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• rA: the rate of formation of species A per unit volume [e.g.

, mol/m3•s]
• -rA: the rate of a consumption of species A per unit volume
A  B  products r A  kC A CB
1st order in A, 1st order in B, 2nd order overall
r A  kCAn nth order in A
k1C A
 rA  Michaelis-Menton: common in enzymatic reactions
1  k 2C A

rj depends on concentration and temperature:


 Ea 
 RT 
-rA  A e C
A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature
Reaction Rate
EXAMPLE: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e.,
rB = 0.2 mole/dm3/s

Then A is disappearing at the same rate:


-rA= 0.2 mole/dm3/s
The rate of formation (generation of A) is:
rA= -0.2 mole/dm3/s
Reaction Rate
Consider species j:
1. rj is the rate of formation of species j per unit volume
[e.g. mol/dm3s]
2. rj is a function of concentration, temperature,
pressure, and the type of catalyst (if any)
3. rj is independent of the flow type of reaction system
(batch, plug flow, etc.)
4. rj is an algebraic equation, not a differential equation
(e.g. -rA = kCA or -rA = kCA2)
General Mole Balances
System
Volume, V

Fj0 Gj Fj

 Molar Flow  Molar Flow   Molar Rate   Molar Rate 


 Rate of    Rate of   Generation    Accumulation
       
 Species j in   Species j out  of Species j  of Species j 
dN j
Fj 0  Fj  Gj 
dt
 mole   mole   mole   mole 
          
 time   time   time   time 
General Mole Balances

If spatially uniform:
G j  r jV

If NOT spatially uniform:

 V1
V2
rj1
rj 2
G j1  rj1V1
G j 2  rj 2 V2

General Mole Balances

n
G j   rji Vi
i 1

Take limit
n
Gj   rjiVi   r dV
j
i1 lim V  0 n  
General Mole Balances

System
Volume, V

FA0 GA FA

General Mole Balance on System Volume V

In  Out  Generation  Accumulation


dN A
FA 0  FA   rA dV 
dt
Chapter 1
Batch Reactor - Mole Balances

Batch

dN A
FA0  FA   rAdV 
dt
FA0  FA  0
Well-Mixed  rA dV  rAV

dN A
 rAV
dt
9
Chapter 1
Batch Reactor - Mole Balances

dN A
Integrating dt 
rAV

t  0 N A  N A0
when
t  t NA  NA

NA
dN A
t 
N A0
 rAV

Time necessary to reduce the number of moles of A from NA0 to NA.


Batch Reactors Properties
• Reactants are placed in the reactor, and
the reaction is allowed to proceed for
some amount of time
• Closed system- no addition of reactants
or removal of products during the
reaction
• Unsteady-state conditions- the
composition changes with time
• Ideal batch reactor- vessel is perfectly
mixed
• Concentration and temperature are
spatially constant, but NOT constant in
TIME
Examples of Batch Reactor
Lab-Scale Batch
Typical Commercial Batch
Reactor
Reactor

Motor for agitation


Chapter 1
Batch Reactor - Mole Balances
dN A
FA0  FA   rAdV 
dt
FA0  FA  0

NA
dN A
t 
NA
N A0
 rAV

t
Continuous Stirred Tank Reactor
(CSTR) Properties
• Continuously add reactants and remove
products (open system)
• Inlet stream instantaneously mixes with
bulk of reactor volume
• Ideal batch reactor- assume perfect
mixing occurs in vessel
• Temperature and concentration are
uniform throughout space
• Composition of the exit stream is the
same as that inside reactor (CA,outlet =
CA, tank)
• Steady-state conditions- the reaction rate
is the same at every point and does not
change with time
Examples of CSTRs

Laboratory-Scale Bioreactor

Pfaudler Inc.
Chapter 1
CSTR - Mole Balances

CSTR

dN A
FA 0  FA   rA dV 
dt

dN A
Steady State 0
 dt
Chapter 1
CSTR - Mole Balances

Well Mixed  r dV  r V
A A

FA0  FA  rAV  0

FA 0  FA
V
 rA
CSTR volume necessary to reduce the molar flow
rate from FA0 to FA.

Chapter 1
Plug Flow Reactor - Mole Balances
Plugged Flow Reactor (PFR) Properties
• Also called a tubular reactor
• Cylindrical pipe with openings at
both ends
• Steady movement of material down
length of reactor
• Reactants are consumed as they flow
down the length of the reactor
• Operated at steady state:
• No radial variation in
temperature, concentration, or
reaction rate
• All fluid/gas elements have the
same residence time
Industrial PFRs

Polyethylene reactor:
• 16 inch inner diameter
• Operates at 35,000 psi & 600 °F
• Has a vertical orientation when in use
Courtesy of Autoclave Engineers of Snap-tite, Inc.
Mole Balance – PFR
In a plug flow reactor the composition of the fluid varies from point to point along
a flow path. The material balance must be made for a differential element of
volume ΔV
ΔV

FA0 FA

If we assume the PFR is ideal, the degree of completion is not affected by PFR
shape, only by PFR volume
Chapter 1
Plug Flow Reactor - Mole Balances

V

FA FA

V V  V
 

 In  Out  Generation
at V       0
  at V  V  in V 
FA V  FA V  V  rA V 0
Chapter 1
Plug Flow Reactor - Mole Balances

Rearrange and take limit as ΔV0

FA V  V  FA V
lim  rA
V 0 V

dFA
 rA
dV

This is the volume necessary to reduce the entering molar


flow rate (mol/s) from FA0 to the exit molar flow rate of FA.

Chapter 1
Plug Flow Reactor - Mole Balances

PFR

dN A
FA0  FA   rA dV 
dt
dN A
Steady State 0
dt

FA0  FA   rA dV  0
Plug Flow Reactor - Mole Balances

Differientiate with respect to V

0
dFA
 rA
dFA
 rA
dV dV
FA
dFA
The integral form is: V 
 FA 0
rA

This is the volume necessary to reduce the


entering molar flow rate (mol/s) from FA0 to the
exit molar flow rate of FA.
Packed Bed Reactors (PBR)
• Cylindrical shell, vertically oriented
• Often gravity-driven flow
• Heterogeneous reaction: fixed bed of catalyst
inside
• Reactants enter top and flow through the
packed bed of catalyst
• Concentration gradient of reactant and
product down the length of the reactor
• Reaction occurs on the surface of the catalyst
pellets
• Reaction rate is based on the mass of the
solid catalyst, W, not reactor volume V
Packed Bed Reactor - Mole Balances
W
PBR
FA FA

W W  W
 
FA W   FA W  W   rA W 
dN A
dt
Steady State dN A FA W  W  FA W
0
dt lim  rA
W 0 W
Chapter 1
Packed Bed Reactor - Mole Balances

Rearrange:
dFA
 rA
dW
The integral form to find the catalyst weight is:
FA
 dFA
W 
FA 0
rA

PBR catalyst weight necessary to reduce the


entering molar flow rate FA0 to molar flow rate FA.
Reactor Mole Balances Summary

The GMBE applied to the four major reactor types


(and the general reaction AB)
Reactor Differential Algebraic Integral
NA NA
dN A
Batch dN A
 rAV t 
dt rV
N A0 A
t
CSTR FA 0  FA
V
rA FA
FA
PFR dFA V 
dFA
 rA
dV FA 0
drA
V

FA FA
dFA dFA
PBR
 dW
 rA W 
FA 0
rA
W
Selection of Reactors
Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production
CSTR: most homogeneous liquid-phase flow reactors
• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of the
flow reactors - very large reactors are necessary to obtain high
conversions
PFR: most homogeneous gas-phase flow reactors
• relatively easy to maintain
• usually produces the highest conversion per reactor volume (weight of
catalyst if it is a packed-bed catalyze gas reaction) of any of the flow
reactors
• difficult to control temperature within the reactor
• hot spots can occur
Uses for Various Reactors
• Noncatalytic homogeneous gas • Ethylene polymerization
reactor (high pressure)
• Homogeneous liquid reactor
• Mass polymerization of styrene
• Liquid-liquid reactor • Saponification of fats
• Gas-liquid reactor • Nitric acid production
• Non-catalytic gas-solid reactor
• Iron production
• Fixed bed
• Chlorination of metals
• Fluidized bed
• Ammonia synthesis
• Fixed bed catalytic reactor
• Catalytic cracking (petroleum)
• Fluid bed catalytic reactor
• Hydrodesulphurization of oils
• Gas-liquid-solid reactor
CSTR – Example Problem

Given the following information, Find V


3
0  10 dm 3
min   0  10 dm
min
C A0
V ? C A  0.1C A0
FA0  0C A0
FA  C A

Liquid phase
  0
FA   0CA
CSTR – Example Problem

(1) Mole Balance:


FA0  FA 0C A0  0C A 0 C A0  C A 
V  
 rA  rA  rA

(2) Rate Law:


 rA  kCA

(3) Stoichiometry:
FA FA
CA  
 0
CSTR – Example Problem

(4) Combine:
0 CA 0  CA 
V
kCA
(5) Evaluate:
C A  0.1C A0
 10dm3
C A0  0.1C A0  101  0.1
V  min  3

 
0.23 min 1 0.1C A0  0.230.1
dm

900
V  391 dm 3
2.3
Chapter 2
Define conversion, X

Consider the generic reaction:


a AbB  c C  d D

Chose limiting reactant A as basis of calculation:


b c d
A B  C  D
a a a

Define conversion, X
moles A reacted
X
moles A fed
Chapter 2

 Moles A   Moles A  Moles A


remaining   initially   reacted 
     
NA  N A0  N A0 X
dN A  0  N A0 dX
dN A dX
  N A0  rAV
dt dt
Chapter 2

dN A rAV t 0 X 0

dt N A0 t t X  X

Integrating,
X
dX
t  N A0 
0
 rAV

The necessary t to achieve conversion X.


Chapter 2
CSTR

Consider the generic reaction:


a AbB  c C  d D

Chose limiting reactant A as basis of calculation:


b c d
A B  C  D
a a a

Define conversion, X
moles A reacted
X
moles A fed
Chapter 2
CSTR

dN A
Steady State 0
dt

FA 0  FA

Well Mixed V
rA

 r dV  r V
A A


Chapter 2
CSTR

Moles A Moles A  Moles A


leaving   entering   reacted 
     
FA  FA0  FA0 X

FA0  FA   rA dV  0
FA 0  FA 0  FA 0 X 
V
rA
FA0 X
V
 rA
CSTR volume necessary to achieve conversion X.

Chapter 2
PFR

dFA
 rA
dV
FA  FA0  FA0 X

Steady State dFA  0  FA0 X


dX  rA

dV FA0
Chapter 2
PFR

V 0 X 0
V V X  X

Integrating,
X
FA0
V  dX
0
 rA

PFR volume necessary to achieve conversion X.


Chapter 2

Reactor Mole Balances Summary


in terms of conversion, X
Reactor Differential Algebraic Integral
X
X
dX
Batch N A0
dX
  r AV t  N A0 
dt 0
 rAV
t
FA 0 X
CSTR V
rA
X
dX FA0 dX
PFR FA 0  rA V 
dV  0
 rA
X
X
dX FA0 dX
PBR
 FA 0   rA W 
dW 0
 rA
W
Chapter 2
Levenspiel Plots

Reactor Sizing
Given –rA as a function of conversion, -rA= f(X),
one can size any type of reactor. We do this by
constructing a Levenspiel plot. Here we plot
either (FA0/-rA) or (1/-rA) as a function of X. For
(FA0/-rA) vs. X, the volume of a CSTR and the
volume of a PFR can be represented as the
shaded areas in the Levenspiel Plots shown as:

FA0
 g(X )
 rA
Chapter 2
Levenspiel Plots

FA 0
rA

 X


Chapter 2

CSTR

FA 0 Area = Volume of CSTR

rA  FA0 
V    X 1
  rA  X 1
X1

46
Chapter 2

PFR

47
Chapter 2

Levenspiel Plots
Chapter 2

• The integral to calculate the PFR volume can be


evaluated using method as Simpson’s One-
Third Rule: (See Appendix A.4)
X
FA0 x  1 4 1 
V  dX  FA0    
1
0
 rA 3 
 A r (0)  rA ( X / 2)  rA ( X ) 
 rA ( X 2 )
1
 rA
Other numerical methods are:
1
 Trapezoidal Rule (uses two
 rA ( X 1 )
data points)
1  Simpson’s Three-Eight’s
 rA (0) Rule (uses four data points)
0 X1 X2
 Five-Point Quadrature
Formula
Chapter 2

Reactors in Series

Given: rA as a function of conversion, one can also


design any sequence of reactors in series by
defining X:
total moles of A reacted up to point i
Xi 
moles of A fed to first reactor

Only valid if there are no side streams.

Molar Flow rate of species A at point i:

FAi  FA0  FA0 X i


Chapter 2

Reactors in Series
Chapter 2

Reactors in Series
Reactor 1:

FA1  FA0  FA0 X 1

FA0  FA1 FA0  FA0  FA0 X 1  FA0 X 1


V1   
 rA1  rA1  rA1

FA 0 V1
 rA

X1 X
Chapter 2

Reactors in Series
Reactor 2:
X2
FA0
V2   dX
X1
 rA

FA0 V2
 rA

X1 X2
X
Reactors in Series

Reactor 3:
FA2  FA3  rA3V3  0
FA0  FA0 X 2   FA0  FA0 X 3   rA3V3  0
FA 0 X 3  X 2 
V3 
rA 3

V3
FA 0
 rA

X1 X X2 X3
Reactors in Series

55
Chapter 2

Reactors in Series
Space time τ is the time necessary to process 1
reactor volume of fluid at entrance conditions.

V

0

56

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