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Control of Volatile Organic


Compounds (VOCs)
2
VOCs are liquids or solids that contain
organic carbon (carbon bonded to carbon,
hydrogen, nitrogen, or sulfur, but neither
carbonate carbon as in CaCO
3
nor carbide
carbon as in CaC
2
or CO or CO
2
), which
vaporize at significant rates.
Some VOCs (e.g., benzene) are toxic and
carcinogenic, and are regulated individually
as hazardous pollutants.
3
Most VOCs are believed not very toxic to
humans.
Our principal concern with VOCs is that they
participate in the smog reaction and also in
the formation of secondary particles in the
atmosphere.
Some VOCs are powerful infrared absorbers
and thus contribute to the problem of global
warming.

5
2. VOCs
We may now state, as an approximate rule,
that VOCs are those organic liquids or solids
whose room temperature vapor pressure
are greater than about 0.01 psia (= 0.0007
atm) and whose atmospheric boiling points
are up to about 500
o
F (=260
o
C).
This means most organic compounds with
less than about 12 carbon atoms.
6
Fig. 10.1 contains data for only a few of the
millions of organic chemicals in the VOC
vapor pressure range.
The Clean Air ACT Amendments of 1990 of
the U.S. list 189 compounds that are
considered to be health hazards and that
are to be regulated to prevent or minimize
emissions; most are VOCs.
7
The legal definition used for regulatory
purposes does not set a lower vapor
pressure limition and excludes a large
variety of compounds that have negligible
photochemical reactivity, including methane,
ethane, and most halogenated compounds.
The terms VOC and hydrocarbon (HC) are
not identical, but often are practically
identical.
8
Hydrocarbons are only slightly soluble in
water.
Polar VOCs, which almost all contain an
oxygen or nitrogen atom in addition to
carbons and hydrogens (alcohols, ethers,
aldehydes and ketones, carboxylic acids,
esters, amines, nitriles) are much more
soluble in water.
9
This difference in solubilities makes the
polar VOCs easier to remove from a gas
stream by scrubbing with water, but harder
to remove from water once they dissolve in
it.
Table 10.3 (next slide) shows some typical
values of these solubilities.
Within each chemical family the solubility
decreases with increasing molecular weight.

11
3. Control by Prevention
The ways of doing this for VOCs are
substitution, process modification, and
leakage control.
3.1 Substitution
Water-based paints are concentrated oil-
based paints, emulsified in water.
After water evaporates, the small amount of
organic solvent in the remaining paint must
also evaporate for the paint to harden.
12
For many applications, e.g., house
paint, the water-based paints seem
just as good as oil-based paints.
But water-based paints have not yet
been developed that can produce auto
body finishes as bright, smooth, and
durable as the high-performance oil-
based points and coatings now used.
13
There are numerous other examples where
a less volatile solvent can be substituted for
the more volatile one.
This replacement normally reduces but does
not eliminate the emission of VOCs.
Replacing gasoline as a motor fuel with
compressed natural gas or propane is also
a form of substitution that reduces the
emissions of VOCs.
14
3.2 Process Modification
Replacing gasoline-powered vehicles with
electric-powered vehicles is a form of
process modification that reduces the
emissions of VOCs, as well as emission of
carbon monoxide and nitrogen oxides, in the
place the vehicle is.
On the other hand, it causes other
emissions where the electricity is generated.
15
Many coating, finishing and decoration
processes that at one time depended
on evaporating solvents have been
replaced by others that do not, e.g.,
fluidized-bed powder coating and
ultraviolet lithography.
16
3.3 Leakage Control
3.3.1 Filling, Breathing, and Emptying
Losses
Tank containing liquid VOCs can emit VOC vapors
because of filling and emptying activities as well as
changes in temperature and atmospheric pressure.
These emissions are called filling or displacement
losses, emptying losses, and breathing losses, or,
collectively, working losses.
Fig. 10.2 (next slide) shows a simple tank of some
kind being filled with liquid from a pipeline.

18
For all three kinds of working losses,





where m
i
= mass emission of component i
c
i
= concentration in the displaced gas

-


(3)
i i
volume of air VOC mix concentration of
VOC emission
expelled from the tank VOC in that mix
m Vc
| || |
=
| |
\ .\ .
= A
,
(4)
i i
molar gas
y M
V
=
19
Replacing the vapor mol fraction by
Raoults law, Eq. (1), replacing the gas
molar volume by the ideal gas law, and
substituting in Eq. (3), we find
(5)
i i i i i i i
m x p M x p M P
V P RT RT
= =
A
20
If the tank is emptied a little at a time,
with the incoming air mixing well
with the air already in the tank, then
the gas forced out the vent will have
a benzene concentration close to
the saturated value.
Here we assume an average of the
two, or c
i

in emitted air
= 0.5 c
i

saturated

21
Then using Eqs. (4), (5), and (9),






This value is about 5% as large as the filling
loss shown in Example 4. #
( ) ( )

,
2 2
2 2
3
( )( )
0.5
( )
0.5
(1) (1.45 ) (78 / )
0.5
(14.7 )(10.73 / / )(528 )

benzene final
i
benzene final
air admitted molar gas
i i
o o
y M
m
y
V V
x p M
PRT
psia lb lbmol
psia psi ft lbmol R R
=
| |
=
|
\ .
(
=
(


3
0.00098 / lb benzene ft of air admitted =
22
Breathing, filling, and emptying losses are
minimized by attaching to the vent of the
tank in Fig. 10.2 a pressure-vacuum valve,
also called a vapor conservation value.
These valves remain shut when the
pressure difference across them is small,
typically 0.5 psi positive pressure or 0.062
psi negative.
23
3.3.2 Displacement and Breathing
Losses for Gasoline
The U.S. uses about 350 million gallons
gasoline per day.
Gasoline is a complex mixture, typically
containing perhaps 50 different
hydrocarbons in concentrations of 0.01% or
more, plus traces of many others.
The smallest molecules have 3 carbon
atoms; the largest, 11 or 12.
24
A typical gasoline has an average formula
of about C
8
H
17
and thus an average
molecular weight of about 113.
For any mixture of VOCs, like gasoline, both
the vapor pressure and molecular weight of
the vapor change as the liquid vaporized.
This behavior is sketched in Fig. 10.3 (next
slide).

26
To estimate the displacement and breathing
losses for a mixture like gasoline, we first
observe that only a small fraction of the
gasoline is normally evaporated into the
headspace of its containers.
So the appropriate vapor pressure and
molecular weight are those corresponding
to zero percent vaporized, or roughly 6 psia
and 60 g/mol at 20
o
C = 68
o
F for the gasoline
in Fig. 10.3
27
For large-scale storage, the petroleum
industry store volatile liquids in floating
roof tanks, as shown in Fig. 10.4 (next
slide).

29
The transfer of gasoline from tank
trucks to underground tanks at service
stations now uses the scheme shown
in Fig. 10.5 (next slide).

31
The vent line shown in Fig. 10.5
remains open during tank filling to
prevent any excessive pressure or
vacuum in the system.
The vapor return system recovers
about 95% of the vapor from the tank
being filled, the other 5% exits from the
underground tanks vent.
32
The same kind of technology is used
for the transfer of gasoline from the
underground tank to the customers
vehicle.
The system is sketched in Fig. 10.6
(next slide).

34
The vented vapor is normally passed
through an incinerator that destroys the
VOC before it reaches the ambient air.
The numbers in Fig. 10.6 suggest that this
system reduces displacement losses by
95%, and spillage losses by 62%.
The breathing losses are also reduced
because much less fresh air enters the
storage tank.
35
The vapor pressure of gasoline is specified
by the Reid vapor pressure (RVP), which is
found by a standard test. The value is close
to the true vapor pressure at 100
o
F.
Refiners adjust the RVP of their product by
adjusting the ratio of low-boiling
components (butanes and pentanes) to
higher-boiling components (other
hydrocarbons up to about C
12
).
36
In winter they raise the RVP to
improve the cold-starting properties of
the gasoline.
In summer they lower the RVP
because cold starting is not a problem,
but vapor leak can be.
37
Typical winter RVP values in the
United States are 9 to 15 psi, with the
lowest values in Florida and Hawaii
and the highest values in the colder
states.
Typical summer values are 8 to 10 psi.
38
3.3.3 Seal Leaks
Fig. 10.7 (next slide) shows three
kinds of seals.
(a) static seal
(b) packed seal
(c) rotary seal

40
4. Control by concentration and
Recovery
Most VOCs are valuable fuels or
solvents. For large VOC-containing
gas streams recovery is often
economical, but not often for small
streams.
We can concentrate and recover VOC
by condensation, adsorption, and
absorption.
41
4.1 Condensation
Example 9
We wish to treat an airstream containing
0.005 mol fraction (0.5%, 5000 ppm)
toluene, moving at a flow rate of 1000 scfm
at 100
o
F and 1 atm, so as to remove 99% of
the toluene by cooling, condensation, and
phase separation, as sketched in Fig. 10.8
(next slide).
To what temperature must we cool the
airstream?

43
Solution:
99% recovery will reduce the mol fraction in
the gas stream to 0.005% = 50 ppm.
Assuming the recovered liquid is practically
pure toluene (x
toluene
1), we know that we
must find from Eq. (1) the temperature at
which


4
0.00005 14.7 7.35 10 5
toluene toluene
p y P psi psia Pa

= = = =
44
Using the Antoine equation constants for
toluene in Appendix A, we find that this
corresponds to a temperature of -60
o
C. #
In spite of many difficulties such devices are
used for medium-sized and/or intermittent
flow of gas streams containing VOCs.
Most often the cooling and condensation
occur in stages, with most of the water taken
out in the first stage, which operates just
above 0
o
C.
45
Example 10
The current USEPA requirement for
gasoline bulk-loading terminals is that the
displacement loss from the returning tank
trucks must not exceed 35 mg of VOCs per
liter of gasoline filled.
One common solution to this problem is
sketched in Fig. 10.9 (next slide).

47
The first cooling system takes out much of
the gasoline and most of the water, and the
second, at a lower temperature, takes out
most of the remaining gasoline.
Assuming that the vapor leaving the truck is
at 20
o
C (= 68
o
F), in equilibrium with the
remaining gasoline in the truck, and that the
vapor is 1 mol% water vapor, (a) how cold
must the second chiller cool the displaced
vapor before discharging it to the
atmosphere?
48
Assume that the discharged vapor is in
equilibrium with liquid gasoline at that
temperature, that the gasoline vapor in the
air has a molecular weight of 60, and that its
vapor pressure is given approximately by



which is a fair approximation for 10 RVP
gasoline.
ln ( ) 11.724 (5236.5 ) / (10)
o
p psia R T =
49
(b) What fraction of the gasoline will be
removed in the first stage, which cools
the gas to about 32
o
F?
(c) What is the ratio of ice formed to
gasoline condensed in the second stage?
Solution:
Choose a basis 1 mol of vapor leaving the
tank in stream and record results as
calculated in the following table (next slide).

51
From Eq. (10) we estimate the vapor
pressure of the gasoline as 6.09 psia, from
which we can compute the gasoline mol
fraction as (6.09 psia / 14.7 psia) = 0.414.
Thus for the assumed basis of 1 mol, the
mols of gasoline are 0.414, the mols of
water are 0.01, and those of air (1 - 0.414 -
0.01) = 0.576.
Thus we have a complete description of
stream 1.
52
Next we assume that the air passes
unchanged through the system.
This is equivalent to assuming that no
air dissolves in the gasoline or water
we remove.
Thus we can fill in the row for mols of
air in streams 2 & 3 (0.576).
53
To find the permitted amount of gasoline in
stream 3 we observe that 1 L of gasoline
displaces 1 L of vapor (stream 1):


We will see later the mols of water in stream
3 are neglible, so we can compute
permitted
0.035g 24.056L mol mol gasoline
= =0.0140
emission L gasoline mol 60g mol stream 1
| |

|
\ .
mol fraction
mols gasoline 0.0140
gasoline in 0.024
mols(gasoline+air) (0.0140+0.576)
stream 3
| |
|
= = =
|
|
\ .
54
We are now able to solve part (a).
The vapor pressure of gasoline in stream
3 is equal to the total pressure times the
gasoline mol fraction, (14.7 0.024) =
0.350 psia; solving Eq. (10) for the
temperature corresponding to this
pressure, we find T
3
= 410
o
R = -50.0
o
F.
55
To answer part (b), we estimate the vapor
pressure of gasoline at 32
o
F from Eq. (10),
finding 2.95 psia, and look up the vapor
pressure of water at 32
o
F = 0.089 psia.
Then we find:



And, similarly for water, we find a mol
fraction of 0.006.
mol fraction
vapor pressure gasoline 2.95 psia
gasoline in 0.200
total pressure 14.7 psia
stream 2
| |
|
= = =
|
|
\ .
56
Then by difference we find the mol fraction
of air (1.0 0.2 0.006) = 0.794, from which
the total number of mols in stream 2 is
(0.576 / 0.794) = 0.726.
Thus the mols of gasoline in stream 2 are
(0.726 0.2) = 0.145, and corresponding
for water, 0.004.
Thus the amount of gasoline removed in the
first stage is (0.414 - 0.145) = 0.269 mols, or
(0.269 / 0.414) = 65% of the gasoline in
stream 1.
57
To answer part (c) we must estimate the
vapor pressure of ice at -50.0
o
F.
Extrapolating the values from the steam
table, we find p
ice
0.001 psia 0.
Then the mols of ice formed are 0.004 0 =
0.004, whereas the mols of gasoline
condensed are (0.145 0.014) = 0.131, and
the molar ratio of ice to gasoline is 0.004 /
0.131 = 3%. #
58
4.2 Adsorption
Adsorption means the attachment of
molecules to the surface of a solid.
In contrast, absorption means the
dissolution of molecules within a collecting
medium, which may be liquid or solid.
Generally, absorbed materials are dissolved
into the absorbent, like sugar dissolved in
water.
Adsorbed materials are attached onto the
surface of a material, like dust on a wall.
59
Adsorption is mostly used in air pollution
control to concentrate a pollutant that is
present in dilute form in an air or gas stream.
The adsorbent is most often some kind of
activated carbon.
For large-scale air pollution applications, the
normal procedure is to use several
adsorption beds, as shown in Fig. 10.10
(next slide).

61
When a vessel is being regenerated, steam passes
through it, removing the adsorbed VOCs from the
adsorbent.
The mixture of steam and VOCs coming from the
top of the vessel passes to a water-cooled
condenser that condenses both the VOCs and the
steam.
Both pass in liquid form to a separator, where the
VOCs, which are normally much less dense than
water and have little solubility in water, float on top
and are decanted and sent to solvent recovery.
62
The steam condensate will be
saturated with dissolved VOC.
The VOC concentration may be high
enough to prevent its being sent back
to the steam boiler, or for to be
discharged to a sewer.
63
4.2.1 Adsorbents
The catalyst supports typically have surface
areas of 100 m
2
/g, corresponding to internal
wall thickness of 100 .
Adsorbents like activated carbon often have
surface areas of 1000 m
2
/g, corresponding
to an internal wall thickness of 10 .
This value is only about four times the
interatomic spacing in crystals.
64
To design an adsorber of the type shown in
Fig. 10.10 we must consider both the
adsorbent capacity and the breakthrough
performance of the adsorbent.
4.2.2 Adsorbent Capacity
Fig. 10.11 (next slide) shows the capacity of
adsorbents in the form suggested by Polanyi.

66
Example 11
Using Fig. 10.11, estimate the adsorbent
capacity curves for toluene on a typical
activated carbon at 1.0 atm and 100
o
F and at
300
o
F.
Solution:
From the legend for Fig. 10.11 we see that
curves D through I represent various activated
carbons.
We select curve F, which lies near the middle of
this family of curves.
67
Then we compute the point on w*-P
coordinates for 1 atm, 100
o
F, and an
arbitrarily selected value of 1% toluene
in the gas.
From that point, we calculate the
values for other percent toluene values
by ratios.
68
Here T = 560
o
R and M =92 g/mol.
We estimate
L
, the toluene density at
the normal boiling point of 110.6
o
C, as
0.782 g/cm
3
from the 20
o
C density
(0.8669 g/cm
3
) and the typical
coefficient of thermal expansion for
organic liquids (0.67 10
-3
/
o
F).
69
At atmospheric pressure, the fugacity f can
be replaced by the partial pressure = 0.01
atm and the saturation fugacity f
s
can be
replaced by the vapor pressure.
Using the vapor pressure constants in
Appendix A we estimate a vapor pressure of
1.03 psia = 53 torr = 0.070 atm.
Thus we write:


'
560 0.782 0.07
log log 2.23
1.8 1.8 92 0.01
s L
f T
M f
| |
| |
= =
| |

\ .
\ .
70
From curve F of Fig. 10.11 we read an
ordinate of about 41, so that



We then repeat the calculation for other
values of the mol fraction of toluene in the
gas, and for T= 300
o
C, and plot the results
as shown in Fig. 10.12 (next slide). #
* '
41 lb toluene
0.41 0.782 0.31
100 lb solid adsorbent
L
w = = =

72
Example 12
We wish to treat the airstream in Example 9
to remove practically all the toluene.
If the bed must operate 8 h between
regenerations, how many pounds of
activated carbon must it have (a) if it is only
used once and then thrown away, and (b) if
it is regenerated to an outlet stream toluene
content of 0.5%?
73
Solution:
Here the incoming air flow is


The contained toluene is
-3
n = 1000 scfm 2.595 10 lbmol/scf = 2.595 lbmol/min
2.595 / min 92 / 0.005
1.19 / min 0.0090 /
toluene air toluene toluene
m n M Y lbmol lb lbmol
lb kg s
= =
= =
74
If all the toluene is to be recovered, we must
recover m =
From Fig. 10.12 we read that for a toluene
partial pressure of 0.005 atm at 100
o
F
(38
o
C), w* = 0.29 lb/lb, and at 300
o
F
(149
o
C) it equals 0.11 lb/lb.
1.19 / min 8 60min/ 572 260
toluene
m t lb h h lb kg A = = =
75
Thus, for part (a) we can say that the
amount of adsorbent needed is:


For part (b) the adsorbent is to be reused
and regenerated. The net amount adsorbed
per cycle will be 0.29 0.11 = 0.18 lb/lb,
and the same calculation leads to an
adsorbent requirement of 3180 lb / 1445 kg.
#
*
572
1970 895
0.29 /
m lb
lb kg
w lb lb
= = =
76
4.2.3 Breakthrough Performance
The calculation in Example 10.12
assumes that the adsorbent fills up
with adsorbed material uniformly.
Unfortunately, real adsorbers never
work that well, and some of the
material to be adsorbed breaks
through before the bed has reached
its maximum capacity.
77
The reason for this early breakthrough is
that there is a finite resistance to mass
transfer between the gas and the solid, so
some finite amount of time is needed for
each particle to be loaded with adsorbate.
Fig. 10.13 (next slide) compares the ideal
breakthrough curve with a typical real
breakthrough curve.

79
At some time t
b
less than the ideal time
the concentration in the outlet stream
reaches the breakthrough value
(typically 1% of the inlet value).
A reasonable estimate of the
breakthrough curve can be made
using Fig. 10.14 (next slide).

81
Example 13
Using the data from Example 12, estimate
the breakthrough curve that would be
observed if we started with clean adsorbent.
Assume that the adsorbent is an activated
carbon with a bulk density of 30 lb/ft
3
and a
particle diameter of 0.0128 ft.
The volume of the bed is [1970 lb/ (30 lb/ft
3
)]
= 66 ft
3
.
82
Solution:
If we assume a cubically shaped bed, the
sides of the bed will be 4.03 ( 4) ft.
Then as shown in Appendix E, we may
estimate that a = 14.4/ft and b = 7.4/h.
Thus on Fig. 10.14, N = ax =14.4/ft 4 ft =
57.6 60, so that the estimated
breakthrough behavior of the bed will follow
the curve for N = 60.
83
From Fig. 10.14, the outlet concentration will
become 1% of the inlet concentration at a bt value
of about 36, which corresponds to a time of



This value is 61% of that for perfect filling of the bed
(i.e., no mass transfer resistance). #
Fig. 10.13 is similar to Fig. 10.14 except that Fig.
10.13 is on arithmetic coordinates, whereas Fig.
10.14 is on log-normal coordinates.
36
4.9
7.4/
bt
t h
b h
= = =
84
4.3 Absorption (Scrubbing)
If we can find a liquid solvent in which the
VOC is soluble and in which the remainder
of the contaminated gas stream is insoluble,
then we can use absorption to remove and
concentrate the VOC for recovery and re-
use, or destruction.
Fig. 10.15 (next slide) shows a system of
absorption and stripping.

86
Normally, bubble caps, sieve trays, or
packing is used in the interior of the
absorption column to promote good
countercurrent contact between the
solvent and the gas.
The stripper normally is operated at a
higher temperature and/or a lower
pressure than the absorber.
87
4.3.1 Design of Gas Absorbers and
Strippers
In the device shown in Fig. 10.15, the
basic design variables are the choice
of selective reagent to be used, the
system pressure, the flow rates of the
gas and liquid, the gas velocity in the
column, and the amount of liquid-gas
contact needed to produce the
separation.
88
In Fig. 10.15 both columns operate in
counterflow: the liquid flows down the
column by gravity; the gas flow up the
column, driven by the decrease in pressure
from bottom to top.
This design not only utilizes gravity
efficiently in moving the liquid but also
provides for very efficient contacting.
Fig. 10.16 (next slide) shows why.

90
In Fig. 10.16, the curve at the right shows
the mol fraction in the gas of the component
to be absorbed, y
i
, decreasing from the
bottom to the top.
The curve at the left shows the
concentration of absorbable component that
would be in equilibrium with the liquid
absorbent, y
i
*, which increases from top to
bottom.
91
The relation between y
i
* and the mol
fraction of absorbable component in
the liquid absorbent, x
i
, is complex and
differs from one chemical system to
another.
The simplest description of such
absorption equilibria, for slightly solube
gases, is Henrys law.
92
Henrys law is normally written as



Here P is the absolute pressure, and H
i
the
Henrys law constant for component i, which
is normally a strong function of temperature,
but a weak function of pressure or
concentration.
*
(11)
i
i
i
Py
x
H
=
93
In Fig. 10.16 the transfer of the absorbable
component will be from gas to liquid as long
as y
i
> y
i
*, i.e., the actual concentration in
the gas at that location in the column is
higher than the concentration that would be
in equilibrium with the absorbing liquid.
In the stripper in Fig. 10.15 the relation is
reversed, y
i
< y
i
*, and the absorbable
component flows from liquid to gas.
94
We next perform a material balance on the
transferred component for the small section dh of
the column shown in Fig. 10.16, finding




Here G and L are the molar flows of gas and liquid
(mol/s), excluding the flow of the transferred
components.
( )
( )( )
*
mols of i mols of i mass transfer
transferred transferred capacity per d volume
from the gas to the liquid unit volume

i i i i
GdY LdX KaP y y Adh
| | | | | |
| | |
= =
| | |
| | |
\ . \ . \ .
= = (12)
95
Y
i
and X
i
are the gas and liquid contents of the
transferred component, respectively, expressed in
(mol/mol of nontransferred components).
Adh is the product of the column cross-sectional
area and incremental height, equal to the column
volume corresponding to dh.
Ka is the product of the mass transfer coefficient
and the interfacial area for mass transfer (ft
2
of
transfer area per ft
3
of volume), discussed later, and
P is the system pressure.
96
Example 14
We wish to treat the stream in Example 9,
recovering the toluene by absorption in a
suitable solvent.
Select a suitable solvent, and estimate the
required solvent flow rate.
Solution:
The solubility of toluene in water (see Table
10.3) is low enough that we are unlikely to
use water as a solvent.
97
Our logical choice is an HC with a higher
boiling point than toluene.
In Example 9 the permitted toluene
concentration in the exhaust gas is 50 ppm.
If we assume that we can emit an equal
concentration of the solvent, then its vapor
pressure at column temperature (100
o
F in
that example) must be no more than 50
10
-6
atm.
98
From Fig. 10.1, we see that the highest-
boiling HC shown, n-decane, has a vapor
pressure at 100
o
F of about 0.06 psi = 0.004
atm, which is 80 times too high.
Using the Antoine equation constants, we
find that n-tetradecane (C
14
H
30
, M =198
g/mol) has an acceptable calculated vapor
pressure of 4710
-6
atm at 100
o
F.
We would not use a pure HC as absorbent,
because pure HCs are expensive.
99
But this shows that a hydrocarbon mixture
with a vapor pressure comparable to n-
tetradecane could be used.
This is comparable to the vapor pressure of
diesel fuel.
However, for the rest of this example we will
use n-tetradecane because doing so
simplifies the calculations.
100
We can also calculate from the Antoine equation
that the atmospheric boiling point of n-tetradecane
is 490
o
F, which is the temperature we would
expect at the bottom of the stripper.
Next we integrate the left two terms of Eq. (12) from
the top to the bottom of the column and rearrange,
finding





i bottom i top
i
i i bottom i top
Y Y
Y L
G X X X

A
= =
A
101
From the definitions of Y and X that


so that for small values of y and x


To estimate the Henrys law constant we
observe that Eq. (11) is equivalent to
Raoults law [Eq. (1)], with the vapor
pressure of toluene taking the place of H.
and
1 1
y x
Y X
y x
= =

and (13) Y y X x ~ ~
102
At 100
o
F we know from Example 11 that
p
toluene
0.070 atm, and we use this as an
estimate of H.



On Fig. 10.16 we can draw in the values for
the inlet gas, y
i
= 0.5% = 5000 ppm, and for
the outlet gas, 50 ppm.
* *
*
1
14.3 (14)
0.070
toluene toluene
toluene toluene
toluene
Py atm y
x y
p atm
= = =
103
If we assume that the stripper is 100% effective,
then the stripped solvent will have zero toluene
(and the leftmost curve will go to y
i
* = 0 at the top of
the column).
The maximum conceivable liquid outlet
concentration produces a y
i
* equal to the inlet value
of 5000 ppm.
On Fig. 10.16 that would correspond to the two
curves meeting at the bottom of the column, which
means that the concentration difference driving the
absorption would be zero at the bottom of the
column so that in Eq. (12), dh = 1/0 = .
104
To prevent this, we arbitrarily specify that
the outlet liquid shall have y
i
* = 0.8 y
i
. Thus
we can calculate that


Then we may write
i bottom
x = 0.8 14.3 0.005 = 0.057 (mol fraction)


-
5000 50
0.087
- 0.057 0
i bottom i top i bottom i top
i bottom i top i bottom i top
Y Y y y
L ppm ppm
G X X x x


= ~ = =

105
The molar flow rate of gas is


So the required liquid flow rate is


We can also use the Henrys law expression
to estimate how thoroughly we must strip
the solvent before reusing it.

1000 2.6 1.25 1180
385.3
scf lb mol lb mol lb mol
G
min scf min s min
= = = =

0.087 2.6 0.23 44 20
lb mol lb mol lb kg
L
min min min min
= = = =
106
At the top of the column we also arbitrarily specify
that




This is a difficult but not impossible stripping
requirement.
If we substituted this value of x
i top
into the above
calculation in the place of the assumed value of
zero, it would increase the computed value of L/G
by 1%, which we ignore. #
*
6
4
0.8 0.8 50 40
1 40 10
5.71 10
0.070
toluene toluene
toluene
y y ppm ppm
atm
x
atm

= = =

= =
107
Example 15
Estimate the required column diameter in Example
14.
Solution:
The column diameter is determined almost entirely
by the gas flow rate.
Although the liquid flow rate in (mol/mol) may be
close to that of the gas, the liquid flow rate in
(vol/vol) is seldom more than 10% of the gas
because of the large difference in densities, and it is
practically ignored in sizing the column.
108
Typically, absorption columns will operate at a gas
velocity that is approximately 75% of the flooding velocity.
For most packed absorption columns, the flooding
velocity is predicted from a semitheoretical, graphical
correlation that can be satisfactorily approximated by
log = -1.6798 1.0662 log 0.27098 (log )
2
(15)
where

2 1/ 2
0.2

G
L G c L
G F L
and
g G

o |

' ' | |
+
= =
|
'
\ .
109
Here is dimensionless, with G = the gas mass
velocity = mass flow rate of gas per unit area =
GM/A, and L = the liquid mass velocity = LM/A.
Since is not dimensionless, the quantities in it
must be expressed in the following units (or suitable
conversions): G is in lb/(ft
2
s), F is a
dimensionless packing factor whose values are
presented in tables for various packings, is the
specific gravity of the liquid, is the liquid viscosity
in centipoise, the liquid and gas densities are in
lb/ft
3
, and g
c
= 32.2
110
We know that L/G = 0.087, from which it follows that



The column will operate at 1 atm and 100
o
F, at
which temperature the density of the air stream will
be about 0.071 lbm/ft
3
and that of n-tetradecane
about 47 lbm/ft
3
, so that


/ 198
0.087 0.187
/ 92
L L
G G
LM A M L L
G GM A G M
'
= = = =
'
1/ 2
1/ 2
0.071
0.187 0.0073
47
G
L
L
G

|

' | |
| |
= = =
| |
'
\ .
\ .
111
Log = log 0.0073 = -2.14 for the flooded condition.
Substituting this value in Eq. (15), we find =0.23.
We estimate the viscosity of n-tetradecane at 100
o
F
is 1.6 cp, and its specific gravity is 0.75.
For typical packed columns, F 50, and using the
units with the dimensions specified for Eq. (15), we
compute



0.2 0.2 2
0.23 47 0.071 32.2
0.77
50 0.75 1.6
L G c
at flooding
g lb
G
F ft s
o


'
= = =
+
112
At 75% of flooding G = 0.58 lb/ft
2
/s.
From Example 14 we know that the gas flow
rate is
gas
= 1.25 lb/s. Thus






2 2
2
1.25 /
2.18 0.203
0.58 / /
gas
m
lb s
A ft m
G lb ft s
= = = =
'
2
4 4
2.18 1.66 0.51 D A ft ft m
t t
= = = =
3 2
1.25 /
8.2 2.5 #
(0.071 / )(2.18 )
gas
gas
G
m
lb s ft m
A lb ft ft s s
u

= = = =
m
113
Example 16
Estimate the required column height for the
gas absorption in Examples 14 and 15.
Solution:
we return to Eq. (12) and rearrange the
rightmost two terms to find that


*
(16)
( )( )
i
i i
G
dh dY
KaP y y
=

114
Ka, product of the mass transfer coefficient and the
interfacial area between liquid and gas per unit
volume of the absorber, depends on the chemical
and physical properties of the liquid and the gas
and the geometry of the column internals, whose
function is to provide as large a value of Ka as
possible with a minimum pressure drop.
Kohl and Nielsen present a table of values of Ka
observed in industrial practice for a variety of
absorption systems. These vary from 0.007 to 20
lbmol/h/ft
3
/atm.
115
For this example we will assume that Ka is a
constant = 4.0 lbmol/h/ft
3
/atm.
We have specified that y
i
*
= 0.8 y
i
at both the
top and the bottom of the column.
We may rearrange Eq. (12) so that

( )
i top i bottom i bottom i top
L
Y Y X X
G
=
116
Then we apply Eq. (13) twice, replacing X
and Y by x and y, solve Eq. (14) for y
i
*
, and
substitute into the right side of Eq. (16),
finding
*
( )

[ (1 / ) ( / ) ( / ) )]
1 (1 / ) ( / ) ( / )
ln (17)
(1 / ) (1 / ) ( / ) ( / )
top
i
bottom
i i
top
i
bottom
i B B
T B B
B B B
dy KaPA
N h
G y y
dy
y HG pL H P x HG PL y
y HG PL H P x HG PL y
HG PL y HG PL H P x HG PL y
= =

| |
=
|
+
\ .
( +
=
(
+

}
}
117
Where N is the number of transfer
units, a measure of the difficulty of the
separation; x
B
and y
B
are the liquid and
vapor concentration at the bottom of
the column; and y
T
is the vapor
concentration at the top of the column.
The required column height is linearly
proportional to N.
118








0.070 0.070
0.070 0.805
1 0.087
H atm HG
P atm PL
= = = =
1- 0.195
HG
PL
| |
=
|
\ .
6 6
6 6
1 50 10 0.195 0.070 0.057 0.805 5000 10
ln 16.6
0.195 5000 10 0.195 0.070 0.057 0.805 5000 10
N


( +
= =
(
+

3 2
16.6 0.23 / 60min
26 #
(4 / / / ) 1 2.18
NG lbmol min
h ft
KaPA lbmol h ft atm atm ft h

= = =

119
5. Control by Oxidation
The final fate of VOCs is mostly to be oxidized
to CO
2
and H
2
O, as a fuel either in our engines
or furnaces, in an incinerator, in a biological
treatment device, or in the atmosphere (forming
ozone and fine particles).
VOC containing gas streams that are too
concentrated to be discharged to the
atmosphere but not large enough to be
concentrated and recovered are oxidized before
discharge.
120
5.1 Combustion (Incineration)
Some examples of interests are



The nitrogen and sulfur present in
compounds being incinerated normally enter
the atmosphere partly as N
2
, NO, or NO
2

and SO
2
.
The latter three are pollutants for which we
will deal with later.
2 2
6 6 2 2 2
1
2
7.5 6 3
CO O CO
C H O CO H O
+
+ +
121
For example,


In most incinerators, the chlorine content of the
material burned will leave the incinerator as
hydrochloride acid, HCl.
At incinerator temperatures some metals become
vapors, e.g., mercury, cadmium, zinc.
Their emissions can be a problem.
3 3 2 2 2
2( ) 11.5 6 9 2 CH N O CO H O NO + + +
122
5.1.1 Combustion Kinetics of the
Burning of Gases
Most combustion takes place in the
gas phase. Liquids and solids mostly
vaporize before they burn.
For chemical reactions of any kind in
any phase (gas, liquid, or solid) the
reaction rates are typically expressed
by equations of the form:
123



where r = reaction rate
k = a kinetic rate constant whose
value is strongly dependent on
the temperature but is
independent of the
concentration of the reactants
c
A
= concentration of A
n = reaction order
Decrease in concentration
(18)
of A per unit time
n
A
A
dc
r kc
dt
| |
= = =
|
\ .
124
For most chemical reactions the relation between the kinetic
rate constant k and the temperature T is given to a satisfactory
approximation by the Arrhenius equation:




where A = frequency factor which is related to the frequency
of collisions of the reacting molecules
E = activation energy which is related to the bond
energies in the molecules
R = universal gas constant
T = absolute temperature
Table 10.4 (next slide) lists values of A, E, and k, based on n =
1 for the combustion of a variety of compounds.
exp (19)
E
k A
RT
| |
=
|
\ .

126
A strong simplifying assumption in Table
10.4 is that the concentration of VOC to be
burned is much less than the concentration
of oxygen in the contaminated air stream.
The true kinetic expression is presumably


So the k in Eq. (18) is equivalent to k c
O
2
in
Eq. (20).
2
(20)
VOC
VOC O
dc
r kc c
dt

= =
127
Example 17
Show the calculation leading to the value of
k in Table 10.4 for benzene at 1000
o
F.
Solution:
21
exp
7.43 10 95, 900 /
exp
(1.987 / / )(1000 460) ( /1.8 )
0.00011/ #
o o
E
k A
RT
cal mol
s cal mol K R K R
S
| |
=
|
\ .
| |
=
|
+
\ .
=
128
Example 18
Estimate the time required to destroy 99.9% of the benzene in
a waste gas stream at 1000
o
, 1200
o
, and 1400
o
F.
Solution:
For n=1, we can integrate Eq. (18) from t=0 to t=t, finding



At 1000
o
F,



Repeating the calculation at 1200
o
and 1400
o
F, we find 49 s
and 0.2 s. #
0
0
exp[ ( )] (21)
c
k t t
c
=
0
1 1 1
t= ln ln 62,800 17.4
k 0.00011/ 0.001
c
s h
c s
= = =
129
From Table 10.4 we see that benzene is
one of the more difficult material to burn; it
has one of the lowest values of k.
We also see that it has the highest value of
E, thus showing the highest rate of increase
of k with an increase in T.
Conversely, ethyl mercaptan has the lowest
E and hence the slowest increase of k with
an increase in T.
130
If a mixture of 0.5% benzene and 0.5%
hexane were treated in an incinerator at
1000
o
F, the percent destruction of hexane
might be as predicted with Eq. (21) using
the values in Table 10.4, whereas that of
benzene would be much larger than the
value calculated the same way.
The reason is that the free radicals
generated in the burning of hexane, which is
more easily attacked, will encounter
benzene molecules and attack them.
131
Barnes et al. suggest the following as typical values of
the operating conditions of industrial gas incinerators:








The typical ways of carrying out the combustion of VOCs
are shown in Fig. 10.17 (next slide).
Gas velocity: 25~50 ft/s
Residence time: 0.2 ~ 1 s
Temperature:
Odor control 900 - 1350
o
F
Oxidize hydrocarbons 900 - 1200
o
F
Oxidize CO 1200 - 1450
o
F

133
The biggest drawback with the arrangement
in Fig. 10.17a is the high cost of the fuel.
One way to lower the fuel cost is to put a
heat exchanger into the system, as shown in
Fig. 10.17b.
Unfortunately, the hot-gas-to-cold-gas heat
exchangers are expensive and often have
severs corrosion problems.
134
The second modification of the basic idea is
to put an oxidation catalyst in the retention
chamber.
Such catalysts can cause VOC destruction
reactions to occur at much lower
temperatures than they would without a
catalyst.
Barnes et al. state that the operating
temperature of an afterburner can typically
be reduced from about 1000
o
to 1200
o
F to
about 600
o
F if a catalyst is used.
135
5.1.2 Combustion Kinetics of the
Burning of Solids
The only common fuel that will burn as a
solid is charcoal.
If a solid has a flat surface and is burning,
then we would assume that the burning rate
could be expressed in terms like (mass
burned) / [(amount of exposed surface)
(time)].
Fig. 10.18 (next slide) shows the measured
burning rates for pure carbon.

137
Example 19
How large a spherical carbon particle
can we completely oxidize in an
airstream that is held at 1000 K for 3 s?
Solution:
From Fig. 10.18 we read that the
burning rate at this temperature is
approximately r = 0.018 10
-3
g/cm
2
/s.
138
If we write a mass balance for a spherical
particle whose surface is burning away, we
find

2 2
0 0
2
2
2
( ) 2 ( )
dm dD
D rA r D
dt dt
dD r
dt
r
dD dt
r
D D t t
t
t

= = =
=
=
=
} }
139
Taking D = D
0
at time t
o
and D = 0 at time t,
we find that the largest particle that we can
completely burn in time t has the following
diameter:


Using the value of r given earlier and a
density of 2 g/cm
3
for carbon, we find


0
2
rt
D

=
3 2
5
0
3
0.018 10 / / 3
2 5.4 10 0.54 #
2 /
g cm s s
D cm
g cm


= = =
140
On Fig. 10.18, the coordinates are
logarithmic on the ordinate and some
other value on the abscissa.
One may verify that the abscissa is
(1/T) with the origin taken at the right
instead of the left.
A straight line on such a plot would
obey the Arrhenius equations.
141
Most other combustible materials (e.g.,
wood, tars, coal, etc.) will decompose
(pyrolyze) on heating, giving off combustible
gases.
For wood, the sequence is pyrolyze-
vaporize-mix with air and oxidize to give the
final products, CO
2
and H
2
O.
Because of its very low vapor pressure, pure
carbon does not give off such gaseous
decomposition products.
142
5.1.3 Mixing in Combustion
Reactions
Fig. 10.18 makes clear that mixing is
important for combustion of solids as well as
gases and liquids.
In that figure at low temperatures the
combustion rate is independent of the rate
of air movement across the surface of the
burning carbon.
But at higher temperatures the combustion
rate depends on the air flow rate.
143
At low temperatures molecular diffusion
moves the air into the solid carbon surface
and the carbon dioxide out faster than the
chemical reaction can transform them, so
the chemical reaction determines the overall
reaction rate.
At higher temperatures the chemical
reaction is so fast that it uses up the oxygen
as fast as diffusion can bring it in, and the
overall rate is determined by diffusion
(mixing).
144
5.1.4 Application to Boilers,
Furnaces, Flares, etc.
To get complete combustion with
imperfect mixing, one must supply
excess air in addition to that needed
for stoichiometric combustion in boilers
or furnaces.
Large industrial furnaces operate with
5 to 30% excess air.

145
The mixing problem is especially difficult in
flares. These are safety devices used in oil
refineries and many other processing plants.
All vessels containing fluids under pressure
have high-pressure relief values that open if
the internal pressure of the vessel exceeds
its safe operating value.
The outlet of a refinerys relief values are
piped to a flare, which is an elevated pipe
with pilot lights to ignite any released VOCs.
146
Many flares have steam jets running
constantly to mix air into the gas being
released.
These flares handle significant amounts of
VOCs only during process upsets and
emergencies at the facilities they serve.
For a large release the mixing is inadequate,
and the large, bright orange, smoky flame
from the flare indicates a significant release
of unburned or partly burned VOC.
147
5.2 Biological Oxidation
(Biofiltration)
The ultimate fate of VOCs is to be oxidized
to CO
2
and H
2
O. Many microorganisms will
carry out these reactions fairly quickly at
room temperature.
The typical biofilter (better called a highly
porous biochemical reactor) consists of the
equivalent of a swimming pool, with a set of
gas distributor pipes at the bottom, covered
with several feet of soil or compost or loam
in which the microorganisms live.
148
Typically these devices have soil depths of 3
to 4 ft , void volumes of 50%, upward gas
velocities of 0.005 to 0.5 ft/s, and gas
residence times of 15 to 60 s.
They work much better with polar VOCs,
which are fairly soluble in water than with
HCs whose solubility is much less.
149
6. Choosing a Control Technology
Fig. 10.19 (next slide) shows one
guide to choosing technology, based
only on flow rate and concentration.
Other factors, e.g., the permitted
emission regulation and the special
properties of the contained VOC are
also important.