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 Rate of reaction

Model

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 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

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

(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. Find the reactor temperature for 80 % conversion.

2. 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

conversion

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
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

2. You can then plot for different values of ∆HR

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(θ) vs. T is nonlinear, but Qr(θ) 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

3 2
Volume VR (m ) Diameter db (m) heat exchanger area A (m )
0,1 0,508 0,8
0,16 0,6 1,16
0,25 0,7 1,48
0,4 0,8 2,32
0,63 1 2,87
1 1,2 3,87
1,6 1,4 5,6
2,5 1,6 7,9
4 1,8 9,1
6,3 2 13,1
8 2,2
10 2,4 18,7
12,5 2,4
16 2,8 25
20 2,6
25 3 34,6
32 3,4
40 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

∂Q ∂Tw
= U(T − TW ) = Qwcpw
∂A ∂A
⎡ ⎤
Qw = Qwcpw ⎢⎣1−exp ( −UA/Qwcpw )⎥⎦(T − TWF)

T
Heat Exchangers in CSTR
Types of Heat Exchangers – 2
(3) External Heat Exchanger with Recycle

Heat
exchanger

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

( −ν j )r0i θ
Da i =
c j0

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

reaction order r0 Φ(X) Da

(- ν j ) ⋅ k 0 ⋅ θ
0 k0 1
c j0
1 k 1 ⋅ c j0 1-X j (- ν j ) ⋅ k 1 ⋅ θτ
2 (r = k 2 c ) k2 ⋅c (- ν j ) ⋅ k 2 ⋅ c j 0 ⋅ θτ
2 2 2
j j0 (1-X j )
2 (r = k 2 c k c j ) k 2 ⋅ c k 0 ⋅ c j0 (1-X j )(1- λ X j ) (- ν j ) ⋅ k 2 ⋅ c j0 ⋅ θτ
λ = ν k c j 0 / ν 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)Φ(X)
-vi θ

Relative Cooling Intensity Adiabatic Temperature Increase

cA0
Stanton Number, St = ∆Tad =
vi

St ∆Tad (X)

Heat Exchangers in CSTR

Analysis – 2

St ∆Tad (X)

(2a) Jacketed Heating and Cooling

St (T – TW) = κ (T – TWF) T0 TW
QWcPW
= (T – TWF)
+ QWcPW TWF

(2b) Integral Heat Exchanger

St (T – TW) = κ (T – TWF)

QWcPW
= [1 – exp (- / QWcPW] (T – TWF) T
Heat Exchangers in CSTR
Analysis – 3
(3) Calculation of Reactor Temperature
κ (T – TWF) ∆Tad (X)

(1 + κ) (T – T*W) = ∆Tad (X)

(Tf – κTWF)
where T*W = outlet temperature in
(1 + κ) absence of temperature

(1 + κ) (T – T*W) = ∆Tad Daœ exp (-E/RT)

1 + Daœ 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
Separatrix
Conversion

such as (1) ignition, (2) extinction

and(3) oscillatory behavior.
X

Tmperature
 Heat Removal in CSTR
Nonadiabatic CSTR – 8
(7) General Analysis
(a) Effects of feed temperature (Tf)
(T0 – κTWF)
(1 + κ) (T – T*W) = ∆Tad (X) where T*W =
(1 + κ)

•
Q
Thermal Hysteresis
Heat removal

Heat generation

Heat Removal in CSTR

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

(1 + κ) (T – T*W) = ∆Tad Daœ exp (-E/RT)

1 + Daœ 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

tracer 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, No tracer
t > 0, Add small amount of tracer

Mixing and Residence Time Distribution

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

1
=
τ

τ 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

A→B

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:
(a) Cf 2, 4, 8, 16, 32 kmol/m3
(b) ∆HR -30, -20, -10, -5, 0, 5 x 104 kJ/kmol
Group 1 U° = 50 kJ/(m3minK)-1 Group 7 U° = 400
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

A↔B 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 Group 8 U° = 20
4 K1 = 5 10 U° = 100
6 K1 = 10
conversion