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= =
This equation defines the purge gas requirements for the vacuum purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 13 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
, , flow i flow i
t
x x =
The moles of the species to be diluted that are added to the vessel in the purge gas is:
3 3
2 2
, ,
t t
flow i flow i flow
t t
n x n =
So the mole fraction of the species to be diluted in the final state is:
3
2
3 2
3 1
3 3
,
,
1
t
i flow i
i t
t t
L L
i i flow i
t t
H H
t t
n n
n
P P
x x x
n n P P
+
| | | |
= = = +
| |
\ . \ .
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel.
Example 2: Dilution of Atmospheric Air in a Vacuum Purge
Determine: a) the oxygen concentration and b) the volume of purge gas at STP when a vessel with a
volume of 4 m
3
containing air at 25
o
C and atmospheric pressure is vacuum purged to 600 mmHg with a purge
gas that is 98 mole% nitrogen and 2 mole% oxygen. The purge gas returns the pressure in the vessel to one
atmosphere.
Solution
a)
3 1
,
600 600
1 0.21 0.02 1 0.170
760 760
L L
i i flow i
t t
H H
P P mmHg mmHg
x x x
P P mmHg mmHg
| | | | | | | |
= + = + =
| | | |
\ . \ . \ . \ .
b)
( ) 3
3 2
2
t
H L
flow
t t
t
P P V
n n n
RT
= =
( )
( )( )( )
( )( )
3
2
3
3
760 600 4 298
0.771
760 273
t
flow
STP
H L t
STP
flow
STP STP
flow
n RT
P P V T
V
P P T
mmHg mmHg m K
V m STP
mmHg K
= =
= =
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
2
3 1
3
t
i i
t t
t
P
x x
P
| |
| =
|
\ .
Multiple vacuum purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let
3
t designate the end of the first vacuum purge cycle and the beginning of the second vacuum
purge cycle. Then,
4
t will correspond to a vacuum state and
5
t will correspond to an inert-filled state that is the
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 14 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
end of the second vacuum purge cycle. The mole fraction of the species to be diluted at the conclusion of the
second vacuum purge cycle will be:
4 2 4
5 3 1
5 3 5
t t t
i i i
t t t
t t t
P P P
x x x
P P P
| | | || |
| | | = =
| | |
\ . \ .\ .
If the vacuum and inert-filled pressures are the same for each cycle , 1 j j J = :
2
2 1
1
1
j
j
L
t
H
t
P P j J
P P j J
+
= =
= =
Subscript L designates the low pressure in the cycle (the vacuum state pressure) and subscript H designates
the high pressure in the cycle (the inert-filled state pressure). Measuring time in cycles (the initial time becomes
cycle 0):
0
0
j
L
i i
j
H
P
x x j J
P
| |
= =
|
\ .
The number of such cycles necessary to achieve a target concentration for the species to be diluted is:
0
ln
ln
i
J
i
L
H
x
x
J
P
P
| |
|
|
\ .
=
| |
|
\ .
The total moles of purge gas required are:
( ) 3
2
t
H L
flow
t
J P P V
J n
RT
=
Example 3: Number of Vacuum Purge Cycles
Determine the number of purge cycles to a vacuum pressure of 600 mmHg needed to reduce the
oxygen concentration of atmospheric air to 6 mole% with pure nitrogen.
Solution
The assumption of ideal gas behavior should be valid for these conditions. Sufficient time will have to
be allotted between cycles to ensure that the purge gas mixes thoroughly so the concentration in the vessel is
uniform throughout. Then:
0.06
ln
0.21
5.3
600
ln
760
J
mmHg
mmHg
| |
|
\ .
= =
| |
|
\ .
Six cycles will be required to reduce the oxygen concentration below 6 mole%.
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 15 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
Pressure Purging
If the vessel to be inerted is designed to withstand elevated pressure, an inert atmosphere can be
created by repeatedly pressurizing the vessel by filling with inert gas, allowing the purge and residual gases to
mix, and then relieving the pressure. The three states of interest for the pressure purging process are:
Figure 3a. Initial State for the Vacuum Purging Process
Figure 3b. Pressurized State for the Vacuum Purging Process
Figure 3c. Relieved State for the Vacuum Purging Process
Take the system to be the gas in the process vessel and let:
t
V be the volume of the pressure vessel to be inerted/purged at time t,
i
t
x be the composition of the chemical species to be diluted at time t,
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 16 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
t
P be the absolute pressure in the vessel at time t,
t
T be the absolute temperature in the vessel at time t,
t
n be the total moles in the vessel at time t, and
i
t
n be the moles of the chemical species to be diluted in the vessel at time t.
, flow i
t
x be the mole fraction of the species to be diluted in the purge gas at time t ,
2
1
t
flow
t
n be the moles of purge gas added to the vessel, and
3
t
P is the absolute pressure in the vessel after the pressurized gas is relieved.
The volume of the process vessel is constant throughout the inerting/purging process. For convenience, define:
1 2 3
t t t
V V V V = =
Assume that the ideal gas law holds and that the temperature of the gas in the vessel is the same at all three
states for the inerting/purging process. For convenience, define:
1 2 3
t t t
T T T T = =
For convenience, define:
1
L
t
P P
where:
L
P is the initial pressure (the low pressure) in the pressure purging process.
Then, at the initial state:
1
1
1
1
L
t
i
t
i
t
t
PV
n
RT
n
x
n
=
=
1
1
i L
t
i
t
x PV
n
RT
=
Purge gas is introduced to the vessel increasing the absolute pressure to
2
t
P . For convenience, define:
2
H
t
P P
where:
H
P is the pressure (the high pressure) in the pressure purging process.
The ideal gas law gives the total moles in the vessel.
2
H
t
P V
n
RT
=
The total moles of purge gas added to the vessel are:
( ) 2
2 1
1
t
H L
flow
t t
t
P P V
n n n
RT
= =
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 17 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
This equation defines the purge gas requirements for the pressure purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
, , flow i flow i
t
x x =
The moles of the species to be diluted that are added to the vessel in the purge gas is:
2 2
1 1
, ,
t t
flow i flow i flow
t t
n x n =
So the mole fraction of the species to be diluted in the pressurized state is:
2
1
2 1
2 1
2 2
,
,
1
t
i flow i
i t
t t
L L
i i flow i
t t
H H
t t
n n
n
P P
x x x
n n P P
+
| | | |
= = = +
| |
\ . \ .
Assuming that the composition of the gas is uniform throughout the vessel as the pressure is relieved,
then, the composition of the gas in the vessel at state 3 is the same as at state 2, thus:
3 2 1
,
1
L L
i i i flow i
t t t
H H
P P
x x x x
P P
| | | |
= = +
| |
\ . \ .
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel. Also, the nomenclature has been devised so that the equations for the purge
gas requirements and the composition of the species to be diluted are identical for vacuum and pressure
purging.
Example 3: Dilution of Atmospheric Air in a Pressure Purge
Determine: a) the oxygen concentration and b) the volume of purge gas at STP when a vessel with a
volume of 4 m
3
containing air at 25
o
C and atmospheric pressure is vacuum purged to 1.5 atmospheres with a
purge gas that is 98 mole% nitrogen and 2 mole% oxygen.
Solution
a)
3 1
,
1.5 1.5
1 0.21 0.02 1 0.147
1.0 1.0
L L
i i flow i
t t
H H
P P atm atm
x x x
P P atm atm
| | | | | | | |
= + = + =
| | | |
\ . \ . \ . \ .
b)
( ) 2
2 1
1
t
H L
flow
t t
t
P P V
n n n
RT
= =
( )
( )( )( )
( )( )
2
1
3
3
1.5 1.0 4 298
2.18
1.0 273
t
flow
STP
H L t
STP
flow
STP
STP STP
flow
STP
n RT
P P V T
V
P P T
atm atm m K
V m STP
atm K
= =
= =
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 18 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
1
3 1
2
t
i i
t t
t
P
x x
P
| |
| =
|
\ .
Multiple pressure purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let
3
t designate the end of the first pressure purge cycle and the beginning of the second
pressure purge cycle. Then,
4
t will correspond to a pressurized state and
5
t will correspond to the relieved
state that is the end of the second pressure purge cycle. The mole fraction of the species to be diluted at the
conclusion of the second vacuum purge cycle will be:
4 2 4
5 3 1
5 3 5
t t t
i i i
t t t
t t t
P P P
x x x
P P P
| | | || |
| | | = =
| | |
\ . \ .\ .
If the pressurized and relieved pressures are the same for each cycle , 1 j j J = :
2
2 1
0
0
j
j
L
t
H
t
P P j J
P P j J
+
= =
= =
Subscript L designates the low pressure in the cycle (the relieved state) and subscript H designates the high
pressure in the cycle (the pressurized state). Measuring time in cycles (the initial time becomes cycle 0):
0
0
j
L
i i
j
H
P
x x j J
P
| |
= =
|
\ .
The number of such cycles necessary to achieve a target concentration for the species to be diluted is:
0
ln
ln
i
J
i
L
H
x
x
J
P
P
| |
|
|
\ .
=
| |
|
\ .
The total moles of purge gas required are:
( ) 3
2
t
H L
flow
t
J P P V
J n
RT
=
Again, the equations are identical to those for vacuum purging.
Example 5: Number of Pressure Purge Cycles
Determine the number of purge cycles to a pressure of 1.5 atmospheres needed to reduce the oxygen
concentration of atmospheric air to 6 mole% with pure nitrogen purge gas.
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 19 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
Solution
The assumption of ideal gas behavior should be valid for these conditions. Sufficient time will have to
be allotted after pressurizing to ensure that the purge gas mixes thoroughly so the concentration in the vessel is
uniform throughout. Then:
0.06
ln
0.21
3.1
1.0
ln
1.5
J
atm
atm
| |
|
\ .
= =
| |
|
\ .
Four cycles will be required to reduce the oxygen concentration below 6 mole%.
Siphon Purging
There are two steps in the siphon purging process: 1) displacement of gas in the vessel by filling with a
liquid and 2) displacement of the liquid in the vessel with purge gas. The states of interest for the siphon
purging process are shown in Figure 4.
Figure 4a. Initial State for the Siphon Purging Process
Figure 4b. Liquid-Filled State for the Siphon Purging Process
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 20 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
Figure 4c. Drained State for the Siphon Purging Process
Take the system to be the gas in the process vessel and let:
t
V be the volume of the pressure vessel to be inerted/purged at time t,
( ) g
t
V be the volume of gas in the pressure vessel at time t,
( ) l
t
V be the volume of liquid in the pressure vessel at time t,
( ) i g
t
x be the composition of the chemical species to be diluted in the gas phase at time t,
t
P be the absolute pressure in the vessel at time t,
t
T be the absolute temperature in the vessel at time t,
( ) g
t
n be the total moles in the gas phase in the vessel at time t,
( ) i g
t
n be the moles of the chemical species to be diluted in the gas phase at time t.
, ( ) flow i g
t
x be the mole fraction of the species to be diluted in the purge gas at time t , and
3
2
( )
t
flow g
t
n be the moles of purge gas added to the vessel as the liquid is drained.
The volume of the process vessel is constant throughout the inerting/purging process. For convenience, define:
1 2 3
t t t
V V V V = =
Assume that the ideal gas law holds for the gas phase and that the temperature and pressure of the gas in the
vessel is the same at all three states for the inerting/purging process. For convenience, define:
1 2 3
1 2 3
t t t
t t t
T T T T
P P P P
= =
= =
and:
2
( ) L g
t
V V
where:
L
V is the volume of gas when the vessel is filled with liquid (the low volume). Also, assume
that the liquid is completely drained from the vessel such that:
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 21 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
3
( ) H g
t
V V V =
where:
H
V is the volume of gas when the vessel is drained of liquid (the high volume).
Then, at the initial state:
1
1
1
1
( )
( )
( )
( )
H
g
t
i g
t
i g
t
g
t
PV
n
RT
n
x
n
=
=
1
1
( )
( )
i g H
t
i g
t
x PV
n
RT
=
Liquid is introduced to the vessel displacing the gas. The ideal gas law gives the total moles of gas left in the
vapor space.
2
( )
L
g
t
PV
n
RT
=
Assuming that the composition of the gas is uniform throughout the vessel as the liquid is introduced, then, the
composition of the gas phase in the vessel at state 2 is the same as at the initial state, thus:
2 2
2 1
2
( ) ( )
( ) ( )
( )
i g i g
t t
i g i g
t t
L g
t
n n RT
x x
PV n
= = =
Solving for the moles of the species to be diluted at the vacuum state:
1
2
( )
( )
i g L
t
i g
t
x PV
n
RT
=
The ideal gas law gives the total moles in the vessel after draining the liquid:
3
( )
H
g
t
PV
n
RT
=
The total moles of purge gas added to the vessel are:
( ) 3
2 3 2
( ) ( ) ( )
t
H L
flow g g g
t t t
P V V
n n n
RT
= =
This equation defines the purge gas requirements for the siphon purging process.
Assume that the composition of the species to be diluted in the purge gas is constant during the filling
process. Let:
, ( ) , ( ) flow i g flow i g
t
x x =
The moles of the species to be diluted that are added to the vessel in the purge gas is:
3 3
2 2
, ( ) , ( ) ( )
t t
flow i g flow i g flow g
t t
n x n =
So the mole fraction of the species to be diluted in the gas phase after draining is:
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 22 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
3
3 2 2
3 1
3 3
( ) ( ) , ( )
( ) ( ) , ( )
( ) ( )
1
t
i g i g flow i g
t t t
L L
i g i g flow i g
t t
H H g g
t t
n n n
V V
x x x
V V n n
+
| | | |
= = = +
| |
\ . \ .
Note that residual gas and the purge gas must be well mixed for the composition of the species to be diluted to
be uniform throughout the vessel. The formulas for the purge gas requirements and the composition of the
species to be diluted are the same as those for vacuum and pressure purging with volume substituted for
pressure.
Example 6: Siphon Purging of Air
A 1000-gallon vessel that is filled with air at 760 mmHg and 20
o
C is to be inertied by siphon purging so
that benzene (C
6
H
6
) can be charged to the vessel. How many gallons of water should be to create a 5% margin
of safety in one cycle if the nitrogen purge gas contains 1 mole% oxygen?
Solution
The in-service oxygen concentration for benzene is 11.8 mole% (Table 4). A 5% margin of safety would
give a target oxygen concentration of 6.8 mole%. Assume air to be simple air and note that the ideal gas law
will be valid at these conditions:
3 1
( ) ( ) , ( )
0.068 1 0.21 0.01 1
1000 1000
L L L L
i g i g flow i g
t t
H H
V V V V
x x x
V V gal gal
| | | | | | | |
= = + = +
| | | |
\ . \ . \ . \ .
Solving for the low gas volume:
290
L
V gal =
This is the gas volume when the vessel is filled with liquid. The liquid volume is:
2
2
( )
( )
710
L l
t
l
t
V V V
V gal
= +
=
The purge gas will have a negligible concentration of the chemical species to be diluted in the typical
circumstance. For this case:
2
3 1
3
( )
( ) ( )
( )
g
t
i g i g
t t
g
t
V
x x
V
| |
|
=
|
\ .
Multiple siphon purge cycles may be required to reduce the concentration of the chemical species below its
target value. Let
3
t designate the end of the first siphon purge cycle and the beginning of the second siphon
purge cycle. Then,
4
t will correspond to a liquid-filled state and
5
t will correspond to the drained state that is
the end of the second siphon purge cycle. The mole fraction of the species to be diluted in the gas phase at the
conclusion of the second siphon purge cycle will be:
4 2 4
5 3 1
5 3 5
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
g g g
t t t
i g i g i g
t t t
g g g
t t t
V V V
x x x
V V V
| | | || |
| | |
= =
| | |
\ . \ .\ .
If the liquid-filled and drained gas volumes are the same for each cycle , 1 j j J = :
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 23 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
2
2 1
( )
( )
1
1
j
j
L g
t
H g
t
V V j J
V V j J
+
= =
= =
Subscript L designates the low gas volume in the cycle (the liquid-filled state) and subscript H designates the
high gas volume in the cycle (the drained state). Measuring time in cycles (the initial time becomes cycle 0):
( ) ( )
0
0
j
L
i g i g
j
H
V
x x j J
V
| |
= =
|
\ .
The number of such cycles necessary to achieve a target concentration for the species to be diluted in the gas
phase is:
( )
( )
0
ln
ln
i g
J
i g
L
H
x
x
J
V
V
| |
|
|
\ .
=
| |
|
\ .
The total moles of purge gas required are:
( ) 3
2
( )
t
H L
flow g
t
JP V V
J n
RT
=
Again, the equations are identical to those for vacuum and pressure purging with volume substituted for
pressure.
Example 7: Number of Siphon Purge Cycles
A 1000-gallon vessel that is filled with air at 760 mmHg and 20
o
C is to be inerted by siphon purging so
that benzene (C
6
H
6
) can be charged to the vessel. How many purge cycles using 400 gallons of water would
create a 5% margin of safety using pure nitrogen purge gas?
Solution
The in-service oxygen concentration for benzene is 11.8 mole% (Table 4). A 5% margin of safety would
give a target oxygen concentration of 6.8 mole%. Assume air to be simple air and note that the ideal gas law
will be valid at these conditions. Sufficient time will have to be allotted after draining to ensure that the purge
gas mixes thoroughly so the concentration in the vessel is uniform throughout.
If the filled with 400 gallons of liquid, then the gas phase volume is:
2
( )
1000 400
600
L l L
t
L
V gal V V V gal
V gal
= = + = +
=
0.068
ln
0.21
2.2
600
ln
1000
J
gal
gal
| |
|
\ .
= =
| |
|
\ .
Three cycles will be required to reduce the oxygen concentration below 6.8 mole%.
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 24 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
Sweep-Through Purging
The purge gas is allowed to flow continuously through the vessel in sweep-through purging. The
residual gas in the vessel can be displaced by the purge gas and/or mix with the purge gas. If the inlet and
outlet ports for the purge gas are not placed properly, the purge gas may not displace and/or mix thoroughly
with the residual gas in the vessel. Displacement effects are generally neglected in sweep-through purging.
Displacement is most effective if the flow within the vessel is laminar. Mixing, on the other hand, is most
effective when there is a lot of turbulence in the flow within the vessel. When non-ideal mixing occurs, the purge
gas is said to bypass or short-circuit (simply flow from the inlet to the outlet). Portions of the residual gas in the
vessel (particularly that in corners or indentations in the vessel) will not be displaced from the vessel nor will the
composition be diluted by the purge gas. For sweep-through purging to be effective, it is important for the purge
gas to flow throughout the entire volume of the vessel (no dead volumes or eddies). Figure 3 shows the sweep-
through purge process.
Figure 3. Sweep-Through Purge Process
Take the system to be the gas in the vessel, assume the ideal gas law, and assume the flow, temperature,
pressure, and composition of the purge gas are constant during the process. Further, assume that the
temperature and pressure of the purge gas in, the gas in the vessel, and the gas flow from the vessel are equal,
and let:
t
V be the volume of the pressure vessel to be inerted/purged at time t,
i
t
x be the composition of the chemical species to be diluted at time t,
t
P be the absolute pressure in the vessel at time t,
t
T be the absolute temperature in the vessel at time t,
t
n be the total moles in the vessel at time t, and
i
t
n be the moles of the chemical species to be diluted in the vessel at time t.
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 25 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
, flow in
V be the volumetric flow of purge gas into the vessel,
, flow out
V be the volumetric flow of gas from the vessel,
, flow in
n be the molar flow of purge gas into the vessel,
, flow out
n be the molar flow of gas from the vessel,
, , flow in i
n be the molar flow of the species to be diluted in the purge gas into the vessel,
, , flow out i
n be the molar flow of the species to be diluted in the gas from the vessel,
, , flow in i
x be the mole fraction of the species to be diluted in the purge gas into the vessel,
, , flow out i
x be the mole fraction of the species to be diluted in the gas from the vessel,
, flow in
P be the absolute pressure of the purge gas into the vessel,
, flow out
P be the absolute pressure of the gas from the vessel,
, flow in
T be the absolute temperature of the purge gas into the vessel,
, flow out
T be the absolute temperature of the gas from the vessel,
For convenience, let:
, , flow in flow out
t
T T T T = = =
, , flow in flow out
t
P P P P = = =
t
V V =
The ideal gas law gives the total moles in the system:
t
PV
n
RT
=
The temperature and pressure of the gas and the volume of the vessel are assumed constant, therefore:
0
t
d n
dt
=
Under these assumptions, the total number of moles of gas in the vessel is constant throughout the process.
There are no chemical reactions occurring during the process, thus, the Law of Conservation of Mass can be
written in terms of moles:
, ,
0
t
flow in flow out
d n
n n
dt
= =
The sign convention taken is that the molar flows, both in and out of the system, are positive. Applying the ideal
gas law to the flows:
,
,
,
,
flow in
flow in
flow out
flow out
PV
n
RT
PV
n
RT
=
=
Substituting into the Law of Conservation of Mass:
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 26 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
, , flow in flow out
V V V =
Under the stated assumptions, the volumetric flow into and out of the system are equal. The chemical species
balance for the species to be diluted (oxygen when placing the vessel in service and fuel when removing it from
service) is:
, , , ,
i
t
flow in i flow out i
d n
n n
dt
=
Substituting the definition of the mole fraction for the species to be diluted:
( )
, , , , , ,
i
t t
flow in i flow in flow out i flow out
d x n
x n x n
dt
=
In most cases, the mole fraction of the species to be diluted is negligible in the purge gas. Substituting the ideal
gas law relationships:
, , , ,
i
t
flow in i flow out i
PV
d x
PV PV RT
x x
dt RT RT
| |
|
\ .
=
The volume of the vessel, the volumetric flow of the purge gas, the temperature, and the pressure are all
assumed constant throughout the process, therefore:
( )
, , , ,
i
t
flow in i flow out i
d x
V V x x
dt
=
Assume a very simple model for the mixing of the purge and residual gas in the vessel in which a fraction of the
purge gas mixes perfectly with the residual gas in the vessel and the remainder does not mix at all. The
nonideal mixing factor is the fraction of the purge gas that perfectly mixes. The two fractions combine to form
the gas that exits the vessel. Further assume that the fraction of perfectly mixed purge gas is constant
throughout the process. Let:
mix
f be the nonideal mixing factor.
If the nonideal mixing factor is one, then the purge and residual gases mix perfectly and if it is zero, then the
purge gas flows directly from the inlet to outlet of the vessel. In practice, the nonideal mixing factor is
somewhere between these two limits. Table 4 reports the recommended values for the nonideal mixing factor
for various ventilation conditions in which personnel may be exposed to toxic substances.
Table 4. Nonideal Mixing Factor for Various Ventilation Conditions
Toxicity Recommended Values for the Nonideal Mixing Factor
a
Poor Average Good Excellent
Slight 1/7 1/4 1/3 1/2
Moderate 1/8 1/5 1/4 1/3
High 1/11 1/8 1/7 1/6
a
Values are reciprocals of safety factors reported.
Sax, N. Irving, Dangerous Properties of Industrial Materials, 5
th
Edition, Van Nostrand Reinhold, 61
(1979).
Process vessels, even those that are to be regularly purged, are not often designed to achieve good
mixing of the purge and residual gases. In the absence of vessel design specifically for purging, a value of 1/10
is a reasonable for design under the worst-case scenario.
For this simple mixing model:
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 27 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
( )
, , , , , , , , ,
1
flow out i flow out i flow out mix i flow in mix flow in i flow in
t
n x n f x n f x n = = +
Under the assumptions, the molar flows in and out are equal:
( )
, , , ,
1
flow out i mix i mix flow in i
t
x f x f x = +
Substituting into the component balance:
( ) ( ) ( ) , , , ,
1
i
t
flow in i mix i mix flow in i
t
d x
V V x f x f x
dt
= +
Simplifying and rearranging:
( )
, ,
i
t mix
i flow in i
t
d x
f V
x x
dt V
=
Integrating from the initial time,
1
t :
( )
1
, ,
1
, ,
ln
i flow in i
t mix
i flow in i
t
x x
f V
t t
x x V
| |
| =
|
\ .
The total sweep gas requirements are:
( )
1
1
t
flow
t
V V t t =
The number of turnovers is defined as the volume of sweep gas divided by the volume of the vessel:
( )
1
1
t
flow
t
turnover
V
V t t
N
V V
= =
Example 8: Sweep-Through Purge of Air
Determine the time required for a vessel with a volume of 4 m
3
and filled with atmospheric air to be
purged with a sweep gas of nitrogen containing 1 mole% oxygen at a purge rate of 2 m
3
/min to an oxygen
concentration of 6 mole%.
Solution:
Assume atmospheric air is simple air and take the worst case scenario for mixing:
( )
3
1 3
1
2
10 min 0.06 0.01
ln
0.21 0.01 4
m
t t
m
| |
| |
| |
\ . | |
\ .
=
|
\ .
The elapsed time is:
1
27.7 min t t =
Note that the total volume of sweep gas is:
( ) ( )
3
3
1
2 27.7 min 55.4
min
m
V t t m = =
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 28 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
Almost 14 turnovers are required.
Summary
Sweep-through purging is a simple process that can be accomplished at atmospheric pressure (the
vessel to be purged does not have to be designed for vacuum or pressure conditions). However, mixing
effectiveness is an important consideration in purge gas cost and time. Vessels to be sweep-through purged
should be designed to achieve good mixing.
Homework Problem 258.1.1 (30 points): Sweep-Through Purging
The flavor of certain carbonated beverages is adversely affected by the presence of oxygen in the
gaseous atmosphere above the fluid. Storage vessels are purged of air using carbon dioxide prior to
introduction of the beverage. The storage vessels are horizontal, cylindrical tanks of 2500 barrel capacity (in
this industry, one barrel is 31 US gallons) and the carbon dioxide concentration must be at least 99.9 mole% for
beverage storage. The carbon dioxide flow is 400 acfm (actual cubic feet per minute). The most convenient
(and least expensive) flow connections to a horizontal, cylindrical vessel are all to one cylindrical end. This
configuration minimizes piping and pumping requirements and is independent of thermal expansion of the
vessel length on heating and cooling. Thus, it is common for the purge inlet and exhaust ports to be on the
same end of the storage vessel. This is, of course, not the ideal configuration to promote good mixing.
a) If perfect mixing occurred in the vessel, estimate the time required and the number of turnovers
necessary to purge the air from the vessel.
b) Estimate the value of the non-ideal mixing factor and the number of turnovers if 24 hours are required to
purge the air from the vessel.
c) In order to reduce purge gas costs and time, an extension through the exhaust gas port is added so that
the exhaust gas pickup is near the far end of the vessel. In an experiment with the modified vessel, the
desired carbon dioxide concentration was achieved in 10 hours. Estimate the value of the non-ideal
mixing factor and the number of turnovers for the modified configuration.
Solution
a) Assume that there is negligible air in the carbon dioxide purge gas. The non-ideal mixing factor is one
for perfect mixing. Note that air is the species to be diluted in this problem.
( )
1
, ,
1
, ,
ln
i flow in i
t mix
i flow in i
t
x x
f V
t t
x x V
| |
| =
|
\ .
( )
( )
( )
1
3
31 0.001
2500 ln
1.000
2.98
7.48 60 min
1 400
gal
bbl
bbl
t t hr
gal
cfm
ft hr
| | | |
| |
\ . \ .
= =
| |
| |
| |
\ .
\ .
( )
1
1
t
flow
t
turnover
V
V t t
N
V V
= =
( ) ( )
( )
3
7.48 60 min
400 2.98
6.91
31
2500
turnover
gal
cfm hr
ft hr
N
gal
bbl
bbl
| |
| |
| |
\ .
\ .
= =
| |
|
\ .
b)
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 29 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
( )
( )
3
31 0.001
2500 ln
1.000
0.124
7.48 60 min
400 24
mix
gal
bbl
bbl
f
gal
cfm hr
ft hr
| | | |
| |
\ . \ .
= =
| |
| |
| |
\ .
\ .
( ) ( )
( )
3
7.48 60 min
400 24
55.6
31
2500
turnover
gal
cfm hr
ft hr
N
gal
bbl
bbl
| |
| |
| |
\ .
\ .
= =
| |
|
\ .
The non-ideal mixing factor has a value of approximately 1/8 that is indicative of poor mixing. The poor mixing
leads to long purge times and a large number of turnovers.
c)
( )
( )
3
31 0.001
2500 ln
1.000
0.298
7.48 60 min
400 10
mix
gal
bbl
bbl
f
gal
cfm hr
ft hr
| | | |
| |
\ . \ .
= =
| |
| |
| |
\ .
\ .
( ) ( )
( )
3
7.48 60 min
400 10
23.2
31
2500
turnover
gal
cfm hr
ft hr
N
gal
bbl
bbl
| |
| |
| |
\ .
\ .
= =
| |
|
\ .
The non-ideal mixing factor has a value of approximately 3/10 that is indicative of good mixing. The improved
mixing greatly reduces purge time and carbon dioxide consumption.
Homework Problem 258.1.2 (30 points): Vacuum Purging
The flavor of certain carbonated beverages is adversely affected by the presence of oxygen in the
gaseous atmosphere above the fluid. Storage vessels are purged of air using carbon dioxide prior to
introduction of the beverage. The storage vessels are horizontal, cylindrical tanks of 2500 barrel capacity (in
this industry, one barrel is 31 US gallons) and are rated for perfect vacuum. The carbon dioxide concentration
must be at least 99.9 mole% for beverage storage. A jet ejector is available that will draw a vacuum pressure of
10 inches of mercury. Determine the number of vacuum purge cycles and the volume of purge gas at 25
o
C and
1 atmosphere necessary to purge the air from the vessel.
Solution
0
ln
ln
i
J
i
L
H
x
x
J
P
P
| |
|
|
\ .
=
| |
|
\ .
0.001
ln
1.000
17.0
29.92 10.0
ln
29.92
J
inHg inHg
inHg
| |
|
\ .
= =
| |
|
\ .
CHE 258 CHEMICAL PROCESS SAFETY MODULE 1
Neil L. Book Document1 Page 30 of 30
Oliver C. Sitton Department of Chemical Engineering
Douglas K. Ludlow University of Missouri-Rolla Copyright 2000
The total moles of purge gas required are:
( )
( )( )
( )
3
2
31 3.785
10.0 2500
17 68.2
29.92 1000
0.082 298
t
H L
flow
t
gal lit
inHg bbl
J P P V bbl gal
J n kgmole
RT lit atm inHg mole
K
mole K atm kgmole
| |
| |
| |
\ .
\ .
= = =
| | | |
| |
| | |
\ .
\ . \ .
( ) ( )
3
3
2
2
6
1000
17 68.2 0.082 298
28.3 10
1
t
flow flow t
t
flow
t
flow
mole lit atm
kgmole K
Jn RT
kgmole mole K
J V x lit
P atm
| | | |
| |
\ .\ .
= = =
The number of turnovers at these conditions is:
( )
3
2
6
28.3 10
96.6
31 3.785
2500
t
flow
t
turnover
J V
x lit
N
V gal lit
bbl
bbl gal
= = =
| |
| |
| |
\ .
\ .