Professional Documents
Culture Documents
Gas Transfer
Gas Transfer
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.
Liquid
Gas transfer to the liquid is absorption
A subtle distinction
Volatilization Stripping
-
2 APPLICATIONS
Stripping
1. H2S
2.
CO2
3.
O2
4.
Trace organics
5.
NH3 stripping
Absorption
1. O2
2.
SO2
3.
Cl2
(Absorption -
chlorine disinfection)
4.
O3
3 EQUILIBRIUM RELATIONSHIPS
(1)
where
Cs = saturation concentration
He = Henrys law coefficient
Pi = partial pressure of the gas
Units - One always has to make some mistakes with Henrys law coefficient. Practice
converting the units.
Frequently, He is expressed in terms of atmm3/mole then P is in terms of atm, and Cs is
in mole/m3.
Symbols for Henrys law coefficient.
He - general - dont know the units or types.
2 2
H = atmm3/mole or l /t
Hc = dimensionless - often more convenient.
Hc =
C*g (mg / L)
C L (mg / L)
16.04 P M W
TS
where
P = vapor pressure of pure solution in mm Hg
2
(2)
MW = molecular weight
T = temperature K
S = solubility of the solution in mg/L
Hc =
H
RT
(3)
where
R = gas constant 8.2 x 10-5 [atm m3/mol-K].
The greater the Henrys 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 Henrys coefficient and decreases gas
solubility.
3.1 Mehods to determine H or Hc.
The EPICS procedure (No. 4 above) is usually the easiest and most accurate method for
measuring Henrys 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 Henrys law coefficient and
M = mass of gas.
Now use two bottles, with different liquid volumes, VL1 VL2 and apply the same
equation, as follows:
(7)
M1 = C L1 (VL1 + Hc VG1 )
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
C L1
(9)
(VL1 + H c VG1 ) = L2 (VL2 + H c VG2 )
M1
M2
Solves for Hc, as follows:
Hc =
VL2 rVL1
rVG1 VG2
(10)
where
C M
r = L1 2
C L2 M1
(11)
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).
(12)
where
He Henrys law coefficient
R Universal gas constant
H heat of absorption (< 0)
T absolute temperature
Hc
Cs
Henrys is only good for gaseous part of the dissolved gas. For example, consider sulfur
dioxide, which is equilibrium with sulfurous acid, as follows:
SO2 + H2O HSO3- + H+
[H+ ][HSO3 ]
-2
Ka =
= 1.7 x 10
[SO2 ]
+
(13)
(14)
(15)
-2
1.7 x 10 [SO 2 ]
[H ] =
(1.8 [SO 2 ])
+
Cs =
0.2095
-6 gmole O2
4 = 4.98 x 10
gmole H2 O
4.01x10
C s = 4.98 x 10
-6
32g O 2 gmole O 2
-6 g
= 8.86 x 10
g
18g H 2 O gmole H 2O
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:
kL = 2
where
tc
D
tc
(20)
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.
Interface
Pb
Pi
Bulk
Gas
CLi
Bulk
Liquid
CLb
L
stagnant
liquid
film
stagnant
gas
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 Henrys Law
Let No (
mass
) represent the mass transfer of oxygen at steady state conditions:
time
N oG = NoL
(no accumulation in gas of liquid films)
(22)
PM
P M
N oG = k Ga b w i w
RT
RT
N oL = k La (C Li C Lb )
where
DO 2 L
[length]
L
[time]
DO 2 G [length]
kG = gas film mass transfer coefficient =
,
G
[time]
(23)
(24)
[length]2
DO2L = diffusion coefficient of oxygen in liquid film,
[time]
[length]2
DO2G = diffusion coefficient of oxygen in gas film,
[time]
L = liquid film (boundary layer) thickness, [length]
G = 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.
(25)
(26)
Pi = H CLi
(27)
where
2
[length]
H = Henrys coefficient for O2 in water,
[time]2
C* = Concentration of oxygen in water in equilibrium with bulk gas partial
[mass]
pressure,
[length]2
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 Henrys coefficient = H W , [ - ]
RT
we get
*
kG Hc C HcC Li = k L (CLi CLb )
(28)
(29)
(30)
k H C* + k C
L Lb C
= k L G c
Lb
k L + kGH c
k H C* + k C k C k H C
L Lb
L Lb
G c Lb
= k L G c
kL + k GHc
k H C* k H C
G c Lb
= k L G c
+
k
k
GH c
L
k k H
= L G c C*
C Lb
k L + k GH c
k
= k L
C* CLb
L +1
k GHc
(31)
(32)
(33)
(34)
(35)
Now let
kL
= KL
kL
+1
kGH c
(36)
where
KL = overall mass transfer coefficient,
we get
[mass]
[time]
N o = K L C* C Lb
(37)
*
N o = K G Pb P
(38)
where
*
= Partial pressure of oxygen in gas in equilibrium with bulk liquid
P
[mass]
*
P
concentration,
= HCLb
2
[length][time]
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
=D 2
t
z
CL
(39)
(40)
(41)
then
C'
L 3 = sC'
t
2 C'
2 C'
L 2 = D 2
Z
Z
so
10
(42)
(43)
sC' = D
2
C'
Z 2
(44)
Solution in
C' = B1e
Z sD
+ B2 e
Z s D
(45)
at boundary, z = 0
C' = C* C L
0
C o' = Co ' e st dt =
Co '
s
(46)
Therefore
B2 =
at the exit boundary
C'o
s
C ' = 0
we get
C o ' Z
C' =
e
s
s
D
(47)
Z
2 Dt
(48)
definition of Erfc is
erfc =
so we get
2 Z2
df
e
C'
C CL
2
= *
=
C o' C C L
Z 2
(49)
-
Dt
Z2
4Dt d
Z
2 Dt
11
(50)
(51)
(52)
(53)
Interface
fresh water replaces the film
t =
A(t) t =
=
rs
(54)
renewal time
old surface area (area x length of contact)
rate of production of fresh surface area.
(55)
(56)
1 = A(t)dt = 1
(57)
= Ke rst dt
(58)
A(t) = rs e rs t
substitute into equation (51)
(59)
0
N o = (C CL )
*
N o = 2(C
D rs t
r e dt
t s
12
2
1 2D
CL )rs
e d
0
(60)
(61)
where = rst
r D 1 2 1 2
N o = 2(C* CL ) s
2
12
(62)
= 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 Henrys 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
Consider a mass balance on a single rising bubble.
CL
C*L
CG
Vb =
dCg
dt
13
(64)
where
Vb
Ab
CL
=
=
CL =
=
Vb
d(C*L Hc )
= K L (Ab )(C L C*L )
dt
dC*L
KL Ab
dt
* =
C L CL
HcVb
(65)
(66)
now, we let
VG
= gas retention time
QG
Z Z
vb = s
= bubble velocity
tr
tr =
where
Zs
Z
=
=
n
VL
VG
=
=
=
=
=
AB
(68)
= B L =a L
Vb
VB
VL nVb VL VG
VG
where
(67)
(69)
dCL
KL aVL
K aV
dt = L L dt
* =
C L CL
Hc VG
H cQ G t r
ln C L C*L =
where
K L aVL t
+K
QG Hc t r
K = integration coefficient.
14
(70)
(71)
at t = 0
ln C L C*L
t= 0 =
(72)
C
*
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
=
CL
QG Hc t r
(73)
K L aVL t
C*L
Q GH c t r
1
=e
CL
(74)
K L aVL t
C*L
= 1 e Q GH c t r
CL
(75)
Remember that
C*L =
CG
Hc
CL =
and
CG
Hc
CG
C H
C*L
=
= G *c
C L Hc CL H c CG
K L aVL t
tr
CG
Q GH c
* = 1 e
CG
(76)
(77)
CG
= saturation factor. We are only interested in t = tr (bubbles existing in
C*G
the liquid), so t/tr = 1.
Define Sd =
K L aVL
= (Zs )
QG Hc
Let
(78)
Zs denotes that is a function of depth. KLa will be a function of depth, bubble size,
temperature, and other system parameters. will be a constant for a given system at
steady state conditions.
Now we perform a balance on the entire reactor, liquid phase.
VL
dC L
= Q G C GI Q G CGE
dt
(79)
VL
dC L
= QG C L Hc
dt
(80)
assume CGI = 0
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
(81)
= Q G CL Hc[1 e (Z s ) ]
dt
ln
CL
QG Hc
=
Sd (t t o )
C Lo
VL
(82)
CL
vs. t
C Lo
Slope =
-Q G H c
Sd
VL
(83)
K L = D tc
for penetration
for surface renewal
K L = D rc
(84)
(85)
(86)
let
where
K L a VOC
= VOC
DO 2
= VOC
DO 2
0.5 n 1.0
12
K La O2
(88)
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.
Generally for surface aeration
16
dC VOC
= K L a VOC (C L C*L )
dt
K L a VOC
= VOC
DO 2
(89)
0.6
where Hc > 1
KLa O 2
(90)
(91)
Use
RL
RL
=
R T RL + R G
1
1
=
=
R
1
1+ G 1 +
k
RL
Hc G
kL
R D
= L VOC
R T DO 2
17
(93)
(94)