"An ounce of careful plant design is worth ten pounds of reconstruction.

"

LECTURE 12: LABORATORY AND INDUSTRIAL CATALYTIC

REACTORS: SELECTION, APPLICATIONS, AND DATA ANALYSIS
I. Introduction
A. Why study reactors?
B. Definition and classification of reactors
C. Reactor/process design perspective: from the laboratory to the full-scale plant
D. Selection of reactors in the laboratory and plant
II. Laboratory and Bench Scale Reactors
A. Kinds
B. Criteria for selection of lab/bench scale reactors; applications
III. Plant Reactors
A. Common types
B. Fixed catalyst bed reactors: characteristics, advantages, limitations
C. Fluidized beds: characteristics, advantages, limitations
D. Criteria for selection
IV. Collecting, Analyzing and Reporting Data from Laboratory Reactors
A. General approach and guidelines
B. Criteria for choosing catalyst form and pretreatment, reaction conditions
C. Choosing mode of reactor operation; differential and integral reactors
D. Analyzing and reporting data from laboratory reactors
1. Analysis of rate data: objectives and approach
2. Integral analysis
3. Differential analysis
V. Examples
New HDS Unit, ARCO Carson, CA Refinery
 I. Introduction
A. Why study reactors?
1. The design of catalyst and reactor
are closely interrelated.
2. Design of catalytic processes
requires a knowledge reactor
design, operation optimization and
selection
3. Progress in improving our standard
of living depends on our ability to
design reactors
4. Our personal existence depends on
controlling cellular reactions in our
body while that of the human race
hangs on the outcome of enormous
global reactions.
 B. Definition and Classification of Reactors
1. What is a Reactor?
a. A device that encloses the reaction space, and which houses the
catalyst and reacting media.
b. A container to which reactants are fed and products removed, that
provides for the control of reaction conditions.

2. Classification of Reactors
a. Size
b. Methods of charging/discharging: batch or steady-state flow
c. Motion of particles with respect to each other
d. Fluid flow type: tubular or mixed-fluid
Table 12.1 Classification of Catalytic Reactors
Basis for Classification Classes Examples

Size Laboratory 0.5 cm diam. tubular microreactor (0.1-1 g catalyst)

Bench scale 2.5 cm diam. x 30-50 cm long tubular reactor (50-200 g catalyst)
Pilot scale 7.5 cm diam x 6-10 m long tubular reactor (20-100 kg catalyst)
Plant scale 1-6 m diam x 20-50 m long tubular reactor (20-100 metric tons cat.)
Methods of charging and Batch Stirred liquid and solids
discharging Flow, steady state a. tubular, fixed catalyst bed
b. slurry, mixed fluid, mixed solids

Motion of catalyst Fixed Tubular fixed solids (fixed bed)

particles relative to each Relative motion a. fluidized bed
other b. slurry bubble column

Fluid flow Tubular, plug flow Turbulent gas in tubular fixed bed Slurry reactor with mechanical
Mixed fluid flow stirring
 Hardware Scientific & Scientific &
and Engineering Engineering
Software Tasks Disciplines

Discover
Reaction
Laboratory
C. Reactor/process Reactor
Intrinsic
Catalyst Prop.
Diff., Mas s Trans
Chemical Kinetics
and Catalysis
Kinetics

design perspective Kinetic Model

Development

Reaction
Rate/Selectivity & Engineering &
Rate Equation
Mathematics
Reactor Model
Development

Reactor Model Reactor /Process

Design

Fig. 12.1 Structure of Catalytic Process Catalytic Reactor

Design
Development [adapted from J. M. Smith,
Chem. Eng. Prog., 64, 78 (1968)].
Pilot Plant Process Design
Reactor Economics

Finl. Plant Design

& Economic
Studies

Large Scale
Plant
 D. Choosing reactors in the lab and plant
Reactors are used for many different purposes:
1. to study the mechanisms and kinetics of chemical reactions to
provide data for validation of process simulations
2. to investigate process performance over a range of process
variables
3. to obtain design data
4. to produce energy, materials and products.
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
II. Common Lab and Bench Scale Reactors

1. fixed bed tubular

2. stirred gas, fixed bed
3. stirred liquid/gas, stirred catalyst
4. fluid bed
5. fixed bed, transient gas flow

Laboratory and bench-scale reactors vary greatly in size,

complexity, cost, and application.
Table 12.2 Laboratory and Bench-Scale Catalytic Reactors
Classes Class Examples Features
Fixed bed tubular Laboratory 0.5 cm diam tubular microreactor (0.1-1 g catalyst,
differential/integral solid catalyst, gas fluid; glass or metal
Bench-scale integral 2.5 cm diam. x 30-50 cm long tubular reactor (50-200 g
catalyst); solid catalyst, gas or liquid fluid; metal

Stirred gas, fixed bed
Stirred liquid/gas, stirred
catalyst
Stirred batch microreactor, 1 g catalyst, glass or met.
Batch recycle microreactor, 1 g catalyst, glass or met.
Berty bench-scale, 2-200 g cat., 10-100 atm, stainless steel,
Carberry circulating gas
bench-scale, 2-200 g cat., 10-100 atm, stainless steel,
spinning catalyst basket
Stirred batch bench-scale, 2-50 g cat., 1-200 atm, glass or metal
Bubble slurry heterogeneous or homogeneous catalyst

Fluid bed Laboratory microreactor, 1-5 g cat, 1 atm, glass bench-scale, 50-
Bench-scale transport 200 g catal, 1-10 atm, metal
Recirculating transport

Fixed bed, transient gas Pulse flow microreactor, 0.1-1 g catalyst, glass or metal, 1 atm
flow TPD/TPSR
Radio tracer exchange
MS/Transient response
Frequency response
Fig. 12.2 Features of
representative laboratory
reactors [Levenspiel, 1979].
10/30 female joint

10/30 male joint

9 mm O-ring joint

4 ft. preheater coil of

2 mm capillary tubing
Thermocouple guide of
2mm capillary tubing
7"

Figure 12.3 Laboratory Pyrex

FBR reactor (courtesy of the BYU
Catalysis Laboratory).
Catalyst space

Fritted disc
Figure 12.4 Berty internal recycle reactor.
Gas-Liquid CSTR (UCSB) Batch Reactor (UCSB)
Bench scale reactor
(courtesy of Shell Corp.)
II. Laboratory and Bench Scale Reactors
B. Criteria for selection of lab and bench-scale reactors;
applications
1. Satisfying intended application
2. Avoiding deactivation
3. Avoiding inter- and intra- particle heat and mass transport limitations
4. Minimizing temperature and concentration gradients
5. Maintaining ideal flow patterns
6. Maximizing the accuracy of concentration and temperature
measurements
7. Minimizing construction and operating costs
Table 12.3 Seven Criteria for Selection of Laboratory and Bench-Scale
Catalytic Reactors
Criterion
1. Satisfy purpose of measurement (i.e.,
application)
2. Avoid catalyst deactivation where
possible; where not, decide if fast or
slow
3. Avoid inter- and intra-particle heat
and mass transport limitations
4. Minimize temperature and
concentration gradients
5. Maintain ideal flow patterns
6. Maximize accuracy of concentration
and temperature measurements
7. Minimize construction and
operating costs
Issues Involved/Measures of/Methods to Meet Criterion
Measure: (1) intrinsic activity/selectivity, (2) kinetics of reaction and
deactivation
Obtain mechanistic understanding
Simulate process
See Chap. 5 (B&F) on avoiding different kinds of catalyst deactivation
Fast decay causes activity and selectivity disguises and requires use of
transient or transport reactor
Slow decay best studied using CSTR or differential reactor
Thiele modulus less than 0.5; small particles or thin catalyst layer
Minimize film thickness with high flow rates, turbulence
Operate at low conversions
Use CSTR or differential reactor
Gradients cause activity and selectivity disguises
Maximize mixing in batch reactor and CSTR; use inerts
Use CSTR or differential reactor where possible
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
Table 12.4 Applications of Lab/Bench Test Reactors
Reactor Type Catalyst Selection Reactor/Design Fundamental Process
Activity/Selectivity Mechanism Simulation
Life Kinetics
Integral
Adiabatic X (overall avg. conv.) X X
Isothermal X (overall conv. at T) X X
Differential
Single Pass X (intrinsic) X (intrinsic) X (eliminate)
Recycle X (intrinsic) X (intrinsic) X (eliminate)
Stirred gas X (intrinsic) X (kinetics) X (intrinsic) X (eliminate) X (model)
Fluid bed/ X (fast deact.) X (fast deact.) X (fast X
Transport deact.)
Micro-pulse X (comparative, initial) X
Transient X (elem. X X (model)
steps)
Common Types of Catalytic Plant Reactors
1. Fixed-bed Reactors
a. Packed beds of pellet or monoliths
b. Multi-tubular reactors with cooling
c. Slow-moving pellet beds
d. Three-phase trickle bed reactors

2. Fluid-bed and Slurry Reactors

a. “Stationary” gas-phase
b. Gas-phase
c. Liquid-phase
i. Slurry
ii. Bubble Column
iii. Ebulating bed
Table 12.5 Characteristics of Plant-Scale Fixed Bed Reactors
Advantages Disadvantages
1. Ideal plug (or mixed) flow 1. Poor heat transfer in a large fixed bed.
2. Simple analysis a. Temp. control and measurement difficult
3. Low cost, low maintenance b. Thermal catalyst degradation
4. Little loss or attrition c. Non uniform rates.
5. Greater variation in operating conditions and contact 2. Non uniform flow patterns e.g. channeling
times is possible 3. Swelling of the catalyst; deformation of the reactor
6. Usually a high ratio of catalyst to reactants 4. Regeneration or replacement of the catalyst is
long residence time complete reaction difficult - shut down is required.
7 Little wear on catalyst and equipment 5. Plugging, high pressure drop for small beads or
8. Only practical, economical reactor at very high pellets - ∆P is very expensive.
pressures 6. Pore diffusional problems intrude in large pellets

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
B. Fixed-bed reactors: characteristics, advantages,
limitations

Advantages:
• Flexible- large variation in operating conditions and contact times
is possible
• Efficient- long residence time enables a near complete reaction
• Generally low-cost, low-maintenance reactors

Disadvantages:
• Poor heat transfer with attendant poor temperature control
• Difficulty in regenerating or replacing spent catalyst
 a.. Reactants Inlet

Liquid Or
Feed Gaseous
Bath

Reactor Reactor
Inert balls Tube Tube

Catalyst
Gas Or
Liquid
Flow

Outlet
Product

Product

Figure 12.5 Commercial

fixed-bed, adiabatic catalytic
reactor.

Fig. 12.6 Commercial fixed-bed reactor designs for controlling

temperature: (a) multi-tubular heat-exchange reactor, (b) series of
fixed-bed, adiabatic reactors with interstage heating or cooling.
Table 12.6
Characteristics of Plant-Scale Fluidized and Slurry Bed Reactors
Advantages
1. Frequent regeneration of the catalyst
possible.
2. Rapid mixing of solids in fluid beds means
uniform gas composition.
3. Isothermal operation and efficient
temperature control is practical.
4. Small-diameter particles in fluid minimize
pore diffusional resistance.
5. Improved thermal efficiency because of
high heat transfer rates.
6. In the case of highly exothermic, liquid
phase reactions, slurry reactors are less
complex and less expensive than heat-
exchange-tubular systems.
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.
Figure 12.7 Liquid-phase slurry reactors: (a) forced-circulation,
slurry-bed reactor, (b) bubble-column, slurry-bed reactor.
Figure 12.8 Batch-slurry reactor for hydrogenation
of specialty chemicals.
Fig. 12.9 Design of typical FCC transfer-line (riser)
reactor with fluidized-bed regenerator.
 a. Products b. Products
Flue gas
Cyclone Riser
reactor Cyclone
Flue Reactor
gas
Catalyst Catalyst stripper
Regenerator stripper
Overflow Steam
well Steam
Regenerator
Reactor
feed

Air
Steam Air
Reactor
feed

Figure 12.10 Commercial FCC riser reaction designs (a) Exxon, (b) UOP.
Fluid Cat Cracker (Chevron) Stacked Fluid Cat Cracker (UOP)
Shell Cat-Cracker All-riser Cracking FCC Unit
Criteria for Selection of Plant Reactors
1. General Criteria.
a. deactivation rate and regeneration policy
b. reaction conditions
c. catalyst strength and attrition resistance
d. process economics
2. Role of Cp/(-DHr)

Fig. 12.11 (a) Operating line for a

highly exothermic reaction in an ideal
tubular reactor with pure reactant and
(b) corresponding reciprocal rate versus
conversion curve and area V/FAo for a
CSTR. (c) Operating line for a highly
exothermic reaction in an ideal tubular
reactor with dilute reactant and (d)
corresponding reciprocal rate versus
conversion curve and area V/FAo for a
PFR.
3. Optimal Temperature Progression

Figure 12.12 Optimum temperature progression (and locus of

maximum rates) of (a) reversible endothermic reaction and (b)
reversible exothermic reactions.
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.
 Collecting, Analyzing and Reporting Data
from Laboratory Reactors
Different purposes:
1. activity/selectivity and life data for catalyst selection
2. chemical reaction mechanistic and kinetic data for understanding the
reaction at a fundamental level, modeling the reaction process, and/or
designing reactors
3. process variable data over a wide range of conditions for purposes of
designing large-scale reactors, experimentally validating models and
optimizing the catalytic process.

Data collection typically involves three major steps (Fig. 12.14):

1. selection of a reaction and catalyst
2. selection of a reactor type
3. analysis of the data
 new experiments

Select Select reactor

and conditions Data Analysis
Reaction
and Criteria Batch Data mechanism
Catalyst Flow Integral rate expression
CSTR Differential process optimization
Plug - integral Initial Rates
or differential

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].

1. Catalyst Properties and Characterization

a. Catalysts/surfaces should be carefully prepared and pretreated so as to be free of
solid contaminants such as sulfur, chlorides, and carbon that might affect
activity.
b. Support effects should be avoided by studying reactions on single crystals of the
active catalytic phase, e.g., metal, metal films, and/or relatively highly-
concentrated, poorly-dispersed supported metals. Preparation methods should be
used which minimize decoration of the metal surface, e.g., decomposition of
metal carbonyls on supports. Supported base metal catalysts need to be well-
reduced to avoid complications due to unreduced metal oxides.
c. In the case of structure-sensitive reactions, effects of surface structure and/or
dispersion need to be taken into account.
d. Metal dispersion/surface area should be measured using proven and/or standard
(ASTM) methods, e.g., hydrogen chemisorption or titration rather than CO
chemisorption for metals.
e. Methods of preparation and characterization should be reported in detail.
Methods for calculating surface area and dispersion should also be carefully
reported. Reporting these methods and the surface area or dispersion of catalyst
samples should be a requirement for publication of specific activity data.
 Table 12.7 Continued
2. Reaction Conditions
a. TOF and kinetic data must be measured in the absence of pore diffusional
restrictions, film mass transfer limitations, and heat transfer limitations
(generally at low temperature and low conversion). Experimental evidence and
calculations based on well-known criteria (e.g., the Thiele modulus for pore
diffusional resistance) should be provided in publications to demonstrate that
the data were obtained in the absence of these effects.
b. TOF and kinetic data must be measured in the absence of deactivation effects,
e.g., poisoning, coking, and sintering. The burden of proof that such effects are
absent should be on the authors of a publication.
c. TOF data should be collected over wide ranges of temperature and reactant
concentrations to facilitate valid comparison with data from other laboratories
and to provide meaningful data for determining temperature and concentration
dependencies.
d. TOF data should be reported at specified conditions of temperature, reactant
concentrations, and conversion. These specifications should be used by
reviewers and editors as a minimum reporting requirement for publication in a
journal.
Analyzing and reporting data from laboratory
reactors

1. Analysis of rate data: objectives

a. finding a rate equation
b. determining catalyst activity, selectivity and activity stability
c. determining the effects of important process variables such as
temperature, pressure, reactant concentrations, and space velocity
on activity, selectivity and stability

2. Extracting rate constants and concentration dependencies

a. Integral analysis
b. Differential analysis
 Figure 12.15
Test for integral analysis of rate data involving plot of
W/FAo versus integrated reciprocal rate. x
x
W x
F x
x
Integral Analysis of Rate Data x dx
o (-rA)

Integral analysis of rate data involves the following steps:

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 b
slope = -rA'
XX slope =
(a) Differential analysis to obtain X
reaction rates. (b) Plot to obtain
X X
reaction orders. XA 0.5 X X ln (-rA) X
X X
X X
Differential Analysis X
0
of Rate Data 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 CAα, 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.