reaction with rate constant k. Alternatively, given ttoutik), you also know the Laplace transform of the differential distribution of residence time (e.g., k[f(t)] = exp(—t/t) for a PER). This fact resolves what was long a mystery in chemical engineering science. What is f i) for an open system governed by the axial dispersion model Chapter 9 shows that the conversion in an open system is identical to that of a closed system. Thus, the residence time distributions must be the same. It cannot be directly measured in an open system because time spent outside the system boundaries does not count as residence but does affect the tracer measurements. 

One method of characterising the residence time distribution is by means of the E-curve or external-age distribution function. This defines the fraction of material in the reactor exit which has spent time between t and t -i- dt in the reactor. The response to a pulse input of tracer in the inlet flow to the reactor gives rise to an outlet response in the form of an E-curve. This is shown below in Fig. 3.20. 

In a real stirred tank with bypassing or short-cut flow (Fig. 3.22), highly concentrated tracer comes out early, and the residence time distribution depends on the fraction a of the flow in the bypass (Fig. 3.23). The tailing of the response curve is caused by the perfect mixing in the main part of the tank. 

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 residence time distributions can be measured by applying tracer pulses and step changes as explained in Sec. 3.2.9. The response curves are best normalised such that the dimensionless time is... 

This program is designed to simulate tracer experiments for residence time distributions based on a cascade of 1 to 8 tanks-in-series. An nth-order reaction can be run, and the steady-state conversion can be obtained. The important parameters to change are as follows for the tracer experiments k, CAINIT, and CAO ( = 0 for E curve, = 1 for F curve). For reaction studies, the parameters to change are n, k, CAO, and CAINIT. 

In Section 11.1.3.2 we considered a model of reactor performance in which the actual reactor is simulated by a cascade of equal-sized continuous stirred tank reactors operating in series. We indicated how the residence time distribution function can be used to determine the number of tanks that best model the tracer measurement data. Once this parameter has been determined, the techniques discussed in Section 8.3.2 can be used to determine the effluent conversion level. 

Reactive Tracer. If the tracer is reactive, the measured concentrations reflect both mixing characteristics and decay of the tracer. Therefore, the data must be adjusted, such that the residence time distribution within the reactor can be obtained. Example 19-3 illustrates how to adjust the data following a step input of a reactive tracer. 

Residence time distribution (RTD). In the case of elutriation of tracer... 

Residence time distributions can be determined in practice by injecting a non-reactive tracer material into the input flow to the reactor and measuring the output response characteristics in a similar manner to that described previously in Section 2.1.1. 

A system of N continuous stirred-tank reactors is used to carry out a first-order isothermal reaction. A simulated pulse tracer experiment can be made on the reactor system, and the results can be used to evaluate the steady state conversion from the residence time distribution function (E-curve). A comparison can be made between reactor performance and that calculated from the simulated tracer data. 

Evaluate the conversion for first-order reaction from a tracer pulse response curve using the method in example CSTRPULSE. Show that although the residence time distributions may be the same in the two cases, the overall chemical conversion is not, excepting for the case of first-order reaction. 

For isothermal, first-order chemical reactions, the mole balances form a system of linear equations. A non-ideal reactor can then be modeled as a collection of Lagrangian fluid elements moving independe n tly through the system. When parameterized by the amount of time it has spent in the system (i.e., its residence time), each fluid element behaves as abatch reactor. The species concentrations for such a system can be completely characterized by the inlet concentrations, the chemical rate constants, and the residence time distribution (RTD) of the reactor. The latter can be found from simple tracer experiments carried out under identical flow conditions. A brief overview of RTD theory is given below. 

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