Basic Balances on Reactive

Processes
Academic Resource Center
Motivation
This topic was chosen because it is believed to
be one of the core principles of chemical
processes
Students would first need to learn this
foundation of process balances before building
more specific skills
Introduction
The knowledge of writing balances on reactive
processes can be applied in many places:
power plants, pharmaceutical plants, etc
Usually, one would first need to draw a
flowchart depicting the various processes
Then, for most of the course, students will
need to calculate the flow rates and
compositions of all the flows in the flowchart
The General Balance Equation
Accumulation = In Out + Generation - Consumption
Accumulation: buildup within system
In: enters through system boundaries
Out: leaves through system boundaries
Generation: produced within system
Consumption: consumed within system
The Idea of Control Volume
The irregular shape may represent any process unit
(evaporator, reactor, condenser, etc.)
We draw a rectangle around the unit to represent the
desired control volume
Then, the general balance equation is applied to this
control volume
Whatever that is entering the rectangle is the In
Whatever that is exiting the rectangle is the Out
Whatever that is being produced/consumed in the rectangle is
the Generation/Consumption
Whatever that remains in the rectangle is the Accumulation
Process
Unit
m
in
(kg CH
4
)
m
out
(kg CH
4
)
Three Different Balances
Three different balances may be written to
determine an unknown flow rate for a reactive
process:
a) Molecular Species Balances
b) Atomic Species Balances
c) Extent of Reaction
Example 1
Let us consider the dehydrogenation of
ethane:
Assuming 100 kmol/min of ethane is fed to the
reactor and the molar flow rate of hydrogen in
the product stream is 40 kmol/min
2 4 2 6 2
H H C H C +
Solution to Example 1
Since most analyses would be done at steady-
state (accumulation = 0), the general balance
equation is reduced to the following:
In + Generation = Out + Consumption
This example will now be solved using the
three different balances introduced earlier:
a) Molecular Species Balances
b) Atomic Species Balances
c) Extent of Reaction
1a) Molecular Species Balances
Usually used when a reaction is involved
Thus, there should be some species that are
being generated and some other species that
are being consumed
Once a generation/consumption term has
been calculated, the other terms can be
calculated directly from stoichiometric
equation
1a) Molecular Species Balances
H
2
: generation = output
C
2
H
6
: input = output + consumption
C
2
H
4
: generation = output
min / 40 min) / (
2 2
2
H kmol generated H kmol Gen
H
=
|
|
.
|

\
|
+ =
generated H kmol
consumed H C kmol generated H kmol
n
2
6 2 2
1
1
1
min
40
100
min / 60
6 2 1
H C kmol n =
2
2
4 2 2
1
1
min
40
n
generated H kmol
generated H C kmol generated H kmol
=
|
|
.
|

\
|
min / 40
4 2 2
H C kmol n =
Process
Unit
100 kmol C
2
H
6
/min 40 kmol H
2
/min
(kmol C
2
H
6
/min)
(kmol C
2
H
4
/min)
1
n
2
n
2 4 2 6 2
H H C H C +
1b) Atomic Species Balances
Usually leads to most straightforward solution
procedure, especially when more than one
reaction is involved
Since atomic species can neither be generated
nor consumed, all atomic balances take the
form of input = output
1b) Atomic Species Balances
C:
H:
Solving simultaneously gives
Process
Unit
100 kmol C
2
H
6
/min 40 kmol H
2
/min
(kmol C
2
H
6
/min)
(kmol C
2
H
4
/min)
1
n
2
n
2 4 2 6 2
H H C H C +
2 1
4 2
4 2 2
6 2
6 2 1
6 2
6 2
100
1
2
min 1
2
min 1
2
min
100
n n
H C kmol
C kmol H C kmol n
H C kmol
C kmol H C kmol n
H C kmol
C kmol H C kmol


+ =
|
|
.
|

\
|
+
|
|
.
|

\
|
=
|
|
.
|

\
|
2 1
2 1
4 6 520
) 4 ( ) 6 ( ) 2 ( 40 ) 6 ( 100
n n
n n


+ =
+ + =
min / 60
6 2 1
H C kmol n =
min / 40
4 2 2
H C kmol n =
1c) Extent of Reaction
As for the molecular species balances, this
method is usually used when a reaction is
involved
However, this method tends to be more useful
when there are multiple reactions
Recall:
is the stoichiometric coefficient
Reactants: -ve Products: +ve
is the extent of reaction
v


i i i
n n + =
0
1c) Extent of Reaction
H
2
(=1):
C
2
H
6
(=-1):
C
2
H
4
(=1):
Process
Unit
100 kmol C
2
H
6
/min 40 kmol H
2
/min
(kmol C
2
H
6
/min)
(kmol C
2
H
4
/min)
1
n
2
n
2 4 2 6 2
H H C H C +
) ( 1 0 min / 40
2
+ = H kmol
min / 40kmol =
60 40 100 ) 1 ( 100
1
= = + = n
40 ) ( 1 0
2
= + = n
min / 60
6 2 1
H C kmol n =
min / 40
4 2 2
H C kmol n =
Example 2
Dehydrogenation of Propane
The process is to be designed for a 95% overall
conversion of propane. The reaction products are
separated into two streams:
the first, which contains H2, C3H6, and 0.555% of the
propane that leaves the reactor, is taken off as product;
the second stream, which contains the balance of the
unreacted propane and 5% of the propylene in the first
stream, is recycled to the reactor.
Calculate the composition of the product, the ratio
(moles recycled)/(mole fresh feed), and the single-pass
conversion
2 6 3 8 3
H H C H C +
Solution to Example 2
Basis: 100 mol fresh feed
Product composition: n
6
/(n
6
+n
7
+n
8
)
Recycle ratio: (n
9
+n
10
)/100
Single-pass conversion: 100%*(n
1
-n
3
)/n
1
Need: n
1
, n
3
, n
6
, n
7
, n
8
, n
9
, n
10
Separator Reactor
Fresh feed
100 mol C3H8
n
9
mol C
3
H
8
n
10
mol C
3
H
6
Recycle
Product
n
6
mol C
3
H
8
n
7
mol C
3
H
6
n
8
mol H
2
n
3
mol C
3
H
8
n
4
mol C
3
H
6
n
5
mol H
2
n
1
mol C
3
H
8
n
2
mol C
3
H
6
Example 2: Discussion
This time we have multiple units and a mixing
point, therefore, we can draw a control volume
around each unit, mixing point, and around
the overall process
95% overall conversion of propane.
0.555% of propane that leaves the reactor,
n
6
= 0.00555*n
3
->
5% of the propylene in the first stream,
n10 = 0.05*n7 -> to be solved later
n
6
= 0.05*100 = 5 mol C
3
H
8
n
3
= 5/0.00555 = 900 mol C
3
H
8
2 a) Molecular Species Balances
Overall system
C
3
H
6
: generation = out
H
2
: generation = out
7
8 3
6 3 8 3
1
1
min
95
n
consumed H C mol
generated H C mol consumed H C mol
=
|
|
.
|

\
|
n
7
= 95 mol C
3
H
6
8
8 3
2 8 3
1
1
min
95
n
consumed H C mol
generated H mol consumed H C mol
=
|
|
.
|

\
|
n
8
= 95 mol H
2
n
6
= 5 mol C
3
H
8
n
7
= 95 mol C
3
H
6
n
8
= 95 mol H
2
2.6 mol% C
3
H
8
48.7 mol% C
3
H
6
48.7 mol% H
2
2 a) Molecular Species Balances
Separator: In = Out (no reaction)
C
3
H
8
n
3
= n
6
+n
9
->
C
3
H
6
Recall: n
10
= 0.05*n
7
->
n
4
= n
7
+ n
10
->
Border is dashed because we did not need n
4
H
2
n
5
= n
8
n
9
= n
3
-n
6
= 900-5 = 895 mol C
3
H
8
n
10
= 0.05*95 = 4.75 mol C
3
H
6
n
4
= 95+4.75=99.75 mol C
3
H
6
n
5
= 95 mol H
2
2 a) Molecular Species Balances
Mixing Point: In = Out (no reaction)
C
3
H
8
100+n
9
= n
1
->
C
3
H
6
n
10
= n
2
->
Recycle ratio = (n
9
+n
10
)/100
Single-pass conversion = 100%*(n
1
-n
3
)/n
1
n
1
= 100+895 = 995 mol C
3
H
8
n
2
= 4.75 mol C
3
H
6
feed fresh mol
recycle mol
9.00
9.6%
2 b) Atomic Species Balances
Overall System: In = Out
C:
H:
Product composition:
) 3 ( ) 3 ( 5 ) 3 ( ) 3 ( ) 3 ( 100
7 7 6
n n n + = + =
n
7
= 95 mol C
3
H
6
) 2 ( ) 6 ( 95 ) 8 ( 5 ) 2 ( ) 6 ( ) 8 ( ) 8 ( 100
8 8 7 6
n n n n + + = + + =
n
8
= 95 mol H
2
n
6
= 5 mol C
3
H
8
n
7
= 95 mol C
3
H
6
n
8
= 95 mol H
2
2.6 mol% C
3
H
8
48.7 mol% C
3
H
6
48.7 mol% H
2
2 b) Atomic Species Balances
Separator: In = Out
Recall: n
10
= 0.05*n
7
->
C:
H:
We have 2 equations and 3 unknowns (n
4
, n
5
, n
10
)
Since we know that no H
2
is recycled, n
5
= n
8
,
thus, the unknowns can be found by solving the
equations simultaneously
] 1 [ ) 3 ( 75 . 4 ) 3 ( ) 3 ( 95 ) 3 ( 5 ) 3 ( ) 3 ( 900
) 3 ( ) 3 ( ) 3 ( ) 3 ( ) 3 ( ) 3 (
9 4
10 9 7 6 4 3
+ + + = +
+ + + = +
n n
n n n n n n
n
10
= 0.05*95 = 4.75 mol C
3
H
6
] 2 [ ) 6 ( 75 . 4 ) 8 ( ) 2 ( 95 ) 6 ( 95 ) 8 ( 5 ) 2 ( ) 6 ( ) 8 ( 900
) 6 ( ) 8 ( ) 2 ( ) 6 ( ) 8 ( ) 2 ( ) 6 ( ) 8 (
9 5 4
10 9 8 7 6 5 4 3
+ + + + = + +
+ + + + = + +
n n n
n n n n n n n n
n
4
= 99.75 mol C
3
H
6
n
5
= 95 mol H
2
n
9
= 895 mol C
3
H
8
2 b) Atomic Species Balances
Mixing Point: In = Out
C:
H:
Now, we have 2 equations and 2 unknowns (n
1
,
n
2
)
Recycle ratio = (n
9
+n
10
)/100
Single-pass conversion = 100%*(n
1
-n
3
)/n
1
] 3 [ ) 3 ( ) 3 ( ) 3 ( 75 . 4 ) 3 ( 895 300
) 3 ( ) 3 ( ) 3 ( ) 3 ( ) 3 ( 100
2 1
2 1 10 9
n n
n n n n
+ = + +
+ = + +
] 4 [ ) 6 ( ) 8 ( ) 6 ( 75 . 4 ) 8 ( 895 800
) 6 ( ) 8 ( ) 6 ( ) 8 ( ) 8 ( 100
2 1
2 1 10 9
n n
n n n n
+ = + +
+ = + +
n
1
= 100+895 = 995 mol C
3
H
8
n
2
= 4.75 mol C
3
H
6
feed fresh mol
recycle mol
9.00
9.6%
Example 2: Further Discussion
As can be seen above, the problem can be solved
simply by analyzing only the overall system, separator,
and mixing point
Furthermore, since these units do not involve reactions,
the extent of reaction method does not apply
Also, for the separating and mixing sections, the
molecular species balances method leads to simpler
calculations as compared to the atomic species
balances method
It is also worthy to note here that you can use different
methods at different points
E.g. It may be easier to solve the overall system balance
using atomic species balances, then use molecular species
balances to solve for the other points
Problem 1
Incomplete Combustion of Methane
Methane is burned with air in a continuous steady-
state combustion reactor to yield a mixture of carbon
monoxide, carbon dioxide, and water. The reactions
taking place are
The feed to the reactor contains 7.80 mole% CH
4
,
19.4% O
2
, and 72.8% N
2
. The percentage conversion of
methane is 90.0%, and the gas leaving the reactor
contains 8 mol CO
2
/mol CO. Calculate the molar
composition of the product stream.
) 2 ( 2 2
) 1 ( 2
2
3
2 2 2 4
2 2 4
O H CO O CH
O H CO O CH
+ +
+ +
Hints
Basis = 100 mol Feed
Process
Unit
0.078 mol CH
4
/mol
0.194 mol O
2
/mol
0.728 mol N
2
/mol
n
H
2
O
mol H
2
O
n
O
2
mol O
2
n
N
2
mol N
2
100 mol
n
CH
4
mol CH
4
n
CO
mol CO
n
CO
2
mol CO
2
Problem 2
The reaction between ethylene and hydrogen
bromide to form ethyl bromide is carried out in
a continuous reactor. The product stream is
analyzed and found to contain 51.7 mole%
C
2
H
5
Br and 17.3% HBr. The feed to the reactor
contains only ethylene and hydrogen bromide.
If the molar flow rate of the feed stream is 165
mol/s, what is the extend of reaction?
Problem 3
Methane and oxygen react in the presence of a
catalyst to form formaldehyde. In a parallel
reaction, methane is oxidized to carbon dioxide
and water:
The feed to the reactor contains equimolar
amounts of methane and oxygen. Assume a basis
of 100 mol feed/s. The fractional conversion of
methane is 0.9. and the fractional yield of
formaldehyde is 0.855.
Calculate the two extents of reaction and the
molar composition of the reactor output stream.
O H CO O CH
O H HCHO O CH
2 2 2 4
2 2 4
2 2 + +
+ +
References
Felder, Richard M. Elementary principles of
chemical processes. New York: John Wiley,
1999. Print.