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GasTransfer PDF
GasTransfer PDF
GasTransfer PDF
0 GAS TRANSFER
An important process used in water and wastewater treatment. Also very important when
analyzing the impact of pollutants on the environment, such as discharging partially
treated wastewaters to the stream.
Gas/Liquid Interface
Liquid
A subtle distinction
Volatilization - Stripping due to natural phenomenon.
Stripping - Stripping due to a mechanical device - aeration.
2 APPLICATIONS
Stripping
1. H2S Sour water in refineries, taste and odor removed in drinking
water treatment, unwanted loss of H2S in septic sewers
causing pipe corrosion.
Absorption
1. O2 (In treatment plants - biological ~ 60% of the energy
consumption)
(water treatment - oxidation of Fe+2, Mn+2) - River aeration
1
2. SO2 (Absorption for dechlorination)
3. Cl2 (Absorption -
chlorine disinfection)
3 EQUILIBRIUM RELATIONSHIPS
Liquid ⇔ Gas
CsHe = Pi (1)
where
Cs = saturation concentration
He = Henry’s law coefficient
Pi = partial pressure of the gas
Units - One always has to make some mistakes with Henry’s law coefficient. Practice
converting the units.
Frequently, He is expressed in terms of atm⋅m3/mole then P is in terms of atm, and Cs is
in mole/m3.
where
P = vapor pressure of pure solution in mm Hg
2
MW = molecular weight
T = temperature K
S = solubility of the solution in mg/L
H
Hc = (3)
RT
where
R = gas constant ≡ 8.2 x 10-5 [atm m3/mol-K].
The greater the Henry’s law coefficient, the greater the volatility and the less solubility.
It is valid for dilute solutions and non-reacting gases at near ambient pressure and
temperature. Ionic strength increases the Henry’s coefficient and decreases gas
solubility.
The EPICS procedure (No. 4 above) is usually the easiest and most accurate method for
measuring Henry’s coefficients.
M = CL VL + CG VG (4)
M = C L VL + (HcCL )VG (5)
M = CL (C L + H c VG ) (6)
where
CL = liquid phase concentration,
VL = liquid volume,
CG = gas phase concentration,
VG = gas volume,
Hc = dimensionless Henry’s law coefficient and
M = mass of gas.
Now use two bottles, with different liquid volumes, VL1 ≠ VL2 and apply the same
equation, as follows:
M1 = C L1 (VL1 + Hc VG1 ) (7)
M2 = CL2 (VL2 + H cVG2 ) (8)
3
After dividing equation 7 by M1 and 8 by M2, the left hand sides become unity, so we can
equate the two, as follows:
C L1 C
(VL1 + H c VG1 ) = L2 (VL2 + H c VG2 ) (9)
M1 M2
Advantages
We do not need to measure M2 and M1 - we only need to measure their ratio. The
ratio can be determined gravimetrically or through some other procedure.
Similary, we only need the ratio of CL1 and CL2, which can be measured as a ratio,
as opposed to an absolute concentration (e.g., ratio of peak heights on the GC, as
opposed to the actual concentration).
d(ln H e ) ΔH
= (12)
d(1/ T) R
where
He ≡ Henry’s law coefficient
R ≡ Universal gas constant
ΔH ≡ heat of absorption (< 0)
T ≡ absolute temperature
Cs Hc
T T
4
Henry’s is only good for gaseous part of the dissolved gas. For example, consider sulfur
dioxide, which is equilibrium with sulfurous acid, as follows:
[H+ ][HSO−3 ] -2
Ka = = 1.7 x 10 (14)
[SO2 ]
+ −
[H ][HSO3 ] = 1.7 x 10 -2 [SO 2 ]
[SO2 ]
[H + ] = 1.7 x 10 -2
[HSO3− ]
-2
+ 1.7 x 10 [SO 2 ]
[H ] =
(1.8 − [SO 2 ])
0.2095 -6 gmole O2
Cs = 4 = 4.98 x 10
4.01x10 gmole H2 O
-6 32g O 2 gmole O 2 -6 g
C s = 4.98 x 10 x = 8.86 x 10
18g H 2 O gmole H 2O g
5
31, pp. 365-389.
4.1 Theories
We can derive the three theories, but the overall difference and conclusions will relate to
the impact of D upon kL , as follows,
Two Film:
kL ≈ D (molecular diffusivity)
Penetration:
D
kL = 2 (20)
tc
where tc = contact time
Note that transfer is greatest for the shortest contact time. kL tends to zero for long
contact times.
Surface Renewal
k L ≈ D rc (21)
where rc is a surface renewal rate, related to the rate of production of fresh surface.
We can derive the theories as follows, beginning with two film and progressing with
increasing complexity.
6
4.2 Two Film Theory
Interface
Pb
• Pi
Bulk
• Bulk
Gas
CLi • Liquid
•
CLb
δG δL
stagnant stagnant
gas liquid
film film
Assumptions:
1. Linear concentration profile through stagnant film
2. Steady state conditions
3. Instantaneous equilibrium
4. Transport by bulk diffusion is not limiting
5. Dilute solutions, therefore apply Henry’s Law
mass
Let No ( ) represent the mass transfer of oxygen at steady state conditions:
time
N oG = NoL (no accumulation in gas of liquid films) (22)
7
[length]2
DO2L = diffusion coefficient of oxygen in liquid film,
[time]
[length]2
DO2G = diffusion coefficient of oxygen in gas film,
[time]
δL = liquid film (boundary layer) thickness, [length]
δG = gas film (boundary layer) thickness, [length]
a = interfacial area, [length]2
[mass]
CLi = concentration of oxygen in liquid film at interface,
[length]3
[mass]
CLb = concentration of oxygen in bulk liquid,
[length]3
[mass]
Pi = partial pressure of oxygen in gas film at interface,
[length][time]2
[mass]
Pb = partial pressure of oxygen in bulk gas,
[length][time]2
MW = molecular weight.
The goal is to solve for interfacial concentration, CLi, because this quantity is essentially
impossible to determine. Substitute (26) and (27) [eliminate a] into (25) and let
⎛M ⎞
H = dimensionless Henry’s coefficient = H ⋅ ⎜ W ⎟ , [ - ]
⎝ RT ⎠
we get
( )
kG Hc C∞ − HcC Li = k L (CLi − CLb )
*
(28)
8
Solve for CLi
C Li(k L + k GHc ) = k GHc C*∞ + k L CLb (29)
k G H c C*∞ + k L CLb
C Li = (30)
k L + k GHc
= k L
k
L +1 ∞ (
C* − CLb ) (35)
k GHc
Now let
kL
= KL (36)
kL
+1
kGH c
where
[mass]
KL = overall mass transfer coefficient,
[time]
we get
(
N o = K L C*∞ − C Lb ) (37)
( *
N o = K G Pb − P∞ ) (38)
where
*
P∞ = Partial pressure of oxygen in gas in equilibrium with bulk liquid
concentration,
[mass]
[length][time]2
*
P∞ = HCLb { }
9
4.3 Penetration Theory
We assume a non-steady-state film, which at the moment of film formation, curtains the
bulk concentrations in both the gas and liquid phases.
interface
bulk liquid
C* 2
∂C ∂ C
C =D 2
∂t ∂z
CL
δz
0 z
10
2
∂ C'
sC' = D (44)
∂Z 2
Solution in
Z sD −Z s D
C' = B1e + B2 e (45)
at boundary, z = 0
C' = C* − C L
0
Co '
C o' = ∫ Co ' e −st dt = (46)
∞
s
Therefore
C'o
B2 =
s
definition of Erfc is
2 ∞ − Z2
erfc α = ∫ e df (49)
τ α
Z2
C' C − CL 2 ∞ - Z
so we get = *
C o' C − C L
=
π ∫Z 2 Dt
e 4Dt d
2 Dt
(50)
D *
= −2 (C − C L ) (53)
tc
11
4.4 Surface Renewal
Interface
fresh water replaces the film
12
*
= 2(C − CL ) Drs (63)
The three theories produce similar results in that they envision two resistances, gas and
liquid, and the proportion of the total resistance is dependent upon the Henry’s law
coefficient. High coefficients mean high liquid phase resistance and low gas phase
resistance.
There are important differences in the implications of the theories when one must
consider the impact of contaminants (surfactants) on gas transfer and when one tries to
predict the transfer rate of one gas (e.g., a VOC like benzene) from the transfer rate of
another gas (e.g., oxygen). This is related to the molecular diffusivity, D or D1/2. Most
experimental observations for the power of D are between 0.5 and 1.0, with higher
turbulence being closer to 1/2.
Volatile Organic Compounds transfer is the new concern for wastewater treatment plants.
Such compounds include:
Benzene
Toluene
TCE
TCA
CL
C*L
CG
dCg
Vb = = K L a(A b ) *(CL − C*L ) (64)
dt
13
where Vb = single bubble volume (l3)
Ab = area of a single bubble (l2)
CL = liquid VOC concentration
*
CL = equilibrium VOC liquid concentration
= CG/Hc
d(C*L Hc )
Vb = K L (Ab )(C L − C*L ) (65)
dt
dC*L KL Ab
* = dt (66)
C L − CL HcVb
now, we let
VG
tr = = gas retention time (67)
QG
Z −Z
vb = s = bubble velocity (68)
tr
A b A B nA b VL A V V
= = ⋅ = B⋅ L =a L (69)
Vb VB VL nVb VL VG VG
K L aVL t
ln C L − C*L = − +K (71)
QG Hc t r
14
at t = 0
ln C L − C*L t= 0 = C (72)
*
at t = 0, the has is entering the liquid is air, which is clean. Therefore, C L = 0, then C =
ln CL.
*
C − CL −KL aVL t
ln L = (73)
CL QG Hc t r
K L aVL t
− ⋅
C*L
1− =e Q GH c t r
(74)
CL
K L aVL t
− ⋅
C*L
= 1 − e Q GH c t r (75)
CL
Remember that
*
CG CG
C*L = and CL =
Hc Hc
C*L CG C H
= = G *c (76)
C L Hc CL H c CG
K L aVL t
− ⋅
CG Q GH c tr
* = 1− e (77)
CG
CG
Define Sd = = saturation factor. We are only interested in t = tr (bubbles existing in
C*G
the liquid), so t/tr = 1.
K L aVL
Let = φ (Zs ) (78)
QG ⋅ Hc
Zs denotes that φ is a function of depth. KLa will be a function of depth, bubble size,
temperature, and other system parameters. φ will be a constant for a given system at
steady state conditions.
dC L
VL = Q G C GI − Q G CGE (79)
dt
assume CGI = 0
dC L
VL = − QG C L Hc (80)
dt
15
if the gas is in equilibrium with the liquid; however, we know the value of CGE, from
equations (78) and (79).
VL dC L
dt [
= − Q G CL ⋅ Hc[1 − e − φ(Z s ) ] ] (81)
integrating
CL − QG Hc
ln = Sd (t − t o ) (82)
C Lo VL
CL
Plot ln vs. t
C Lo
-Q G H c
Slope = Sd (83)
VL
Experimental observations of n show that the model ranges between surface renewal and
two-film (1.0). We define two resistance theories as the two-film theory with n variable
from 0.5 to 1.0, as required to fit the experimental conditions.
16
dC VOC
= K L a VOC (C L − C*L ) (89)
dt
0.6
⎡D ⎤
K L a VOC = ⎢ VOC ⎥ KLa O 2 where Hc > 1
⎣ DO 2 ⎦
RL RL
Under these cases use the ratio of =
R T RL + R G
1 1
= = (93)
R 1
1+ G 1 + k
RL Hc G
kL
n
R ⎡D ⎤
Use ψm = L ⎢ VOC ⎥ (94)
R T ⎣ DO 2 ⎦
with 0.5 ≤ n ≤ 1.0
17