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Absorption of nitrogen oxides was studied in three packed columns in series. Two
were 254 mm ID and 6 m tall, the third was 800 mm ID and 3 m tall. Absorption
f was alsostudied in two packed columns of 800 mm ID, 7 and 10 m tall, operated
in series. Solutions of mixed nitric and sulfuric acids were used as absorbents. Specific
rates of absorption were measured using a stirred cell with a flat interface.
A mathematical model is developed for an adiabatic operation. The gas phase
reactions and equilibria, gas phase mass transfer, interface equilibria, and liquid
phase reactions are included in the model. Heterogeneous gas-liquid equilibria are
included in the model for the first time. The variation in the rates of absorption
with chemical reaction (of NOb N203, and N204) with respect to acid concentration
is considered. The formation of nitric acid in the gas phase is also considered in the
model. Favorable agreement is shown between the model predictions and the ex-
perimental observations.
Introduction
Absorption of NOx gas is an important step in the manu- For the process design of NO< absorption towers, it is nec-
facture of nitric acid. The removal of NO. from the off-gases/ essary to understand the combined effects of several equilibria,
flue gases has received considerable attention due to stringent the rates of mass transfer, and chemical reaction. Further,
f statutory regulations' for a clean environment. substantial heat effects are associated with NO. absorption;
Absorption of NOx gas is probably the most complex when therefore, temperature variations need to be taken into account
compared with other absorption operations. The reasons are: in the process design, There have been outstanding attempts
I. The NOx gas is a mixture of several components consisting in this direction. For instance, Koval and Peters (1960),
of N20, NO, N02, N20J, N204, N20s, etc., and the absorption Andrew and Hanson (1961), Koukolik and Marek (1968),
of NO. gas in water results into two oxyacids, nitric acid and Carleton and Valentin (1968), Hoftizer and Kwanten (1972),
nitrous acid. Makhotkin and Shamsutdinov (1976), Holma and Sohlo (1979),
2. Several reversible and irreversible reactions occur in bbth Emig et al. (1979), Counce and Perona (1979a,b, 1980, 1983),
gas and liquid phases. Joshi et al. (1985), and Selby and Counce (1988) have reported
3. Simultaneous absorption of many gases occurs followed various aspect,s of the process design of packed columns, plate
by chemical reaction. Also, simultaneous desorption of many columns, and packed bubble columns used for the manufacture
gases occurs preceded by chemical reaction. For example, the of nitric acid, These attempts will be strengthened if the fol-
absorption of N02, N203' and N204 is accompanied by chem- lowing important features are included in the-'process design.
ical reaction whereas the desorption of NO, N02, and HN02 I. The rates of absorption of N02, N203' and N204 in nitric
is preceded by chemical reaction. acid are different from those in water. The rates decrease with
4. Heterogeneous equilibria prevail between gas phase and .
an increase in the concentration of nitric acid.
liquid phase components. 2. It is known that, for a given set of partial pressures of
Sherwood et al. (1975) and Joshi et al. (1985) have reviewed NO, N02, and N204' there exists a certain limiting concentra-
these aspects of NO. absorption. tion of nitric acid beyond which no absorption of N204 and
N02 occurs (Carberry, 1958). This heterogeneous equilibrium
Correspondence concerning this arllde should be addressed to j. B. Jo~hi. substantially reduces (even three !O four times) the rates of
.-p'..; ~
absorption of NOz. NZ03. and NZ04, and the extent of re- Table 1. Gas Phase Reactions
duction increases as the nitric acid concentration approaches Eq. No. Equilibrium and Rate Constants
the equilibrium value. This aspect has not been included in the
mathematical models reported so far. I loglO K, = 652.lIT - 0.7356 atm - I.S - I
2 loglo K2 = 2,993/T - 9.226 "atm-'
3. A substantial quantity of nitric acid is formed in the gas
3 log,o KJ = 2,072/ T - 7.234 atm - I
phase. particularly at high temperatures and high partial pres- 4 log,o K4=2,051.l7/T-6.7328 atm-I
sures of NOx- Therefore, HNO) formation needs to be included 5 log,o K5 = 2,OO3.8/T- 8.757 atm-'
in the mathematical model.
4. A detailed energy balance also needs to be incorporated
in the model.
The mathematical model presented in this work includes the constants Kz . . . K5 were reported by Joshi et al. (1985) and
above four features. are summarized in Table I.
Simulation of large-size absorbers increases confidence in Rates of Gas Phase Mass Transfer. The concentration pro-
the model development. In the published literature. although files for the gas film are shown in Figure 1. The volumetric
some experimental data have been collected on pilot-scale ab- rates of gas phase mass transfer are given by the following
sorbers, the absorbent was invariably water except in the in- equations:
vestigation carried out by Counce and Perona (1983). There
is scant information available regarding large-scale simulation. RaNO.G= (k~)NO [PNO- p~o] (6)
Further. there has been no study when the nitric acid contains
? some other electrolyte. Therefore, it was thought desirable to
simulate large-scale absorbers. Solutions of mixed nitric and
RaNOZ.G = (kG~)NOZ [P~oz - PNOZ] (7)
vations.
RaNZ03.G = (k~)NZO) [P~Z03 - PNZ03] (9)
~
NO
PNO
2NO + 02-2N02- P
N02
2N02 ~ N20,,-PN
- 20 4
3HN02
NOi'NOit-H20 ~ 2HNOt-PHHO
2
1
P~N02
i
PH 0
I
BULK GAS I I
GAS FILM I I LlOUID FILM I
IBULK LIQUID
I
P~203 (14)
N204(/) + H20(/) - HN02(/) + HN03(/) (21)
K3= .
(PNO) (PN02)
HN02 in bulk in the liquid phase is considered to be decom-
. posing to form nitric acid:
)2
(PHN02
K4=. .
(PNO) (PN02)
.
(PH20)
(15)
3HN02(/) - HN03(/) + 2NO(/) + H20(/) (22)
HN03 and H20 are at their saturation concentrations at the Mass Transfer with Chemical Reaction in the Liquid
o~erface. The vapor pressure of H20 or HN03 over aqueous Film. The concentration profiles for different species in the
sulfuric acid solution is a function of temperature and nitric liquid film are given in Figure 1. It has been illustrated by
acid concentration: Joshi et al. (1985) that the absorption ofN02, NP3, and N204
is accompanied by chemical reaction within the liquid film.
p~20=f [T, conc(HN03)] (16)
However, absorption of NOx is also limited by nitric acid
concentration in the liquid phase bulk and the partial pressure
(17)
PHN03= f[T, cone (HN03)] of NO at the interface. Carberry (1958) made a plot of max-
imum attainable concentration of nitric acid as a function of
P~ Hx= [A *]x
(18) parameter K6 defined as
2N02(l) + H20(/) - HN03(/) + HN02(l) (19) InKH = 2.188 X 107 12.58 - 4.571 X 104 11.424W (24)
.
2. Liquid holdup is uniform throughout the column
force is thus the difference between the interfacial and limiting
3. Gases follow ideal gas behavior
partial pressures of N02, N204, N203, and HN02.
4. The column operates at steady state
The volumetric absorption rates of different species are:
Mass Balance. Mass balance across a differential heigh!
dh at height h from the bottom, Figure 2, results in the fol.
RaN02.L=~ (HNo2)3/2 [2/3 (kD)NOil2 (Pf-l02-P~02)3/2 (29) lowing differential equations.
Component balance in gas phase
RaN204.L =~ HN204 [(kD)N20JI/2 (P~204 - P~204) (30)
a. Divalent nitrogen balance
RaN203.L =~ HN203 [(kD)N20i/2 (P~203 - P~203) (31)
.
RaHN02.L = kL~ HHN02 (PHN02 - b
PHN02) (32)
GAS OUT IN
Nitrous acid in bulk decomposes to form HN03 and NO in ~LlQUID
the liquid phase. Since the latter has limited solubility, it de-
sorbs. The rate of desorption of NO is given as
4 2 1 2
RaNO.L =)" RaN203.L +)" RaN204.L + )"RaN02.L + )"RaHN02,L
(33)
.
and HNO 3 at mter f ace. . PNO,
i
RaN204.G,
2. Partial pressures of NO, N02, N204, N203, HN02, H20,
i I i I I
RaN20.G, RaHN02.G, RaHN03.G, RaH20,G
1
dh
H
-~
,
'
' '
acid (at the top of the column) are known. The equations were ...... .......
10
solved simultaneously by the fourth-order ", ,
Runge-Kutta
method. To start the integration procedure, the concentration o ',3
of oUtgoing nitric acid (at the bottom of the column) was o 10 15 20 25 30 35
'0 '5 50
assumed. Integration was carried out up to the top of the WEIGHT PERCENT,NITRIC ACID
column. A comparison was made between the calculated and Figure 3. Effect of nitric acid concentration on e;
the actual concentration of nitric acid. For convergence, the of NOx absorption.
guess value at the bottom of the column was varied using the NOx flow rate 0.99 x IO-'kmol/s
=
method of interval halving. Inerts flow rate=2.15x 1O-4kmol/s
Liquid inlet temperature
303 K
Liquid superficiaJ velocity=
5. Solution of heat balance equations -Air = 7 mm/s
flow rate 5.1 X 10-4 kmol/s
=
From steps 1-4 the concentrations of all the species are
'Uu Air flow rate
=0.0 kmol/s
known at the inlet and exit of a differential height. The rates
of chemical reaction and mass transfer are also known. As-
suming that all the sensible heat is taken up by the liquid phase,
Figure 3 shows the relative importance of the rate dep
the change in temperature across the differential height was
ences on the :--JHO)concentration and the heterogeneous e
estimated. For this purpose Eqs. DI-D27, appendix D, were
libria. In one set of experiments (solid lines) air was adde
used.
NOr gas, whereas in the second set (broken lines) air was
added. In both of the sets the rate dependence on HNO) ,
centration has a small effect on the extent of NOr remo
Discussion of the Model However, the heterogeneous equilibria markedly influence
In the mathematical model developed in this work, four new rates of absorption. First of all, the heterogeneous equilil
features have been included: successfully predict the maximum attainable
I. The reduction in the rates of absorption of :--JOz, :--JzO), HNO) for a given gas phase NO, composition concentratior
and temperat
and :--J.O.!with respect to HNO) concentration was included (for instance, 54% in set I and 39070in set 2). If this feat
by seJ;cting appropriate values of H(kD)'/z in Eqs. 29, 30, is not included, then it can be seen from Figure 3 that
and 31. The values of H(kD)lIz for the case of absorption in extent of NO, removal does not depend appreciably on HN
Water have been summarized by Joshi et al. (1985). The var- concentration.
iation of [H( kD)I'ZJNz04 with respect to HNO) concentration The role of heterogeneous
equilibria with respect to N
has been reported by Lefers and Van der Berg (1982). The composition is shown in Figure 4. It can be seen that the extc
same variation was assumed in the case of NOz and NzO) of NOr removal strongly depends upon HNO)
absorption. The effect of energy balance is shown in Figureconcentratio
5. It can
2. The heterogeneous equilibria between gas and liquid phase seen that the rise in temperature, as expected, reduces the exte
species have been included through Eqs. 23-28. of absorption. Therefore, the extent of NO; removal in tJ
3. Complete heat balance has been established. isothermal case is higher than in the adiabatic case. It is obviol
4. Provision was made for the formation of HNO) in the that the difference in these two cases will depend upon tt
gas phase, Eq. 5. temperllture difference across the column.
Some results will now 5e given to demonstrate the relative The formation of HNO) in the gas phase was found to t
importance of these features. substantial when NO~ partial pressure and temperature af
high. It was found that the gas phase HNO, formation ca
328
March 1991 Vol. 37, No.3
AIChE Journa
I 80
idation. These two opposite factors result in an optimum flow
i
.\ I rate. Joshi et al. (1985) have discussed this subject in detail.
-llI
Experimental Work and Discussion
60
Measurement of specific rates of absorption
::
..
For the estimation of rates of absorption, it is desirable to
o know the values of diffusivity, rate constant, and orders with
Z
II.
o
'0 respect to different species. The measurement of these indio
....
vidual parameters is extremely difficult. Fortunately, the rates
~ of absorption can be determined if we know the value of the
o>
% combined parameter Hx(kD)V2 as described by Eqs. 29, 30,
UI
ex: 20 and 31.
Experiments for determining Hx(kD)V2 values for N02 and
N204 in water and mixed solutions of nitric and sulfuric acids
7 were conducted in a stirred cell of 95 mm ID. Temperature
was maintained by using a constant-temperature bath. The
o
o 0'2 0,' 0-6 0-8 ,.0 experimental setup is shown in Figure 8.
N0',/ tt" A gas stream constituting 19-20% NOt was obtained as a
Figure 4. Effect of nitric acid concentration on extent
product gas from the pilot plant for producing oxalic acid.
of NOx absorption.
The gas stream was at 65C and contained water vapor. The
I stream was passed through a condenser where the outlet tem-
I Packed column dia. ;
0.6 m, hI. ; 1.0 m
U Packing; 38 mm Intalox saddles
,5 Liquid superficial veloc. ; 6 mm/s
Gas superficial veloc. ; 0.1 m/s
kaO; 1.25 x 10-' kmol/mJ's'(kN/m')
!nt kLa; 1.5x 10-"5-1
'00
0';125 m'/mJ
Liquid inlet temp. ; 298 K ,
Total press.; 101.33 kN/m' 2
NO, gas partial press.; 10 kN/m'
Case I. Model predictions excluding heterogeneous equilibria and 80
,3
rate dependence on nitric acid concentration
Case 2. Model predictions excluding heterogeneous equilibria and ::
including rate dependence on nitric acid concentration ..
Case 3. Model predictions including heterogeneous equilibria and 0
Z 60
rate dependence on HNOJ concentration
II.
Line No. Case HNO, Outlet Conc.. wI. 07. 0
Any -'<
1
ld. 2
>
2 15
ui. 3 2 30
~'0
UI
4 2 45 a:
.10
5 15
:tJI 6 30
'no 7 45
al.
h~
'la contribute up to 20070to the overall rate of absorption when 0.5 ,.0 ,.5 2.0
of NO" IN" is 0.1 and at 30C. The contriburion was found to HEIGHT IN METERS
.re increase with an increase in temperature.
.re Figure 5. Effect of isothermal/adiabatic operation on
The effect of temperature on the extent of NO" removal is
he shown in Figure 6. At low HNO) concentrations, NO< removal extent of NOx absorption.
0, is practically independent of temperature. However, at high Packed column dia. ;
0,6 m
Packing; 38 mm Intalox saddles
HNO) concentrations an optimum temperature was observed. Liquid superficial veloc.; 4 mm/s
0, At low temperatures, NO oxidation and the formation of N204 Gas superficial veloc. ; 0, I m/ s
:TIt kaO;4.9x 1O-4kmol/mJ's.(kN/m')
are favored. However, the value of absorption parameter kLa;2.36x IO-"s-I
:'11, H(kD)I/2 increases with an increase in temperature. The com- 0';154 m'/mJ
Je Liquid temp. ; 323 K at 0 m hI.
bined effect of the above two factors results in an optimum
:Jt Total press. ; 709.0 kN/m'
temperature. It may be emphasized that the relative importance NO, gas partial press.; 77 kN/m' -
~e
of the above two factors depends upon HNO) concentration NO'/N';0,5
~\
and column height. Line No. HNO, Cone" WI. 070 Case
~ The effect of air flow rate on the extent of NO< removal is . 1 10 Isothermal
shown in Figure 7. It can be seen that NO" absorption is 2 10 Adiabatic
Ie maximum when the air flow rme is 4 x 10-4 kmol/s. An in- 3 30 Isothermal
te 4 30 Adiabatic
crease in the air flow rate increases the oxygen partial pressure, 5 50 1sothermal
~ 6 50
whereas it decreases the gas phase residence time for NO ox- Adiabatic
70
10 'I.
--20'1.
60
100
;:: -30'1.
90
>C >C
a a
z 50 z 80
I>.
I>. '0 'I. a 70
a ....I
I
<t ~60 1.10
-4 kmol/s
a NO. FLOW
~% '0 %
IU 50 COl FLOW
=
2'15.U)4kmol(s
=
LI.I 0::
0:: NO"/NO~ = 2.5
30
INLET HNO, CONCENTRATION = 0 'I, wt/wt
50 'I.
INLET TEMPERATURE = 303 K
SUPERFICIAL LIQUID VELOCITY =
7 mm Is
20 10
5 10 15 20 25 30 35 50 55
'0 '5
TEMPERATURE, "c
o ,
o 2 6 8 10 12
Figure 6. Effect of temperature and nitric acid concen. AIR FLOW RATE IN k malls. 104
tration on extent of NO" absorption. Figure 7. Effect of air flow rate on extent of NO" al
Packed column ilia. =0.6 m, hI. = 0.5 m sorption
Packing = 38 mm Intalox saddles
Liquid superficial veloc. = 6 mm/s
Gas superficial veloc. =0.1 m/s
kaD= 1.25 x 1O-3kmollm3.s.(kN/m2) for NO
kLa= 1.5 x 1O-2.s-1 of NOz. The gas stream was introduced to the stirred Cf
a~125 m2/m3 through a rotameter. The flow rate was adjusted'in such a w,
Total press. = 303.33 kN/m'
NO, gas partial press. = 33 kN/m2 that the extent of absorption was less than 10070.This elirn
NO'/N" = 0.05 nated the uncertainty regarding gas phase backmixing becau
O2 partial press. = 10"10excess the extreme plug flow and back mixed behaviors will differ tl
H20 partial press. = satUrated
rates of absorption by about 5070. We assumed complete
backmixed behavior.
perature was controlled to equal the desired temperature in In all the experiments, the absorbent quantity was 120 rn
the stirred cell. The gas stream leaving the condenser was and absorption was carried out for 300 s. During this peri,
saturated with water vapor. It was analyzed for divalent and there was no appreciable change in the absorbent quanti
tetravalent nitrogen oxides. Over 96070of NOx was in the form because of either evaporation or condensation,
WATER IN
CD STrRRED CELL 95 mm DIAMETER
WATER EJECTOR
o CONSTANT TEMPERATURE BATH
CD TEMPERATURE CONTROLLER
o HEATING PAD
G)
TT
o ROTAMETER
G) WATER JET EJECTOR
CD
CD
Figure 8. Experimental setup in stirred cell.
that the value decreases with an increase in the concentration 5 2.70x 10-6 36.36
of nitric acid. Further, [H(kD)1/2]NZ04 was found to increase 10 2.168xlO-1i 38.55
with an increase in temperature. It was thought desirable to 15 1.44 x 1O-1i 41.93
'-.. 20 O.519x 10-6 47.97
develop a correlation for [H(kD)II2]NZ04 in the range of tem-
Table 5. Details of Experimental Setup generated in the manufacture of oxalic acid. The prqcess con-
sists of oxidation of monosaccharides using mixed acid (40 wt.
Column 1 Column 2 Column 3 11/0sulfuric acid and 14-15 wt. 11/0nitric acid). The oxidation
Diameter 0.254 m 0.254 m 0.8 m reactions are as follows (Kirk and Othmer, 1981):
Packed height 4.8 m 4.8 m 1.5 m
(a) C6H1206 + 12HNOJ-3CzHz04' 2HzO + 31'1z0 + 3NO
Total height 6.0 m 6.0 m 3.0 m
+ 9 NOz
Packing type Pall ring Pall ring Intalox saddle (b) 4C6H1206 + 18HNOJ + 3HzO-12CzHz04' 2HzO
Size 16 mm 16mm 25 mm
Material SS 316 SS 316 Ceramic + 9NzO
2 2 I
(c) C6H 1206 + 6HNOJ - 3CzHz04 . 2HzO + 6NO
No. support plates (d) C6H1Z06+ 12HNOJ-6COz+ 12HzO+6NO+6NOz
Liquid distributor 1 1 I
Plate heat exchanger 2.5 m2 2.5 m2 None These reactions were carried out in two stirred-tank reactOr~
Pump operated in series. The off-gases consist main!y of NOx ane
Capacity, m3/hr 3 3 9 carbon dioxide (some COz is generated due to complete oxi,
Head. m water 18 18 22.5 dation). The volumetric flow rate of this stream was measurec
Material Polypro- Polypro. SS 316
pylene
using a precalibrated orifice meter. To this stream, a measurec
pylene
quantity of air was continuously added. The gaseous mixtUfi
Experimental Conditions was passed through a column that provided sufficient residenci
5-6 mm/s 5-6 mm/s time (Joshi et aI., 1985) for 9511/0conversion of divalent t(
VL 5-6 mm/s
10.5 5.6 3 tetravalent nitrogen oxides. The oxidized stream formed th
HN03 cone., wt. 070
1,350 1,350 1,350 gaseous feed for column 1. Some NOx absorption occurred il
PL, kg/m3
Va, m/s 0.2-0.3 0.2-0.25 0.2-0.25 column 1 and the remaining gases entered column 2 and sub
070NOx at inlet 20-23 8-12 3-6
sequently column 3.
The liquid product from the reactors consisted of sulfuri
acid (40 wt. 11/0),product oxalic acid (11-12 wt. 11/0),and ur
Absorption of NDx in a series of packed columns reacted nitric acid (0.5 wt. 11/0).Oxalic acid was separated b
cooling crystallization. The mother liquor was used for th
Experiments were conducted in three continuous, counter-
recovery of NO, gases and entered the liquid circulation 100
currently operated packed columns in series. Details pertaining
of column 3. The average composition of the liquid phase fc
to column dimensions and internals are given in Table 5. The
column 3 is given in Table 5. The overflow from the colum
first two columns were 0.254 m ID and 6 m tall. The third
3 stOrage tank was added to the circulation loop of column:
column was 0.8 mID. and 3 m tall. The experimental setup
and overflow of the column 2 stOrage tank was added to tt
is shown in Figure 9.
circulation loop of column 1. The overflow of column 1 w:
These three columns were used for the recovery of NOx gases
C.1 =COLUMN1
C2 =COLUMN 2
C3 =COLUMN 3
CP1 = CENTRIFUGAL PUMP 1
CP 2 = CENTRIFUGAL PUMP 2
R1 = ROTAMETER 1
R2 = ROTAMETER 2
R3 = ROTAMETER 3
SP 1 =SAMPLE POINT 1
R3 SP 2 =SAMPLE POINT 2
SP 3 = SAMPLE POINT 3
@)
CP 2 CP3
CP1
\.
'........
Table (I. Comparison between Model Predictions and
Experimental Observations VENT
4
Total gas flow =:.] x 10- kmol/s
NO, flow
= 1.78 x 10-4 kmolls
NO'IN" =0.72
Air flow = 4.] 7 X 10-4 kmolls
-_.~_.~._~.~--~-------
---
Column] Column 2 Column 3
ActUal Removal of No" GJo
Simulation 52.27 12.9 4.85
Experiment 59.5 12.3 4.9
ActUal NO'IN' at Outlet
Simulation 0.63 0.655 0.688
Experiment 0.565 0.629 0.70
Equilibrium Removal of
NO" GJo
Simulation 54.1 13.2 5.1
Average Conc. GJo
Nitric acid 11.25 6.05 3.1
Sulfuric acid 40.25 41.0 41.5
Pressure Atm. Atm. Atm.
Liquid Temp.. .C
At inlet 31 31 31
At our let OIL
Simulation 3:.3 31.7 32 HZS04
Experiment 36.0 32.0 32
~
.\IChE
March 1991 V III. 37. "III. J
334
"
In'
Absorption of NOx gases was carried out in 254 mm and R = universal gas constant, (m3. kN/m2)/(kmol. K)
800 mm ID packed columns. A favorable agreement was ob- Rax L = rate of absorption of component x, kmoll(m3s)
is served between the model predictions and experimental ob- Rax:o = rate of gas phase mass transfer of component x,'
. )L' 5
servations.
kmoll(m3s)
ReL = Reynolds number for liquid
)i 5 s = exponent, Eq. 55
S = cross-sectional area of column, m2
Notation Seo = Schmidt number for gas
T = temperature, K
a = interfacial area, m2/m3 t!.T = temperature difference, K
a~ = dry area of packing per unit volume, m2/m3 VL = superficial liquid velocity, m/s
[A.]
= saturation concentration of gas phase reactant in Vo = superficial gas velocity, m/s
liquid phase W = wt. frac. HN03 in aqueous nitric acid solution
e~ = average specific heat of liquid phase, kcallkmol. K WN = wt. O?o HN03 in mixed acid
dh = differential height of column Xx = kmol x ions per kmol water
dp = nominal size of packings, m (X). = component X at exit of differential volume
Dx = diffusivity of component x, m2/s (X)f
= component X formed in differential volume
Do = diffusivity in gas phase, m2/s (X);
= component X at inlet of differential volume
[era-
DL = diffusivity in liquid phase, m2/s (X)o = component X oxidized in differential volume
~isan f
= friction factOr (X)v
= component X vaporized in differential volume
,
het- F = packing factor X(g) = component X in gas phase
G = flow rate of inerts, kmoll s
G.
X(/)
= component X in aqueous phase
ares, = mass flow rate of gas stream kg/m2. s YT = total moles gas per mol inert
h = height from bottOm of packed bed, m Yx mol gaseous component x per mol inert
1 the H = tOtal height of packed column, m ( Yx). = Yx at exit of differential height
:quid H(kD) 112= absorption factOr for fast pseudo first-order reaction, ( Yx); = Yx at inlet of differential height
kmol/m2. (kN/m2). s =
[[Om YN. = kmol reactive nitrogen per kmol inerts
H,(kD)';2 = absorption factOr for fast pseudofirst-order reaction YNO. = kmol divalent nitrogen per kmol inerts
. ~able for component x, kmollm2. (kN/m2). s YHo. kmol water in form of oxyacids and free water in gas
tions 2 =
lli = standard heat of reaction, kcallkmol phase per kmol inerts
con- H., = solubility in electrolyte, kmol/m3. (kN/m2) Z = coefficient, Eq. 55
tions HNO = solubility of NO in water, kmollm3. (kN/m2)
51770. Hw = solubility in water, kmollm3'(kN/m2)
ed in ko = physical gas-side mass transfer coefficient,
kmollm2. s. (kN/m2) Greek letters
mm
KH = heterogeneous equilibrium constant, Eqs. 35, 36 ex = coefficient, Eq. C3
nthe kL = physical liquid-side mass transfer coefficient, m/s {3 exponent of superficial liquid velocity, Eq. C3
=
1i by k, = forward reaction rate constant for reaction n exponent of nominal packing diameter, Eq. C3
'Y=
:true k - n = backward reaction rate constant for reaction n ." = coefficiem, Eq. C9
K, = equilibrium constant for reaction n PL = density of liquid, kg/m3
tions
K6 = heterogeneous equilibrium constant, Eqs. 34, 36 Po = density of gas, kg/m3
\0, I = characteristic length of packing, m /Joo= viscosity of gas
L = flow rate of liquid, kmol/s /JoL= viscosity of liquid
L.
= mass velocity of liquid, kg/m2. s /Jow= viscosity oi water
Lw = latent heat of vaporization of water, kcallkmol = voidage
mO mass flow rate of liquid, kmolls
= EO = fractional gas holdup
iour m = coefficient, Eq. 61 EL = fractional liquid holdup
n = exponent, Eq. 61 ES = fractional solid holdup
N.
.~nd = tOtal moles NO,
NO. = total moles divalent nitrogen oxides
NO!, = tOtal moles tetravalent nitrogen oxides Subscripts
.and p, partial pressure of inert in bulk of gas
= a absorption
p, =
= parrial pressure of component x in bulk of gas e exit condition
p; limiting partial pressure of component x at gas-liquid =
= f formation
interface =
p~ = partial pressure of component x at gas-liquid interface G. (g) = gas phase
::a\~ p; I = inlet condition
i
= partial pressure of component x in bulk of gas phase L, (/) liquid phase
ab- Pm = power consumed per unit weight of gas holdup, m2/s3 =
T = total
Pr = toral pressure of gas, kN/m2
.::J>= pressure drop in packed column v = vapor
(acid x = x in NO,
Q, = heat changes due to formation of N20] in bulk gas,
trred
kcaJ/ s
!~ :n
Q2 = heat changes due to formation of N20, in bulk gas,
~, In kcal/ s
Literature Cited
\ere
Q] heat changes due
=
kcal/s
to formation of HNO] in bulk gas, -
Andrew, S. P. S.. and D. Hanson, "The Dynamics' of Nitrous Gas
t;en-
Q, Absorption," Chem. Eng. Sci., 14, 105 (1961).
t ihe = heat changes due l0 formation of HN02 in bulk gas,
kcal/ s Carberry, J., "Some Remarks on Chemical Equilibrium and Kinetics
td at Q, in the Nitrogen Dioxide-Water System," Chem. Eng. Scl.. 9, 189
= heat changes due to oxidation of NO in bulk gas,
~es: kcal/ s - (1958).
Q6 = heat changes due to water evaporation in bulk gas, Carleton. A. J.. and F. H. Valentin, Proc. 4th Eur. Symp. Chem.
t kcal/ s Reaction Eng. (suppl. Chem. Eng. Scl.), Pergamon. Oxford, 361
\
Qc = total heat changes in gas phase, kcal/s (1968).
QL = toral heat changes in liquid phase, kcalls Carra, G., and R. L. Pigford, Ind. Eng. Chem. Fundam.. 22, 329
<~~ ) Qr = total heat change, kcal/s (1983 ).
YT= Y"o+ Y'Io~+ Y'I~().j+ Y'I~(),+ YHNO] For known molar concentrations of inerts, oxygen, t
NO~. and NO" to (N") ratio, equilibrium partial pressure
-r YHNO, + Y H,O + Y(h -r I (AI)
- - - all the gaseous species in the bulk gas can be estimated
\
336 March 1991 Vol. 37. No. J AIChE JOUi
,
~
solving Eqs. A9-A12 simultaneously for Yr, YNO' YN02' and 8s = - A9
YH o. Compositions of HN03, HN02, N203' and N204 are
(A2) obtzained from equilibria relations, Eqs. A2-A5. 89=3A7
810= -AIO
(A3) Appendix B. Simplification of Eqs. 6-15, 23,
26-35 8ll = - (k~)N02PRi02 - (k~)HN02PHNO/2
(A4) The following two equations are obtained by substituting - (kG~)N203PRi203 - 2(kG~)N204PRi204
Eqs. 6-15, 23, and 26-35 into Eqs. 34 and 35:
812=As
(A5) 1/3]312
A I [PN02 - A2 (p{.;o) + A3 (p{.;oZ)2 - A4 (p~O)2I3]
,.j: :: and
Values for Ct, (3, and 'Y for different pac kings are as in Table
B I [P iNOZ -
i 1/3 I
B 2 ( PNO ) ]3/2 + B JPN02 + B ~ [ (PN02 )
I 2 AI. Mahajani and Joshi (1990) have developed correlations
:\9)
for gas-side and liquid-side mass transfer coefficients based
i ) 213 ] i
- B S ( PNO + B 6 (PN02 ) 2 + B 7 [PINOPN02
i
- i ) 4/3 ]
B 2 ( PNO on turbulence intensity. They have shown that the following
correlation for the gas-side mass transfer coefficient holds for
i I ) 1/2 I ) 213 ]
+ B 9 [( PNOPN02 - B 12 ( PNO + B S ( PNO
I i
) ( PN02 ) all the packings.
i i 1!1 .
+ B 10 ( PN02PNO
062
) 1/2 T' B II =0 (B2) k
(GRT) I (Pm/) 'I PG 1/3 Px
\10) 0.553 (C4)
DG l J1.G
1
J (Sed
G) i
where
where Pm is the power consumption per unit mass of the gas
Ill) BI=3AI
fap vl
B2 = A2 Pm= [6(E-Ed] 4 (C5)
B)
= (kG~ON02 -:
I is the characteristic length of packing; its value depends on
\12) B,=3A) type of packing, Table AI.
B<=A4 Liquid holdup in the packed column is computed as
'oral
B~ = 2K2 (kG'!.)N204
~ of
j 0.7s1d;1.2 (C6)
by EL= l1.53X 1O-4+2.9x IO-SReLO.66(;:)
Bo = 3A5
The solubility of HNOJ and HNOc in water is 2,090 and The rate of heat generation due to N20~ formation is:
0.484 kmol/mJ. (kN/mz), respectively (Joshi et a!., 1985). The
solubility of NO in water is given by the following equation: Q2 = (N204)j ilii) (I:
Q) ([
Hw=solubility in water, kmol/mJ.(kN/mC) = (HNOJ)j ilii6
mC)
Hel = solubility in electrolyte solution, kmol/mJ. (kN I
K,=salting-out parameter = i- +i- +i. 4. The rate of formation of HN02 in the differential elem(
is given by:
i- and i- are contributions of carions and anions of the elec-
trolyte, respectively, to the salting-out parameter and i" is the (HN02)r= (HN02)e - (HN02)i + (HNOzJa (0
5. The rate of heat liberated due to the oxidation of NO is Heat changes due to absorption with chemical
estimated from the knowledge of the rate of NO oxidation. It reaction
Jnda
may be noted that NO is used in the N203 and HN02 formation In the absence of information on heats of dissolution of
:eters
and it is liberated during HN03 formation. gases the information on heats of formation of reactants and
rNO
The mass balance for NO across the differential element is products was used to compute the heats of reactions.
, for
given by: Reactions under consideration for the heat balance are:
over
e the
NO,o = (NO'i- NO,e) - N203,f (1) 2 N02(g) + H20(/) - HN03(/) + HN02(/) (020)
- 112 HN02,f+ 112 HN03,f (DB) (2) N204(g) + H20(/) - HN03(/) + HN02(l) (D2I)
1D3) The rate of water evaporation in the differential element + RaHNO),GMlII + RaHNo2,LMlI2
was obtained by material balance:
+ RaNo,LMlI3) S dh (D26)
iffer~ (H20)u= (H20'e- H20,,)+ 1/2 HN03,f+ 1/2 HN02,f (DI6)
Total heat change in the differential volume is the summation
(H20)u=G (YH2o,e-YH2o,i+1I2 YHNO),e-1I2 YHNO).i of all the heat changes.
(04)
+ 11;2 RaHt>i02.dS dh (DI7) Jfanuscripr received June 12, 1990, and rel'isian received ,Vot', 27, 1990,
(D6)
l1enr
{Oi)
(08)
"::
ID9)
:nent
DIO)