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LECTURE 12: LABORATORY AND INDUSTRIAL CATALYTIC REACTORS: SELECTION, APPLICATIONS, AND DATA ANALYSIS
I. Introduction
A. B. C. D. Why study reactors? Definition and classification of reactors Reactor/process design perspective: from the laboratory to the full-scale plant Selection of reactors in the laboratory and plant
II. III.
Plant Reactors
A. B. C. D. Common types Fixed catalyst bed reactors: characteristics, advantages, limitations Fluidized beds: characteristics, advantages, limitations Criteria for selection General approach and guidelines Criteria for choosing catalyst form and pretreatment, reaction conditions Choosing mode of reactor operation; differential and integral reactors Analyzing and reporting data from laboratory reactors 1. Analysis of rate data: objectives and approach 2. Integral analysis 3. Differential analysis
IV.
V.
Examples
I.
Introduction
b. A container to which reactants are fed and products removed, that provides for the control of reaction conditions.
2. Classification of Reactors
a. b. c. d.
Size Methods of charging/discharging: batch or steady-state flow Motion of particles with respect to each other Fluid flow type: tubular or mixed-fluid
Laboratory Reactor
Intrinsic Kinetics
Chemical Kinetics
Catalyst P rop. and Catalys is Diff., Mass Trans
Kinetic Model Development Reaction Engineering & Mathematics Reactor Model Development
Reactor Model
Fig. 12.1
Structure of Catalytic Process Development [adapted from J. M. Smith, Chem. Eng. Prog., 64, 78 (1968)].
Pilot Plant Reactor
Proces s Design Economic s Finl. Plant Des ign & Economic Studies
Choosing the right reactor is critical to the engineering process and is dictated by many different variables such as
reaction type rate of deactivation economics other process requirements
1. 2. 3. 4. 5.
stirred gas, fixed bed stirred liquid/gas, stirred catalyst fluid bed fixed bed, transient gas flow
Laboratory and bench-scale reactors vary greatly in size, complexity, cost, and application.
Class Examples
Laboratory differential/integral Bench-scale integral Stirred batch Batch recycle Berty Carberry
Features
0.5 cm diam tubular microreactor (0.1-1 g catalyst, solid catalyst, gas fluid; glass or metal 2.5 cm diam. x 30-50 cm long tubular reactor (50-200 g catalyst); solid catalyst, gas or liquid fluid; metal microreactor, 1 g catalyst, glass or met. microreactor, 1 g catalyst, glass or met. bench-scale, 2-200 g cat., 10-100 atm, stainless steel, circulating gas bench-scale, 2-200 g cat., 10-100 atm, stainless steel, spinning catalyst basket
bench-scale, 2-50 g cat., 1-200 atm, glass or metal heterogeneous or homogeneous catalyst
microreactor, 1-5 g cat, 1 atm, glass bench-scale, 50200 g catal, 1-10 atm, metal
Fig. 12.2
9 mm O-ring joint
4 ft. preheater coil of 2 mm capillary tubing Thermocouple guide of 2mm capillary tubing
7"
Figure 12.3
Catalyst space
Fritted disc
2. Avoid catalyst deactivation where possible; where not, decide if fast or slow 3. Avoid inter- and intra-particle heat and mass transport limitations
Minimize mixing and laminar flow in tubular reactors; Maximize mixing and minimize gradients in CSTR Avoid gas or liquid holdup in multi-phase reaction systems
Sensitive analytical methods and well-placed, sensitive probes Sufficiently high product concentrations Select the least expensive reactor that will satisfy the other criteria Consider ways of minimizing size of catalyst and volume of reactant gas
6. Maximize accuracy of concentration and temperature measurements 7. Minimize construction and operating costs
Integral
Adiabatic Isothermal Differential Single Pass Recycle Stirred gas Fluid bed/ Transport Micro-pulse Transient X (intrinsic) X (intrinsic) X (intrinsic) X (fast deact.) X (comparative, initial) X (elem. steps) X (kinetics) X (fast deact.) X (intrinsic) X (intrinsic) X (intrinsic) X (fast deact.) X X X (model) X (eliminate) X (eliminate) X (eliminate) X (model) X X (overall avg. conv.) X (overall conv. at T) X X X X
Overcoming the Disadvantages 1. Monolithic supports overcome disadvantages 2, 5 & 6 2. Temperature control problems are overcome with: a. Recycle b. Internal and external heat exchanges c. Staged reactors d. Cold shot cooling e. Multiple tray reactor - fluid redistributed & cooled between stages. Catalyst is easily removed - varied from tray to tray. f. Use of diluents g. Temperature self regulation with competing reactions, one endo and one exothermic. h. Temp control by selectivity and temporarily poisoning the catalyst
Disadvantages:
Poor heat transfer with attendant poor temperature control Difficulty in regenerating or replacing spent catalyst
a..
Reactants Inlet
Feed
Reactor Tube
Reactor Tube
Outlet Product
Product
Disadvantages
1. Fluidized beds are complicated systems involving multiple reactors, heat exchangers, extensive valving and piping to provide continuous system. 2. $$ Extensive investment. Maintenance is high.
3. Fluid flow is complex in fluidized and slurry bubble columns - less than ideal contacting. Product distribution is changed - less intermediate formed in a series reaction.
4. Only a small variation in residence time possible. Low residence times. Conversion may be limited. 5. Attrition & loss of Catalyst.
b. Flue gas
Air
Figure 12.10 Commercial FCC riser reaction designs (a) Exxon, (b) UOP.
Shell Cat-Cracker
2. Role of Cp/(-DHr)
Fig. 12.13 (a) Use of staged adiabatic tubular fixed-bed reactors with interstage cooling to achieve optimum
temperature progression in the cases of exothermic reversible, exothermic irreversible and endothermic reactions. (b) Design schematic for staged adiabatic fixed-bed reactors with interstage furnace heating for a strongly endothermic reaction such as reforming of methane.
new experiments Select Reaction and Catalyst Select reactor and conditions Batch Flow CSTR Plug - integral or differential Data Analysis Data Integral Differential Initial Rates mechanism rate expression process optimization
Criteria
Figure 12.14 Process of obtaining rate and kinetic data; note that
statistical methods are used in Steps 2 and 3 and in the recycle process.
Table 12.7 Proposed Guidelines for Choosing Catalyst Form, Pretreatment, and
Reaction Conditions and for Reporting of Data [Ribiero et al., 1996].
Figure 12.15
Test for integral analysis of rate data involving plot of W/FAo versus integrated reciprocal rate.
W F x
x x
x dx o (-rA)
1. A series of runs are made in a packed bed at a fixed initial concentration CAo and a fixed temperature while varying the catalyst mass W and/or the initial molar flow rate FAo to generate a range of W/FAo values at different conversions (XA). 2. A candidate rate equation is selected for testing using the design equation for plug flow. First try simpler rate equations, e.g. zero-, first- and second-order irreversible and use differential analysis to scope out possible reaction orders. 3. The left-hand side (W/FAo) and right-hand side (the integral of 1/rA) of the design equation are each evaluated numerically and plotted against each other, as shown in Figure 4.19 to test for linearity. 4. Linearity of the plot (e.g. Figure 12.15) is used as the criterion for judging if the candidate rate equation is a useful model of the data, i.e. consistent with the data. 5. This should be followed by a nonlinear regression with statistical analysis to determine kinetic parameters.
1.0
Fig. 12.16
(a) Differential analysis to obtain reaction rates. (b) Plot to obtain reaction orders.
slope = -rA' X X X X
b X X X ln (-rA) X X
slope = X X
XA 0.5 X X 0
W/FA0
ln CA
Differential analysis of rate data involves the following steps: 1. The identical series of runs (as in integral analysis) are made in a packed bed at a fixed initial concentration CAo and fixed temperature while varying the catalyst mass W and/or the initial molar flow rate FAo to generate a range of W/FAo values at different conversions (XA). 2. A plot of conversion XA versus W/FAo data is made for each set of runs at a fixed temperature. A best fit of the data is made using a simple quadratic or cubic equation, and the corresponding curve is plotted on the same figure, as illustrated in Figure 4.20(a). 3. Tangents to the curve are drawn at regular intervals along the curve corresponding to the best fit, and the slopes of these tangents are evaluated (Figure 12.16a); the slopes on this plot correspond to the reaction rate, i.e. dXA = (rA)[d(W/F)]. Tangents can be evaluated more accurately by differentiating the equation for the best fit of the data and evaluating the derivative at various intervals over the data set. 4. Values of rA versus XA are plotted on linear or log-log plots to determine reaction orders. For example, for an irreversible reaction in which data are fitted by a simple power rate law, rA = k CA , a plot of ln(rA) versus ln(CA) is linear with a slope (Figure 12.16b). 5. Differential analysis is a useful scoping tool to explore forms of the rate expression; however, in the end a nonlinear regression and rigorous statistical analysis is required to obtain kinetic parameters with acceptable accuracy.
References
1. O. Levenspiel, Chemical Reaction Engineering, 2nd and 3rd Eds., John Wiley and Sons, 1972, 1999. 2. O. Levenspiel, The Chemical Reactor Minibook, OSU Bookstores, 1979. 3. J.M. Smith, Chemical Engineering Kinetics, 3rd Ed., McGraw Hill, 1981. 4. "Reactor Technology," Kirk-Othmer: Encyclopedia of Chemical Technology, Vol. 19, 3rd Ed, John Wiley, 1982, pp. 880-914. 5. G.F. Froment and K.B. Bischoff, Chemical Reactor Analysis and Design, John Wiley, 1990. 6. O. Levenspiel, The Chemical Reactor Omnibook, 1993, OSU Bookstores, 1993. 7. C. H. Bartholomew and R. J. Farrauto, Fundamentals of Industrial Catalytic Processes, Chapman and Hall, 2005, Chap. 4.