Course Review

Non-Ideal Reactors Heterogeneous Reaction Systems

Consultation Time: 2-3 pm (22-26 April) E5-03-18

What We Have Covered

Isothermal, Ideal Reactor (Homogeneous Single Reaction) Design
Mole Balance
In Out + Gen = Acc dN A FA0 FA + rA dV = V dt

Output

Rate Law

Design Algorithm
n A

Time (t) Space time () Conversion (X)

rA = kC

1.GMBE, 2.Rate Law 3. Stoich, 4.Combine

Analysis of Rate Law

Kinetics: k and n

P-2

Non-Ideal Reactors
Isothermal, Non-Ideal Reactors (Single reaction)
Models (micromixing)
1.SEG 2.TIS 3.Dispersion 4.Compartment

Output

Rate Law

RTD (macromixing)
n A

rA = kC

1. Pulse injection 2. Step injection

Conversion (X)

P-3

RTD for Chemical Reactors (Unit 7)

Outline the concept of residence time distribution (RTD) as well as the reasons for using this concept in connection with non-ideal reactors. Define the residence time distribution function, E(t), and the cumulative residence time distribution function, F(t), and use the relation between them. Outline and understand the measurement methods for obtaining the residence time distribution. Use experimental results from pulse and step experiments to calculate the mean residence time and the variance. Derive the residence time distribution functions, E(t) and F(t), for ideal reactors (PFR and CSTR). Define the concept of mean residence time, tm, and, for a CSTR as an example, show that this time equals the space-time, . Define the concept of variance about mean residence time, 2, and show that this variance for a CSTR equals the space time squared, 2. Use the information of RTD to diagnose the ills of real reactor systems.
P-4

 Calculate E(t), F(t), tm, and 2

E (t ) = C (t )

C (t )dt

F (t ) = E (t )dt
0

t m = tE (t )dt
0

= (t t m ) 2 E (t )dt
2 0

RTD functions for an ideal reactor Plug flow: CSTR:

P-5

E (t ) = (t )
E (t ) = e
t /

Models (Unit 8)
Outline the concept of macromixing and micromixing. Outline the concept of macrofluid and microfluid. Outline the basic assumptions of the segregation model as well as the cases when this model may be applied. Use the segregation model for calculations on non-ideal reactors. Outline the basic idea of the tanks-in-series model and the dispersion model. Use the TIS model and the dispersion model to solve reactor performance problems with experimental results from tracer experiments. Outline the concept of compartment model, and use this model to predict the performance of non-ideal reactors.

P-6

E(t) t

Models for Predicting Conversion from RTD Data

X = X (t ) E (t )dt
0

Segregation Model

Mixing of globules of different ages occurs here

1st order
Vi = V i = n n

Tanks-inSeries

C1

Cn 1

2 n= 2
Cn

X = 1

1 (1 + i k ) n

2 =
Plug Flow Dispersion Model Dispersion
X = 1

2 Pe ( Per 1 + e r ) st 2 1 order Per

4q exp( (1 + q ) 2 exp( Per ) 2

P-7

qPer qPer ) (1 q ) 2 exp( ) 2 2 4 Da UL q = 1+ ; Da = k ; Per = Per D

Compartment Model = Fractional volume

= Fractional flow rate

Models for Predicting Conversion from RTD Data (Complicated RTD)

F (t )

P-8

P-9

P-10

Heterogeneous Catalytic Reactor Design

Isothermal, Heterogeneous Catalytic Reactor (PBR, Single Reaction) Design
Mole Balance
In Out + Gen = Acc
z=0
Ac

Output

dC Ab U + rA ' b = 0 dz
Overall Rate Law Expression

z + z

z=L

Conversion (X) Catalyst weight (W)

rA ' = f (C Ab )
External mass transfer Internal mass transfer Intrinsic reaction rate

C Ab C As
C A (r )
r

WAr

Bed length (L)

Design Algorithm Synthesize the Rate Law

rate = (kinetic factor)(driving - force group) (adsorption group)

1.GMBE, 2.Rate Law 3. Stoich, 4.Combine

P-11

Overview of Packed Bed Reactor Design

A B
R

CA

C As C Ab

PBR
Ac , L C Ab , v0 , U W , S a , c , b ,

A catalyst pellet
R , d p , ac WAr , kc , DAB

Porous catalyst pellet

C Ab , C As , C A

n , ,
n ) rA ' = (rAs ' ) = (k n ' C As n rA ' = (rAb ' ) = (k n ' C Ab )

dC Ab + rA ' b = 0 U dz
P-12

The Steps to Consider

C As = f (C Ab ) Unit 10 C A = f (C As ) Unit 11

rA ' = f (C A ) Unit 9
1. 2. 3. 4. 5. 6. 7. Mass transfer through external boundary layer Diffusion into pores Adsorption Surface reaction Desorption Diffusion of products out of pores Mass transfer back to bulk fluid

The overall rate of reaction is equal to the rate of the slowest step in the mechanism ratedetermining step.

P-13

Elements of Heterogeneous Catalysis (Unit 9)

Outline the steps in a catalytic reaction and use the concept of a ratelimiting step to derive a rate law. Develop a rate law and linearize it to determine the rate-law parameters from a set of gas-solid reaction rate data. Derive the design equation for a catalytic reactor. Calculate the conversion or catalyst weight for packed bed reactors. Describe the different types of catalyst deactivation. Outline the basic idea to design reactors to solve the catalyst deactivation problems. Calculate the conversion or catalyst weight for moving bed reactors.

P-14

Obtain data from laboratory reactors

An Algorithm for Catalytic Reactor Design

Adsorption Surface reaction Desorption

Synthesize rate law from data

Develop mechanism and rate-limiting step

Estimate rate law parameters

Reactor design

More than 75% of all heterogeneous reactions are surface-reaction-limited.

Irreversible SurfaceReaction-Limited Rate Laws

rate =

(kinetic factor)(driving - force group) (adsorption group)

kPA rA ' = Single site A S B S 1 + K A PA + K B PB kPA Dual site r ' = A S + S B S + S A (1 + K A PA + K B PB )2 kPA PB r ' = A S + B S C S + S A (1 + K A PA + K B PB + K C PC )2 kPA PB Eley-Rideal A S + B ( g ) C S rA ' = 1 + K A PA + K C PC P-15

Catalyst Deactivation
Catalyst deactivation a (t ) = Rate of reaction

rA ' (t ) rA ' (t = 0, fresh )

rA ' = a (t ) rA ' (fresh )

Decay law

da = rd dt

Overcoming catalyst deactivation temperature-time trajectory transport reactors

To offset the decline in chemical reactivity of decaying catalysts: Temperature Time Trajectories Moving-Bed Reactor

T = f (t )

P-16

External Mass Transfer Resistance (Unit 10)

Use mass transfer in the context of reactor calculations. Outline the concept of the film theory for the external mass transfer. Evaluate the effects of fluid flow rate and particle size on the performance of a mass transfer-limited reactor. Derive the reaction rate expressions for slow and rapid reaction on a catalyst surface and outline the assumptions which this derivation is based on. Outline how mass transfer-limited reactions respond to changes in temperature and flow conditions. Design a reactor operating at conditions limited by external mass transfer.

P-17

External Mass Transfer in a Packed-Bed Reactor

Ac

A steady-state mole balance on reactant A (ideal plug flow)

z

z=0

z + z

z=L

dC Ab '' U + rA ac = 0 dz
For reaction at steady state

C Ab
C As

WAr

Boundary layer

'' rA = WAr

External-mass transfer limited

'' rA = kcC Ab

Diffusion across stagnant film surrounding a catalyst pellet

C Ab k c ac = exp z C Ab 0 U

P-18

Summary
Scheme of surface reaction kinetics

Flow and reaction (ideal plug flow)

U dC Ab '' + rA ac = 0 dz

A B
fluid reactants products external transport

The film theory

WAz = kc (C Ab C As )

Correlations of kc
= 2 + 0.6Re1/2Sc1/3 Flow through a packed Sh' = (Re' )1/2 (Sc' )1/3
bed (Thoenes-Kramers) Flow around a spherical particle (Frossling) Sh

internal diffusion

External mass transfer-limited, PBR

'' rA = kcC Ab

adsorption desorption solid sites rxn

ln

ka 1 = c cL 1 X U

P-19

Internal/Pore Diffusion Resistance (Unit 11)

Derive the Thiele modulus. Derive the effectiveness factor for porous catalyst particles with various geometries. Use the concept of the effectiveness factor and outline how this factor can be increased by various operation conditions. Use the Thiele modulus for reactions with diffusion. Distinguish between internal and overall effectiveness factor. Describe how the reaction rate is influenced by parameters such as velocity, particle size and temperature. Design PBR operating under pore-diffusion limited regime.

P-20

Qualitative Analysis
Reactant concentration profiles around and within a porous pellet.

porous catalyst pellet

reaction limited pore diffusion limited

CA b

CAs

C A (x) CA
external mass transfer limited

P-21

+R

For 1st order surface reaction in spherical porous catalysts

rate without any diffusion effects

rA ' = k ' C As
with

2 1

(1 coth 1 1)

Effectiveness factor, a fudge factor which varies between 0 and 1, and which accounts for the resistance to pore diffusion. Thiele modulus, useful for predicting reactor behavior from known kinetic information, thus known k. Effective diffusion coefficient in porous solids.

where

1 = R

k1 ' ' c S a De

P-22

For first-order reaction

Ac C Ab 0
z=0
z

C AbL

C Ab = C Ab 0 e ( b k1 ''S a z ) / U

z + z

z=L
Porous catalyst pellet

C Ab
External resistance

C As

CA
Internal resistance

X = 1 e ( b k1 ''S a L ) / U
=

1 + k1 ' ' S a b / kc ac

12

(1 coth 1 1); 1 = R

k1 ' ' c S a k =R 1 De De

P-23

Dependence of Reaction Rate on dP, U, and T (1st order reaction)

External diffusion
2/3 DAB U 1/ 2 kc 1/ 6 1/ 2 dp

Internal diffusion

Reaction-limited

3 rA = De k1 C As R

rA = k1C Ab

kc U 1/ 2T 11/12
P-24

Summary
Scheme of surface reaction kinetics The Thiele modulus for porous spheres
n 1 n kn R 2C As R knC As reaction rate = = = De De [( C As 0) / R ] diffusion rate 2 n

A B
fluid reactants products external transport

The effectiveness factors

=
= actual overall rate of reaction reaction that would occur if entire surface exposed to C As actual overall rate of reaction reaction that would occur if entire surface exposed to C Ab

Internal diffusion

For large values of Thiele modulus

2 = n +1
1/ 2

adsorption desorption solid sites rxn

P-25