Ideal Reactors

Types of Ideal Reactors

(Semi-)Batch reactor

Continuous stirred tank (CSTR)

Plug-Flow Reactor (PFR)

Recycle reactor

Stirred tank cascade

Ideal Reactors
Reactor Design
Volumetric flow rate

Reaction volume
Model

Rate of reaction

Inlet concentration

Outlet concentration

Outlet = f(inlet, kinetics, contacting pattern)

Ideal Reactors
Batch Reactor 1 Material Balance

Energy Balance (1) constant pressure

(2) constant volume

Ideal Reactors
Batch Reactor 2 Conversion and Temperature Profiles in Batch Reactor
ADIABATIC POLYTROPIC

t
Numerical solution necessary!

Ideal Reactors
CST Reactor Material Balance

mean residence time

steady state conversion

Ideal Reactors
Transient behavior in CSTR

Ideal Reactors
Transient behavior in CSTR

Ideal Reactors
Phenol Production in CSTR

CSTR Reactors
Energy Balance

Where:

of feed stream

CSTR Reactors
Energy Balance

0
feed

CSTR Reactors
Energy Balance

CSTR Reactors
Energy Balance

from material balance

General Energy Balance Equation for CSTR

CSTR
Summary of Energy Balance-1

CSTR
Summary of Energy Balance-1

(1) Please derive the constant volume-ideal gas for a CSTR reactor

CSTR
Energy Balance Special Case: Incompressible fluid

CSTR Reactors
Energy Balance Simplifying Assumptions

(1) Steady-State Condition

0
(2) Liquid Phase (3) Excess Solvent or Diluent

heat capacity is constant independent of pressure

CSTR
Temperature Control in CSTR 1
Aqueous solution of specie A undergoes a reversible isomerization reaction in a 2000 L CSTR.

1. 2.

Find the reactor temperature for 80 % conversion. What are the heat duties of the two heat exchangers ? Approximate the heat capacity of the reaction mixture with that of water.

CSTR
Temperature Control in CSTR 2
(1) Steady-State Condition

Ans. where

CSTR
Temperature Control in CSTR 3

1. (a) Plot conversion versus T (K) for CAf = 0.25, 4, 16. (b) Plot conversion versus T(K) for CAf = 4, if VR is 0.5 or 2 x the given value. (c) Plot conversion versus T(K) for CAf = 4, if activation energy of k1 is 0.5 or 2 x the given values. (d) Plot conversion versus T(K) for CAf = 4, if activation energy of K1 is 0.5 or 2 x the given values. Please summarize your observations.

CSTR
Temperature Control in CSTR 4
(2) Heat duties of the two heat exchangers

conversion

Multiple Steady-State
CSTR
(1) The coupling between material and energy balances in CSTR can lead to complex behavior, (2) The presence of multiple steady-state is possible even for the simplest kinetic mechanism.

Multiple Steady-State
Adiabatic CSTR 1

Multiple Steady-State
Adiabatic CSTR 2
(1) Material Balance

(2) Steady-State, Liquid Phase, Constant Density

Multiple Steady-State
Adiabatic CSTR 3
(3) Heat Capacity is Constant

heat transfer

where:

Multiple Steady-State
Adiabatic CSTR 4
(4) Material and Energy Balance for Adiabatic CSTR

(5) Solve the Nonlinear Equations (a) For isothermal case:

Multiple Steady-State
Adiabatic CSTR 5
(5) (b) For nonisothermal case:

1. Find

and

for for different values of HR

2. You can then plot

conversion

Multiple Steady-State
Adiabatic CSTR 6
(6) Multiple Steady-State (a) Reactions more exothermic than 10 x 104 kJ/kmole, there are multiple steady states, (b) Points at which steady-state curve turns correspond to the ignition and extinction points.

conversion

Multiple Steady-State
Adiabatic CSTR 7
(7) Hysteresis

conversion

ignition

ignition

extinction extinction

decreasing flowrate

decreasing flowrate

Multiple Steady-State
Adiabatic CSTR 8
(8) Stability of Steady-State van Heerden Diagram Dynamic Model

Solving

heat generation

heat removal

Procedure
(1) Qr = Qg then steady state condition occurs, (2) Qg() vs. T is nonlinear, but Qr() vs. T is linear, (3) The resulting plots is known as van Herdeen diagram

Multiple Steady-State
Adiabatic CSTR 9
(8a) van Heerden Diagram

Multiple Steady-State
Adiabatic CSTR 10
(8b) van Heerden Diagram

Multiple Steady-State
Adiabatic CSTR 11
(9) Mechanical Analogy

Single Steady-State A

Ignition Point A

Heat Exchanger in CSTR

Standardized Stirred Tank Reactor Sizes

Volume VR (m ) 0,1 0,16 0,25 0,4 0,63 1 1,6 2,5 4 6,3 8 10 12,5 16 20 25 32 40

Diameter db (m) heat exchanger area A (m ) 0,508 0,8 0,6 1,16 0,7 1,48 0,8 2,32 1 2,87 1,2 3,87 1,4 5,6 1,6 7,9 1,8 9,1 2 13,1 2,2 2,4 18,7 2,4 2,8 25 2,6 3 34,6 3,4 3,6 46

Heat Exchangers in CSTR

Types of Heat Exchangers 1
(1) Jacketed Heating and Cooling

Qw = UA(T- TW) = Q wcpw(T- TWF) = UAQwcpw (T- TWF) UA + Qwcpw

(2) Integrated Heat Exchanger

Tw Q = U(T TW ) = Qwcpw A A Qw = Qwcpw 1exp ( UA/Qwcpw )(T TWF)

Heat Exchangers in CSTR

Types of Heat Exchangers 2
(3) External Heat Exchanger with Recycle

Heat exchanger

Damkhler Number
Ratio between residence time and reaction time
Stable and Unstable Limit Cycle

Da i =
where

( j )r0i c j0

( ri = ri0 ( T ) ( Xi ); r = r0 ( T ) ( X j ) for any reaction)

reaction order
0 1 2 (r = k 2 c )
2 j

r0
k0 k 1 c j0 k2 c
2 j0

(X)
1 1-X j (1-X j )
2

(- j ) k 0 c j0 (- j ) k 1 (- j ) k 2 c j 0

Da

2 (r = k 2 c k c j )

k 2 c k 0 c j0

(1-X j )(1- X j ) (- j ) k 2 c j0 = k c j 0 / jc k 0

e.g. r = k 1( T ) c j = k 1( T ) c j0 (1 X j ) for 1st order kinetics

Da < 0,1 low conversion ;

Da < 100 nearly quantitative conversion

Heat Exchangers in CSTR

Analysis 1
(1) CSTR Energy Balance

cA0 1 Da(T)(X) -vi

Relative Cooling Intensity Stanton Number, St =

Adiabatic Temperature Increase

Tad =

cA0 vi

St

Tad (X)

Heat Exchangers in CSTR

Analysis 2
St
(2a) Jacketed Heating and Cooling

Tad (X)

St (T TW) = (T TWF) =
QWcPW + QWcPW

T0

TW

(T TWF)

TWF

(2b) Integral Heat Exchanger

St (T TW) = (T TWF) =
QWcPW

[1 exp (-

/ QWcPW] (T TWF)

Heat Exchangers in CSTR

Analysis 3
(3) Calculation of Reactor Temperature

(T TWF) (1 + ) (T T*W) = Tad (X)

where T*W =

Tad (X)

(Tf TWF) (1 + )

outlet temperature in absence of temperature

(1 + ) (T T*W) = Tad Da exp (-E/RT) 1 + Da exp (-E/RT)

Heat Removal Heat Generation

Oscillatory Behavior
Nonadiabatic CSTR 1

Oscillatory Behavior
Nonadiabatic CSTR 2
(1) Solving the New Problem

conversion

Oscillatory Behavior
Nonadiabatic CSTR 3
(2) Temperature and Conversion Oscillation 1

Phase Plot
limit cycle

Multiple Steady-State
Nonadiabatic CSTR 4
(3) Initial Conditions

CA0 = 0, T0 = Tf

global attractor

CA0 = CAf, T0 = Tf

Oscillatory Behavior
Nonadiabatic CSTR 5
(4) Temperature and Conversion Oscillation 2

Oscillatory Behavior
Nonadiabatic CSTR 6
(5) Stable and Unstable Limit Cycle

Oscillatory Behavior
Nonadiabatic CSTR 7
(6) Complex Phase Plots

In General: Cooling Capacity > Heat Generation lead to a stable steady-state. Heat Generation > Cooling Capacity usually lead to unstable steady-state such as (1) ignition, (2) extinction and(3) oscillatory behavior.

Conversion

Separatrix

Tmperature

Heat Removal in CSTR

Nonadiabatic CSTR 8
(7) General Analysis (a) Effects of feed temperature (Tf)

(1 + ) (T T*W) = Tad (X)

where T*W =

(T0 TWF) (1 + )

Thermal Hysteresis
Heat removal

Heat generation

Heat Removal in CSTR

Nonadiabatic CSTR 9
(b) Effects of residence time ()

(1 + ) (T T*W) = Tad Da exp (-E/RT) 1 + Da exp (-E/RT)

Q

Flow Hysteresis

TWF

Mixing and Residence Time Distribution

CSTR 1
(1) Fluid Flow Pattern in Reactor (a) Computational Fluid Dynamics (CFD) - fluid mixing is calculated by solving the equations of motion for fluid, - type of fluid flow (e.g., laminar and turbulent), and various transport mechanisms (e.g., molecular and eddy diffusions) must be accounted.

Mixing and Residence Time Distribution

CSTR 2
(b) Residence Time Distribution (RTD) - classical approach based on experimental probe, - do not use any structure of equation of motion, approximate idea of mixing. - at short length scale: condition that maximizes diffusion also enhances mixing and uniformity, at reactor length scale: condition that maximizes convection enhances mixing and uniformity.

Mixing and Residence Time Distribution

CSTR 3
(2) Gedanken Experiment

a tracer c b

(a) Probability function

Mixing and Residence Time Distribution

CSTR 4
(b) RTD Measurement Experimental Method

Cf C0

Cf C0

Mixing and Residence Time Distribution

CSTR 5
(3) CSTR Experiment

Step response experiment t 0, t > 0, No tracer Add small amount of tracer

Mixing and Residence Time Distribution

CSTR 6
(3) CSTR Experiment (a) Material Balance

is the mean residence time

Mixing and Residence Time Distribution

CSTR 7
(4) RTD in CSTR: Step-Change in Concentration

Mixing and Residence Time Distribution

CSTR 8
(5) Mean RTD

2. Describe a Semibatch Reactor (a) Write the governing material balance equation, (b) Write the governing energy balance equation for a incompressible liquid, constant pressure reactor.

Mini-Project 2
CSTR Reactor Group No. 1, 3, 5, 7, 9, 11

AB

Mini-Project 2
CSTR Reactor Group No. 1, 3, 5, 7, 9, 11
(1) Plot Conversion and T versus q (see below) as function of: 2, 4, 8, 16, 32 kmol/m3 (a) Cf (b) HR -30, -20, -10, -5, 0, 5 x 104 kJ/kmol Group 7 U = 400 Group 1 U = 50 kJ/(m3minK)-1 3 U = 100 9 U = 800 5 U = 200 11 U = 1600

conversion

Mini-Project 2
CSTR Reactor Group No. 2, 4, 6, 8, 10

AB

K1 = k1/k-1

Note HR is for the forward reaction, reverse reaction should give - HR

Mini-Project 2
CSTR Reactor Group No. 2, 4, 6, 8, 10
Plot Conversion and T versus q (see below) as function of HR is -30, -20, -10, 5, 0, 5 x 104 kJ/kmol. Group 2 K1 = 1 4 K1 = 5 6 K1 = 10 Group 8 U = 20 10 U = 100

conversion