Chemical Reaction Engineering Mole Balances: Content
Chemical Reaction Engineering Mole Balances: Content
Chemical Reaction Engineering Mole Balances: Content
Mole Balances
1
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Content
Introduction
Reaction Rate
General Mole Balance
Balance on Batch Reactor
Balance on CSTR
Balance on PFR
Packed Bed Reactor
2
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Introduction
What is Chemical Reaction Engineering (CRE) ?
Understanding how chemical reactors work lies at the heart of almost every
chemical processing operation.
CRE is the synthesis of all these factors with the aim of properly designing
and understanding the chemical reactor.
3
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Introduction
4
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Modeling of Digestive System of a Hippopotamus
5
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Stoichiometry
Kinetics
Basic molar balances Reactor volume
Fluid dynamics
Reaction
Stoichiometry
Kinetics: elementary vs non-elementary
Single vs multiple reactions
Reactor
Isothermal vs non-isothermal
Ideal vs nonideal
Steady-state vs nonsteady-state
7
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
in
Continuously Stirred
Tank Reactor (CSTR)
out
Kinetics
Reactor type Conversion
& &
size Material & selectivity
energy
balances
9
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Chemical Identity
• A chemical species is said to have reacted when it has lost its chemical identity.
• The identity of a chemical species is determined by the kind, number, and
configuration of that species’ atoms.
• A chemical species is said to have reacted when it has lost its chemical identity.
2. Combination N2 + O2 2 NO
10
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Reaction Rate
The reaction rate is the rate at which a species looses its chemical identity per unit
volume.
The rate of a reaction (mol/dm3/s) can be expressed as either
the rate of Disappearance: -rA
or as
the rate of Formation (Generation): rA
Consider the isomerization AB
Reaction Rate
The rate of reaction tells us how fast a number of moles of one chemical species are
being consumed to form another chemical species.
It is assumed that the total mass is neither created nor destroyed when a chemical
reaction occurs.
EXAMPLE: AB
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
12
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Reaction Rate
• EXAMPLE: AB
rB = 0.2 mole/dm3/s
13
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Reaction Rate
EXAMPLE:
14
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Reaction Rate
• For a catalytic reaction, we refer to -rA',
which is the rate of disappearance of species A on a per mass of catalyst basis
(mol/gcat/s)
NOTE: dCA/dt is not the rate of reaction
It is simply a mole balance that is only valid for a constant volume batch
system
Consider species j:
rj is the rate of formation of species j per unit volume [e.g. mol/dm3/s]
rj is a function of concentration, temperature, pressure, and the type of catalyst (if
any)
rj is independent of the type of reaction system (batch, plug flow, etc.)
rj is an algebraic equation, not a differential equation
15
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
nth order in A r A kC A n
k1C A
Michaelis-Menton: common in enzymatic reactions rA
1 k 2C A
rj depends on concentration and temperature:
Ea
-rA A e RT C A Arrhenius dependence on temperature
A: pre-exponential factor E A : activation energy
R : ideal gas constant T:temperature
16
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
General Mole Balance
System
Volume, V
Fj0 Gj Fj
1 111
then G j rj x, y, z dx dy dz
000
System volume
21
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
23
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
dN A
Integrating dt
rAV
when t 0 N A N A0
t t NA NA
NA
dN A
t rAV
N A0
25
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Chapter 1
Mole Balance for Batch Reactor
NA
dN A
t rAV
N A0
NA
26
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Continuous Stirred Tank Reactor (CSTR)
27
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
(CSTR) Properties
Laboratory-Scale Bioreactor
29
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
C
j
0 j
V
rj
31
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
32
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
PFR Properties
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. 34
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Mole Balance – PFR
In a plug flow reactor the composition of the fluid varies from point to point along a
flow path. Consequently, the material balance for a reaction component must be
made for a differential element of volume ΔV ΔV
FA0 FA
dNj
Fj0 - Fj + rjV =
dt
dN j Divide by V
Fj Fj rj V Fj Fj rjV 0
V V V dt V V V
V
0
Fj Fj lim dFj
V V V
Fj V V Fj V V→0 rj
rj 0 rj dV
V V
If we assume the PFR is ideal, the degree of completion is not Ideal SS PFR
affected by PFR shape, only by PFR volume Design Eq.
35
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
36
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Packed Bed Reactors (PBR)
37
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
PBR
FAo FA
mol
Units for the rate of a catalytic rxn (rj’) :
s kg catalyst
39
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
FA FA
W W W
dN A
FA W FA W W rA W
dt
Steady State dN A
0
dt
F A W W F A
lim W
rA
W 0 W 40
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Packed Bed Reactor - Mole Balances
Rearrange:
dFA
rA
dW
The integral form to find the catalyst weight is:
FA FA 0
dFA dFA
W rA
FA
rA
FA 0
41
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
42
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Fluidized CSTR
Use basic molar balance to derive a reactor design equation for a fluidized CSTR
containing catalyst particles. The equation should be in terms of catalyst weight (W)
and the reaction rate for an equation that uses solid catalyst. Assume perfect mixing and
steady-state operation of the CSTR.
Fluidized CSTR
44
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
r’j vs rj
Consider a reaction that occurs on a catalyst surface (a heterogeneous
rxn).
How is the reaction rate r’j that is in terms of the weight of catalyst
related to the rate in terms of volume (rj)?
45
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
r’j vs rj
46
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Test
Use your result from the previous question to derive a reactor design equation for
a fluidized CSTR containing catalyst particles. The equation should be in terms of
catalyst weight (W) and the reaction rate for an equation that uses solid catalyst.
Assume perfect mixing and steady-state operation of the CSTR.
Fj0 Fj Need an equation that has W
CSTR design equation: V
rj instead of V and –rj’ instead
of -rj
Step 1: Come up with an equation that relates V to W (V=?W) & substitute this
equivalency into the CSTR design equation.
Fj0 Fj W Fj0 Fj
W V W Substitute W/ρb for V
V
b b rj
V b in design eq: rj
47
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Test Cont.
Step 2: Substitute an expression that relates –rj to –rj’ into the design eq:
mc
la
o
m
l m
o
s
k
g
t
a
l
y
s
t
s
48
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Reactor Mole Balances Summary
The GMBE applied to the four major reactor types
(and the general reaction AB)
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
dFA dFA
PFR
dV
rA V
FA 0
drA
V
FA FA
PBR dFA dFA
dW
rA W
FA 0
rA
W 49
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
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
50
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 1
The reaction A→B is to be carried out isothermally in a continuous-flow reactor.
Calculate the CSTR volume to consume 99% of A (CA=0.01CA0) when the
entering molar flow rate is 5 mol A/h, the volumetric flow rate is constant at 10
dm3/h and the rate is –rA=(3dm3/mol•h)CA2.
Fj C j 0 = 10 dm3/h =
reactor
FA0=5 mol A/h FA=CA where CA = 0.01CA0
d d
N t
j
F
F
r
V
j
j
j
CSTR design eq: In - Out + Gen = Accumulation 0
0
F FA C C A
V A0 V A0
rA rA
Substitute in:
–rA=(3dm3/mol•h)CA2 & CA=0.01CA0
51
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 1 Cont.
V
0.99 10 dm3 h
V 66,000 dm3
3 dm 3
molh 0.01
2
0.5 mol dm 3
52
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 2
The reaction A→B is to be carried out isothermally in a continuous-flow reactor.
Calculate the PFR volume to consume 99% of A (CA=0.01CA0) when the entering
molar flow rate is 5 mol A/h, the volumetric flow rate is constant at 10 dm3/h and
the rate is –rA=(3dm3/mol•h)CA2.
5mol h mol
C A0 = =0.5
3
0 = 10 dm3/h = 10 dm h dm3
Fj C j
reactor
FA0=5 mol A/h FA=CA where CA = 0.01CA0
0.01C A0
dC A dm3 2 dC A V
3 CA dV
dV molh
3 dm3 molh C A0 CA 2 0
53
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 2 Cont.
b a
1 n
b
n
1
n
1
n
1
b
b
x
n
1
n
d
x
x
d
x
b dx 1
REVIEW:
2
n
1
n
1
x
for n≠1:
a
ax x a
1 1 10 dm3 h 1 1 dm3
0.01C C V V
3
3 dm molh
A0 A0
3
3 dm molh
0. 01 0. 5 0.5 m ol
54
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 3
The gas phase reaction A→B+C will be carried out isothermally in a 20 dm3
constant volume, well-mixed batch reactor. 20 moles of pure A is initially placed in
the reactor. If the rate is –rA=kCA and k=0.865 min-1, calculate the time needed to
reduce the number of moles of A in the reactor to 0.2 mol.
d d
N t
j
F
F
r
V
dNA Batch reactor
j
j
In - Out + Gen = Accum 0 rA V
0 dt design eq
55
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Example 3 Cont.
dC A dCA Plug in rate dCA Rearrange
rA V V rA law k C A
dt dt dt & integrate
1 n
b
b a
d
x
l
n
x
l
n
b
l
n
a
REVIEW: ln ba
x
a
for n=1:
min 0.2
Substitute in values for k, NA0, & NA t ln t 5.3 min
0.865 20
56
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888
Industrial Reactors
Liquid-Phase Reactions
Gas-Phase Reactions
57
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Tel. +962 6 535 5000 | 22888