17/01/2017

At the end of this topic, you should

be able to:
1. Describe, differentiate and give
the advantages and
Basic Types of Reactors, and disadvantages between batch,
Rate of Reaction Fundamentals mixed-flow, plug flow, packed-
bed and semi-batch reactors;
Topic 1
Ch.E. 422 2. Apply the Law of Mass Action or
Power Law in writing the rate of
a chemical reaction in terms of
the order of reactants and rate
constant;
©UST Ch.E. Department

At the end of this topic, you should

be able to:
Basic Types of Reactors
3. Express the rate of a chemical  Batch Reactor (BR)
reaction in terms of moles,  Continuous Reactors
concentration, partial and total • Mixed Flow Reactor (MFR) or
pressure; Constant Stirred Tank Reactor (CSTR)
4. Apply several theories in • Plug Flow Reactor (PFR) or Tubular
relating the effect of Reactor (TR)
temperature on the reaction • Packed Bed Reactor (PBR)
rate constant; • Fluidized Bed Reactor (FBR)
 Semi-Batch Reactor (SBR)
©UST Ch.E. Department ©UST Ch.E. Department

1
 17/01/2017

Batch Reactor Batch Reactor

For every batch:
1. Reactants are introduced
2. Reaction allowed to take place.
3. Products are withdrawn.
4. Reactor is cleaned and set up
for the next batch.

tB = t + tD
tB = total time/batch
t = reaction time/batch
tD = downtime/batch
(due to startup,
discharge, cleaning)

©UST Ch.E. Department ©UST Ch.E. Department

Batch Reactors
Advantages Disadvantages
Mixed Flow Reactor
 High conversion  High cost of
at extended labor per unit of Reactants are continuously
reaction time production fed to a well mixed tank
and the products are also
 Versatile  Difficult to withdrawn continuously. At
 Good for pilot maintain large steady state, the
testing scale production concentration of any
 Easy to clean  Long downtime material in the tank is also
the same as that in the
for cleaning
product stream.
reduces
productivity

©UST Ch.E. Department ©UST Ch.E. Department

2
 17/01/2017

Mixed Flow Reactor Mixed Flow Reactor

©UST Ch.E. Department ©UST Ch.E. Department

Mixed Flow Reactors

Advantages Disadvantages
Plug Flow Reactor
 Good  Lower
Reactants are continuously
temperature conversion per
fed to a tube so that what
control reactor volume goes in first also comes out
 Cheap to compared with first. Reaction proceeds
construct other continuous across the reactor length and
 Large heat reactors concentrations vary from
entrance to exit as there is no
capacity  Requires start-up lateral mixing. Radial
 Easy interior period prior to concentrations are however
access steady state assumed constant.

©UST Ch.E. Department ©UST Ch.E. Department

3
 17/01/2017

Plug Flow Reactor Plug Flow Reactor

©UST Ch.E. Department ©UST Ch.E. Department

Plug Flow Reactors

Advantages Disadvantages
Packed Bed Reactor
 Easy maintenance  Reactor
(no moving parts or temperature Reactants are continuously
mechanically simple) difficult to control fed to a packed bed which
 Higher conversion  Hot spots for could be a catalyst or
per reactor volume exothermic another reactant. Reaction
 Unvarying product reactions takes place across the bed
quality  Composition and products exit at the
 Good for rapid variations difficult other end. The bed may be
reactions to control stationary (fixed) or moving
(fluidized).
 Efficient use of
reactor volume
 Good for large
capacities ©UST Ch.E. Department ©UST Ch.E. Department

4
 17/01/2017

Packed Bed Reactors

Fluidized Bed Reactor Advantages Disadvantages
 Higher conversion  Difficult
per catalyst weight temperature control
 Easy to build  Temperature
 Better contact with gradients occur
reactant & catalyst  Catalyst difficult to
 Larger production replace
 Low cost of  Channeling of gas
construction, streams may occur
operation, and  Side reactions
maintenance possible
 Effective at high  Heat transfer
temperatures & difficult
©UST Ch.E. Department pressures ©UST Ch.E. Department

Semi-Batch Reactor Semi-Batch Reactor

Reactants are fed to a well

mixed tank at different
rates. Reaction takes place
and the products are
withdrawn after a set time.
Products are discharged
and reactor is cleaned and
set up for the next batch.

©UST Ch.E. Department ©UST Ch.E. Department

5
 17/01/2017

Limitations of the Course The Rate of Chemical Reaction

 Homogenous, Non-Catalyzed  Symbol is ri expressed as mols of
Chemical Reactions specie I reacting or formed per
 Simple and Complex Reactions time per unit volume reactor or
 Ideal, Isothermal Operation of mass of catalyst
BR, MFR or CSTR and PFR or TR  Preceded by a minus sign (-ri) if
and their combination species is a reactant
 Simple Heteregeneous Reactions  Ex: a A + b B  c C + d D
in PBR or FBR -rA -rB rC rD
 Sample units: mol/s-L; kmol/hr-
©UST Ch.E. Department
m3; mol/s-kg catalyst ©UST Ch.E. Department

Mole/Rate Relations Between

Law of Mass Action or Power Law
Participants
 The rate of a chemical reaction is
 Ex: a A + b B  c C + d D directly proportional to the active
-rA -rB rC rD masses involved, each raised to a
certain power.
NAo -NA NBo -NB NC -NCo N -N  Active mass refers to the
= = = D Do
a b c d concentration of reactant
-rA -r r r  Concentration is usually
= B = C = D expressed as mol/volume;
a b c d Ex: mol/L ; kmol/m3
©UST Ch.E. Department ©UST Ch.E. Department

6
 17/01/2017

Law of Mass Action Basic Terms

 Ex: a A + b B  c C + d D  ki = reaction rate constant for
-rA -rB rC rD species i
 
 α = order of reaction wrt A
N   NB   β = order of reaction wrt B
-rA   A  V
V     n = over-all order of the reaction
  =α+β
N   NB 
-rA = k A  A  V  Elementary Reaction:
V    characterized by a = α and b = β

©UST Ch.E. Department ©UST Ch.E. Department

Law of Mass Action Exercise 1

 Ex: a A + b B  c C + d D  Given the elementary, gas phase,
-rA -rB rC rD reaction: A + 2 B  AB2
   Derive rate equations for A, B
N   NB 
-rA = k A  A  V and AB2
V   
   Give the relations between kA,
N   NB  kB, and kAB2
-rB = k B  A  V
V   
 
N   NB 
rC = k C  A  V
V  
©UST Ch.E. Department ©UST Ch.E. Department

7
 17/01/2017

Other Variables in the Rate Equation Effect of Temperature

 Concentration, Ci = Ni/V  ki = f(T, Other parameters)
 Fractional Conversion of Reactant I  ki = kT f(other parameters)
Xi = (Nio- Ni)/Nio  Where kT = f(T) only
 For Ideal Gas Phase Reactions:  General Equation
• Partial Pressure Pi = Ci R T
E

• Total Pressure P or π = NT RT/V
k T = k 0 Tp e RT
 Exercise 2: Derive rate equation
for A in Exercise 1 in terms of CA, k0 = frequency factor, E = Energy of Activation
XA, PA, and P if feed has 30% A, p = power as espoused by several theories
60%B, 10% Inert by mole ©UST Ch.E. Department ©UST Ch.E. Department

Theories in Place Logarithm Forms

E

 Arrhenius: p = 0(most common) k T = k 0 Tp e RT

E

RT k   E 
kT = k 0 e ln  Tp  = ln(k 0 ) + ln e RT 
 T   
 Collision: p = ½
1

E k  E  1
ln  Tp  = ln(k 0 ) -
R  T 
Straight Line Form
kT = k 0 T 2 e RT
 T 
 Activated Complex: p = 1 a = Y-intercept

E Y= a + bX B = Slope
RT
kT = k 0 T e
©UST Ch.E. Department ©UST Ch.E. Department

8
 17/01/2017

Two Point Form

Log Forms based on Theories
E

E 1 k T = k 0 Tp e RT

ln k T  = ln(k 0 ) -
E
for p = 0 (Arrhenius) 
R  T  For T1 k T1 = k 0 T e p RT1  k T2 
p
 T   RT  RT
E E
1 E   =  2 e 2 1

RT2  k T1   T1 
For T2 k T2 = k 0 T2p e
k  E 1 1
ln  T1  = ln(k 0 ) -   for p = (Collision)
 2 RT 2  k T  T p  
E

E E(T2 T1 )

T   2  1   = e RT2 RT2  e R T1 T2
 k T1  T2  
k  E 1
ln  T  = ln(k 0 ) -   for p = 1 (Activated Complex)
 
T R T R T1T2  k T  T p 
E ln  2  1  
T2  T1  k T1  T2  
 
©UST Ch.E. Department ©UST Ch.E. Department

Arrhenius Related Problems From Levenspiel/Fogler

©UST Ch.E. Department ©UST Ch.E. Department