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Modeling and Simulation of NOx Absorption in


Pilot-Scale Packed Columns

Article in AIChE Journal March 1991


DOI: 10.1002/aic.690370303

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Modeling and Simulation of NOx Absorption in


Pilot-Scale Packed Columns
N. J. Suchak, K. R. Jethani, and J. B. Joshi
Dept. of Chemical Technology, University of Bombay, Matunga, Bombay, 400019, India

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

J AIChE Journal March 1991 Vol. 37, :"10.3 323


\
_c.'. '..
-,;..-<..0,;.. '~~,
':':':';;'l~~';'. ,,'

.-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)

sulfuric acids were used as solvents. A comparison is presented


between the model predictions and the experimental obser- RaNZ04.G = (k~) NZ04 [P~Z04 - PNZ04]
(8)

vations.
RaNZ03.G = (k~)NZO) [P~Z03 - PNZ03] (9)

RaHN03.G = (k~)HN03 [P~NO) - P~N03] (10)


Mathematical Model
Model for overall rate of absorption RaHNOZ.G = (k~)HNO~ [P~NOZ - P~NOZ] (11 )
Gas Phase Reactions and Equilibria. NOx is a mixture of
various nitrogen oxides, NO, NOz. NZ03. and NZ04. In the RaHZO.G = (kG~) HZO [P~zo - p~zo] (12)
presence of water vapor, which is generally the case in most
industrial absorbers, there ~ist the oxyacids HNOz and HN03.
At this stage. the following points may be noted.
All the components of NOx are in equlibrium with each other.
1. In the gas film, the partial pressure of NO changes with
Nitric oxide undergoes irreversible oxidation with oxygen in
respect to distance from the interface up to the bulk gas. It is
the gas phase. The oxidation reaction is expressed as:
likely that the rate of NO oxidation in the film is different
from the rate in the bulk. Further, the transfer of NO is ac-
2NO(g) + OZ(g) -'1 2NOz(g) (I) companied by oxidation. Therefore, there is a possibility of
enhancement in the rate of mass transfer.
~ Joshi et al. (1985) have reviewed the published literature on The volume of the gas film can be estimated on the basis
NO oxidation. It is believed that NO oxidation proceeds by of DG. kG. H, and ~. It was found that the film volume con-
dimerization of :--10followed by oxidation by oxygen to form stitutes about 0.005-0.01 of the tOtal volume. Therefore, the
N~OJ. The oxidation reaction is second order with respect to extent of NO oxidation in the film was negligible and there
NO and first order with respect to oxygen. However, below was no appreciable enhancement in the mass transfer rate of
250 ppm of NOn the reaction is first order in both NO as well NO due to chemical reaction.
as O~. 2. In the gas film NO, NO~, N~O]. Nz04. HNOz. HNO].
Complex equilibria prevail in the gas phase, which .can be and water were assumed to be in equilibrium at all points. The
described by following equations: rates of gas phase mass transfer are likely to change due to
the equilibrium reactions. However, for simplicity. the gas
K:. phase mass transfer rates have been written in the form of
2NO~(g) N~04(g) (2) Eqs. 6 to 12. Similar assumptions have been made by Andrew
""
,,]
and Hanson (1961). Carleton and Valentine (1968). Emig et
(3) al. (1979). and Holma et al. (1979).
NO(g) + NO~(gl -= NzO](g)
Interface Equilibria. At the interface, NO, NO~, N~O],
"4 Nz04. and HNO~ are assumed to be always in equilibrium with
NO(g) + NO~(g) + H~O(g) -= HNO~(g) (4) each other. Thus, at the interface, gas equilibria are defined
by following equations:
"5 (5)
3NO~) + H~O(g) ... 2HN01(~1 + NO(g)
K,. = PN~04 , (13)
- (PNO~)-
The reaction rate constant k) and the gas phase equilibria

324 March 1991\ Vol. 37, No.3 AIChE Journal

~
NO

PNO
2NO + 02-2N02- P
N02

2N02 ~ N20,,-PN
- 20 4

NQ..-N02 ~ N203-PN H,O


-- 20 3 HNO'+T'

3HN02

3N02 + H20 ~ 2HN03- PNHO HN03 T HN02


+ NO 3

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

Figure 1. Mechanism of NOx absorption into water.

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

where x denotes the component. The values of Hx have been


compiled by Joshi et al. (1985). K6 = (p bP~o) 3/2 (23)
N204
Liquid Phase Reactions. Nitrogen oxides when absorbed
in aqueous sulfuric acid solution, form nitrous and nitric acid. An empirical equation (Matasa and Tonca, 1973) obtained
The followi~g reactions occur in the liquid phase: from various plots is of the form:

2N02(l) + H20(/) - HN03(/) + HN02(l) (19) InKH = 2.188 X 107 12.58 - 4.571 X 104 11.424W (24)

N203(/) + H20(/) - 2HN02(l) (20) where

March 1991 Vol. 37, No.3 325


AIChE Journal
",,,.~.,_,:,.,~ ,,<;.;.,,:...
~,~",""","",'i"'t: .'-_:-:':'~_":".""'U";;":,;,,~,,~,,,,,~"':"1(

KH= ~o =Kr2 K6 (101.33)2 (25) RaNO.L - RaNO.G = (RaN203.L - RaN203.C)


PNo2
+ 112(RaHNo2.L - RaHN02.C) (3~
and W is the maximum attainable HN03 concentration in
weight fraction. The method for determining K6 in the presence Equations 16-18, 24, and 25 were solved incl.ependentIy whil
of sulfuric acid is !:iiscussed later. Eqs. 6-15, 23, and 26-35 are coupled algebraic equations. 1
The limiting partial pressures of N02, N203, and HN02 order to attain convergence under varied parametric condi
based on heterogeneous equilibria would be tions, it was found necessary to reduce them to a set of tW
equations in terms of ~o and
~02' The procedure is describel
112 in appendix B.
PNo2-
b
- ( ) P~204
K2
(26)

Model for column performance


b
PN203 = K 3 PNOb b
PN02 (27)
Model Equations. The packed column has been modele,
b b b b for simulation studies. The following assumptions were made
PHN02 = (K 4 PNo PN02 PH20 ) 112 (28) I. Gas and liquid phases flow in a countercurrent plug flo\l
manner
No absorption takes place when~204
=d204' The net driving

.
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)

'0' Overall Volumetric Rates of Absorption. Overall rates of


absorption are computed by solving Eqs. 6-18 and 23-33.
There are twenty-three equations, whereas the unknowns are:
1. Volumetric rates of gas phase mass transfer: RaNO.G,
RaN02.G,

.
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

PN02' PN204' PN203' PHN02' PH20'


Plmo3
3. Heterogeneous equilibrium parameter
b b b b K6' limit\,ng partial
pressures
PN204' PN02'
4. Rates of mass transfer with chemical reaction in the liquid
film: RaN02.L, RaN203.L, RaN20;L, RaHN02.L
5. Rate of desorption of NO from liquid to gas phase RaNO.L
PN203' PHN02
Ih

Two more equations are needed to make the model consistent.


These are provided by the material balance of divalent and
tetravalent nitrogen oxides across the interface.
The N02 balance at the interface gives: l
GAS IN I
1

(RaN02'C - RaN02.d =.2(RaN204.L - RaN204,C) L (QUID OUT

+ (RaN203.L -RaN203.C) + 112 (RaHN02,L -RaHN02.C) (34)


I"
D
~
Figure 2. Differential element for mass and energy bal.
The NO balance at the interface gives:
ances.
326 March 1~1 Vol. 37, No.3 AIChE Journal

-~
,
'
' '

"'. ""'.' '


,y
"'''"'i.,~~~{''.',:'',''.'':\''',.,.'",.,:"',,,,('\i:"'"",?",:o.o',".~,!:~i;',~:".,.".-'t: t

dYNO' S [F O 2 Table 2. Heats of Reaction


P NO) PU2 Ec,-RaNO.c,+RaN20,.C,
~= -c l'''i( "
Std. Heat of
Reaction (25C)
+ 0.5 (RaHN02.C - RaHNO"C>J (36) Reactions kJ x 10"
ReaClions in GaS Phase
b. Balance for total reactive nitrogen
"
2NO
'"
+ 02(Ri - 2N02", t.H, = - 5.7
per kmol NO oxidized
dYI" S. ' 2N02(,,- N~04(g) t.H, = - 5.72
[
dh = - c - RaNO.C T RaI'02'C + 2RaN20,.C + 2RaN204.C per kmol N~O" formed
NO,g) + N02tg)- N20J(g) t.H,,=-3.99
... RaHNO,.C + RaHN02,d (37) per kmol N~O) formed
3N02(g) + H~Otg)-2HN03(g) + NOtg) tJi6= - 1.77
per kmol HNO, formed
c. Water-vapor balance
NO,,) + N02(g) + H~O(g)-2 HN02tg) t.H-= -2.05
I per kmol HN02 formed
dYH,o' S
(38)
~= -c [RaH20.C+ 1!2RaHNo,.c+ 1!2RaHNo2.d
Eq. 020 per kmol
ReaClions in the Liquid Phase
NO, absorbed t.H, = - 5.36
Eq. 021 per kmol N~O" absorbed t.H9= - 5.03
d. Oxygen balance Eq. 022 per kmol N~O, absorbed t:..HIO=-3.99
Eq. 023 per kmol HNO, decomposed t.H1, = + 2.39
dYo, 1S Eq. 024 per kmol HNO, absorbed t.H'1 = - 3.92
.= -2 C [kJ (p~O)2 (P02) Ed (39)
dh Eq. 025 per kmol of HN02 absorbed t.H12 = - 4.14

Component balance in liquid phase


e. Balance for nitric acid

dX HNO, S T=~mOC~ (41)

~ =- L [4!3RaN204.L + 2/3RaN203.L + RaHNO"C

where T is the temperature change across the differential ele-


+ 2/3RaN02.L + 1/3RaHNo2.L1 (40) ment. Further details pertaining to the heat balance are given
in appendix D.

Equations 36-40 are coupled linear differential equations. To-


o tal mass balance is established across the differentia) height Method of Solution
on solving these equations simultaneously. The method of solution involved the following five steps.
Estimation of Design Parameters. Mahajani and Joshi
(1990) have developed general design procedures and derived
1. Estimation of gas phase composition
rational correlations for hydrodynamics and mass transfer
characteristics in packed columns. The design parameters in- Equations A9-All, appendix A, form a set of four simul-
clude gas- and liquid-side mass transfer coefficients and ef- taneous algebraic equations. The four unknowns are the moll
mol inerts of NO, N02, H20, and total moles in the gas phase.
. fective interfacial area. In addition, we need to know the values
or "ffusivity and solubility. Details are given in appendix C. Equations were solved numerically by the Newton-Raphson
upecific rates of absorption of N204 were measured exper- matrix method for nonlinear equations.
imentally to estimate H(kD)l/2 values. This is discussed in a
later section.
2. Estimation of interface composition
Heat Balance. Oxidation of NO, formation of N203 and
N204 in the gas phase, absorption of N02, N203' N204' and For the estimation of interface composition, we need to solve
the liquid phase reactions are exothermic. The decomposition twenty-one equations simultaneously, Eqs. 6-18, 23, and 26-
of HN02, however, is endothermic. Because of these reactions, 32. The intricate algebraic reductions of these twenty-one equa-
significant heat changes occur. The values of physicochemical tions into two polynomial equations, Eqs. Al and A2, has
parameters such as reaction rate constants, equilibrium con- obviated the need for a scaling algorithm. The variables se-
stants, solubilities, vapor pressures, and diffusivities depend lected-the interfacial partial pressures of NO and N02-are
upon temperature. Heat, liberated because of various reactions always present in greater magnitude than other components
in the gas and liquid phases, has been included in Table 2. It of NOx' These two equations were numerically solved by the
will be assumed that the heat liberated is taken up by the liquid Newton-Raphson and Gauss-Jordan method. The main ob-
phase and the interface is always saturated with water vapor. jective behind using this composite technique, which was al-
Further, it was ~ssumed that at any point in the column, the gebraic and analytical in nature, was to achieve a single positive
gas and liquid phase temperatures are the same. finite solution with minimum numerical iterations. Substitut-
If QT is the total heat change per unit time in the differential ing these values in Eqs. 13-15, 23, and 26-28 results in the
element, then the temperature change under adiabatic condi- interfacial and limiting partial pressure values of N204' N203,
tions is given by: and HN02.

AIChE Journal March 1991 Vol. 37, No.3 327


3. Estimation of H;JkD)~/2
values
Absorption of NOz, NzO), and NZ04 in water has been
extensively studied in the literature. Joshi et al. (1985) have 90
critically reviewed the previous work. Kameoka and Pigford
(1977) have shown that the rates of absorption of NZ04 in
water and aqueous sulfuric acid solution are practically the 80
same. They carried out experiments with 0.09 NHzS04 solu-
tions. At higher concentrations of sulfuric acid, the rates are 70
likely to decrease. Further, in the present work the absorbent 1. MODEL EXCLUDING
HETEROGENEOUS
is a mixture of sulfuric and nitric acids at different concen- EQUILIBRIA AND RATE DEPENOENCE
.:; 60
trations. The kinetics of absorption of NO, in mixed acid z ON HNO, CONCENTRATION
...
solutions has not been studied in the past. Therefore, it was o
2. MODEL EXCLUDING
HETEROGENEOUS
thought desirable to undertake a systematic investigation. The ~ 50 EQUiliBRIA AND INCLUDING RATE
o> DEPENDENCE ON HNO,CONCENTRATION
details are given later. %
...
a: 3. MODEL INCLUDING HETEROGENEOUS
.... '0
z EQUlll BRIA AND RATE DEPENDENCE
4. Solutions of ordinary differential equations ...
u ON HNO, CONCENTRATION
a: 30
Equations 36-40 are five coupled ordinary differential equa- ...
Q.
tions. Further, they constitute a boundary value problem. The
flow rate and composition of the incoming gas phase are known.
Similarly, the flow rate and concentration of incoming mixed
20
-- : -..--- -- - -
-=':-":---: 21

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

" AIChE Journal March 1991 Vol. 37, :'110.3 329


,..,o:..~._~'~'i:;.;;;..:;~~,-,.;4..",~ . ~,~::.,,;n,~

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

0~TO G) TEMPERATURE TRANSMETER


(CONTACT THERMOMETER)

CD TEMPERATURE CONTROLLER

o HEATING PAD

G)
TT
o ROTAMETER
G) WATER JET EJECTOR

CD

-4-- GAS STREAM FROM PROCESS


20 'f, NO. (96 'f, NO.)

CD
Figure 8. Experimental setup in stirred cell.

330 Mardh 1991 Vol. 37. ~(). 3 AIChE Jour

'''''-.,,--,. ..-,'~" ;'.,


"-"'~:<:..~~~t
The effect of stirrer speed was investigated in the range of Table 3. Experimental Values of [H(kDl/2]N204 for 40%
0.167 to 1.33 rls. The liquid surface was flat, without any Sulfuric Acid
vortex. It was observed that the specific rate of absorption was
070 NOx= 19
independent of the stirrer speed when the speed exceeded 0.67 Temp. 30.C
rls. This also indicates that there is no effect of gas- and liquid- Sulfuric acid cone., 40 wt. 0,10
side mass transfer coefficients (kG and kd when the speed
Nitric Acid [H(kD) 112)N204'.
exceeds 0.67 rls. It also indicates complete homogeneity of wt.O,1o [kmol/m3. s(kN/m2) x 106
the liquid phase. Since the absorption operation was found to
be independent of kL, it means that absorption does not con- 0.0 2.95
5.0 2.60
form to the instantaneous reaction regime. All the above evi- 10.0 2.29
dence indicates that the absorption operation falls in a fast 15.0 1.12
pseudo mth-order reaction regime. 20.0 0.60
Water, 40070sulfuric acid, and mixed acid solutions con- Nitric acid, 0.0 wt. 0,10
It taining nitric acid and 40% sulfuric acid were used as absorb- Sulfuric acid, 40 wt. 0,10
ents. A few experiments were also conducted to evaluate the Temp. [H(kD) I12)N204'
effect of temperature on the values of the absorption parameter .C [kmol/m2. s(kN/m2) X 106
Hx(kD)~2. 40 3.3
Tetravalent nitrogen oxides (NO!) constituted more than 20 2.8
96070of the NOx gas used in the experiments. Under these
[H(kD)II2]N,O.' 30'C for water=7.6x 10-6 kmol/m'.s(kN/m')
conditions the partial pressure of divalent nitrogen oxides
tpNo and PN20J)was negligible. It was expected that the values
ab.
of [H312(2/3 kD)1I2]N02 and [H(kD)II2]N204 in H2S04 would
be lower than those in water due to the presence of electrolyte. perature and concentration covered in this work. The following
It was assumed that correlations were found to hold.
For mixed acid solutions:
cell
[HJ/2 (2/3kD) 1/2]N02.water H(kD) 1I2]N204.water
way [H(kD) 1I2]N204 x 1O-5e-6263.7IRT (I - 1.616
[H3/2 (2/3kD)
(42) = 3.66 X 10-2 W:"
:imi- 1I2]N02.H2S04 [H (kD) 1I2]N204.H2S04
ause -1.267x 1O-3W~) (45)
~the
The specific rate of formation of HNOJ by the absorption
etely
of NOx gas is given by the following equation:
For water and nitric acid (Lefers and Van der Berg, 1982):
mL
-fioei RHNOJ = 4/3RNZ04 + 2/3RN02 Wi( I
[H( kD) 1/Z]N204 IO[-3.215 -IA2~ - WII.8JJe-I.285.JIT (46)
ntity =
= 4/3 [H( kD) 1I2]N204.H2S04 PN204

[H(kD) 1/2]'1204values in the presence of 40% sulfuric acid


+2/3 [H3/2(2/3kD)1I2]N02,H2S04 (PN02)J/2 (43)
were found to be much lower than those found in water. This
- is because the activity of water decreases in the presence of
The interfacial partial pressures of N02 and N204 are related sulfuric acid. The values of [H(kD) 1/2]given by Eqs. 45 and
by Eq. 13. The following equation is obtained by substituting 46 were used for the estimation of K6 values for mixed acids.
Eqs. 13 and 42 in Eq. 43: The equivalent nitric acid concentration was estimated on the
basis of the same [H(kD) 1/2] values. Table 4 gives the values
..,
[H(kD) I''''
'"]NZ04.HZS04(K2(PNOZ)"
i for nitric acid concentration equivalent to mixed acid concen-
RHNOJ=4/3
tration. These values were used for determining K6 from Eq.
25.
[H3/2
2 (2/3kD)1/2]NO"water The values of [H(kD) 1/2]N20Jand [HJ/2(2/3 kD) 1'2]'102were
+3 [H ( kD ) 112] N204.water
- I
(PNO 312 (44)
assumed to vary (with respect to concentration of acids and
, tem?erature) in an identical manner to that of [H(kD) 1/2]'1204'
The value of [H(kD) li2]NZ04.HZS04 was obtained from Eq.
44 by using the experimental values of the specific rate of
formation of HNOJ.
The value of [H(kD) 1/2]N204for water was found to be
Table 4. Nitric Acid Concentration EquivalenCto Mixed
7,6x 10-6 kmol/m2.s.(kNlm2) at 30.C. This value is in agree-
Acid Concentration
ment with those reported in the literature (Sherwood et aI.,
1975; Joshi et aI., 1985). The values of H(kD)I/2 for NZ04 at Wt. 0,10HNO, [H(kD) 1/2]'1,04 Equiv. wt. 0,10
various acid concentrations are given in Table 3. It can be seen
.
in 400,10H2S04 at 30'C - HNO, in Water

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-

~al AIChE Journal March 1991 Vol. 37, :"-10. 3 331


i
.~,~~ '......
,.
.~" -'

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

CP3 CENTRIFUGAL PUMP 3


=

R1 = ROTAMETER 1
R2 = ROTAMETER 2

R3 = ROTAMETER 3

PHE 1 = PLATE HEAT EXCHANGER 1

NOX,AIR PHE 2 = PLATE HEAT EXCHANGER 2

SP 1 =SAMPLE POINT 1
R3 SP 2 =SAMPLE POINT 2
SP 3 = SAMPLE POINT 3

@)

CP 2 CP3
CP1

Figure 9. Three.column absorption system.

Vol. 37, No.3 cUChE JoUi


332 Mar~h 1991

\.
'........
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

recycled \0 the reactors after adjusting acid concentration (by


adding concentrated nitric and sulfuric acids). The liquid phase
in all three columns was circulated \0 get a sufficiently good @ @
flow rate for wening of the packings. In each recycle srream,
the plate heat exchanger was incorporated to maintain the
temperature within :I::I 0c.
The composition of the gas and the temperarure were meas-
y CP1
y CP2
ured at the inlets and outlets of the columns. The liquid phase
concentrations and flow rates were also measured. Liquid phase Figure 10. Two-column absorption system.
concentration was measured by fixing the acid mixture in an Ct, C2, columns
CP I, CP2, centrifugal pumps
excess quantity of sodium hydroxide. The concentrations of R I, R2, rmameters
sodium nitrate and sodium sulfate were measured using an ion PHE, plate heat exchanger
chromatograph. Calibration charts were constructed by using SPI, SP2, sample points
standard samples of NaN03 and Na2S04' The liquid phase
flow rate was measured by using a precalibrated rotameter.
Table 7. Details of Experimental Setup Details pertaining to the superficial gas velocity, superficial
liquid velocity, temperature of operation, and the concentra-
Column 1 Column 2
tions of various species are given Table 5. The percentage
Diameter 0.80 m 0.80 m removal of NOx in all the columns is summarized in Table 6.
Packed height 6.0m 6.0 m
Total height
For the purpose of comparison, the results of model predictions
7.0 m 10.0 m
are also given in Table 6. A favorable comparison (within I5OJo
Packing type Intalox saddle Intalox saddle for column I and within 5% for columns 2 and 3) can be seen
Size 37 mm 37 mm
Material between the predicted and experimental values of conversion
Ceramic Ceramic
with respect to NOx' The predicted temperarure of the column
No. support plates 2 2
Liquid distribuwr I outlet is somewhat higher than the measured temperature.
I I
Plate heat exchanger 15.0 m2 None
This was because the column was not insulated and the heat
Pump
losses were not included in the model.
Capacity, m3/h Experiments were also carried out in two 0.8 m ID packed
15 15
Head, m of water 25 25
columns operated in series. The flow sheet is given in Figure
Material SS 316 SS 316 10. The qualitative description of the process is the same as
that for Figure 9. The details of the equipment are given in
Experimental Conditions Table 7. A comparison between model predictions and exper-
VL 5-6 mmls 5-6 mmls imental observations is given in Table 8. It can be seen that
HN03 cone., wI. OJo 6.0 2.5 the agreement is within 5%. It may be emphasized that the
PL, kg/m3 1,350 1,350
VG, mls inlet values of NO. IN. are markedly different for the first
0.14 0.14
OJoNO, at inlet
14
columns in Tables 6 and 8, and even then the agreement is
7
good.

AIChE Journal March 1991 Vol. 37, No.3 333


.
.
._j,,"'t.I...~J.'
-
._- /.'"

90 Table 9. Extent of NOx Removal in 250 mm ID Colum


7.1 X 10-4 kmol
Total flow rate of gas phase
1.78 x 10-4 kmc
80 Flow rate of NO,
(U2
NO" IN" ratio at boltom
4.l7x 10-4 km(
Flow rate of air
~ 70 Column details are given in Table 5
u
'" Superficial liquid velocity 6 mm/s
"'"
Q.. 60 Mixed acid concentration is given in Table 6
z
o
... Removal of NO. at I m height. "10
Simulation 39.2
~
o
50
COLUMN DIAMETER = 1.Z5m 41.7
VI Experimental
CD
..
SUPERFICIAL LIQUID VELOCITY = 6 mm/s Extent of removal at 4.8 m height is given in Ta':>le 6
o. '0 = 0,333
No. AT THE BOTTOM
NO" /
z
...
PERCENTAGE NO. AT THE INLET = Z, 'Column I, Table 5
o AVERAGE TEMPERATURE 33.C
I-
30 =
z TOTAL PRESSURE ~ 101 '33 kN / m
heights, the extent of NO, removal is controlled by he
UJ
l-
X TOTAL GAS FLOW RATE = 2."9s",o3kmo~./S geneous equilibrium. Thus, Tables 6 and 8 show a compa
UJZO
FLOW RATE OF NO, = 6 '10' kmol.Is between predictions and experimental observations wherl
FLOW RATE OF AIR = ,.81. x'0') kmol~/ s erogeneous equilibrium was practically established.
10 In order to check the validity of the mass transfer
Eqs. 29-32, the extent of NOx removal was measured i
o
3 , 5 6 8 250 mm ID column (column 1 in Table 5). The gas and I
o
HEIGHT FROM THE BOTTOM, m samples were withdrawn at a distance of 1 m from the bt
and at the top of the column. The results are given in
Figure 11. Effect of column height on the extent of NOx
absorption. 9. In 1 m packed height, heterogeneous equilibrium cond
are not established and the rate of mass transfer is th(
trolling step. The agreement between the model predi
The extent of NOx absorption increases with an increase in and experimental observations can be seen to be within
the packed height, Figure II. It can be seen from Figure II It may be noted that in all five packed columns stud
that the rate of NO, absorption is high in the bottom region. this work, most of the liquid phase was recycled, as she
However, the rate becomes very low when the packed height Figures 9 and IQ. As a result, the HNO:! concentration
exceeds about -+m. At the bottom, the partial pressures of liquid phase attains a constant composition. as report
NO:! and N:P. are high compared with the equilibrium partial Counce and Perona (1983). This was indeed found to t
pressures for a given nitric acid concentration, Eqs. 23-28. in the present set of experiments. Therefore, the contrib
[0 the extent 0
Therefore, the rate of NO, absorption, Eqs. 29-32, is high at of HNO:! formation and decomposition
the bottom. As the height increases, the driving force contin- absorption were not considered in the present model.
uously decreases. Above a certain height-say 4 m in Figure
II-the overall absorption operation is controlled by the ox- Conclusions
idation of NO in the gas phase. Therefore. for large packed
A mathematical model has been developed in whic
new features have been included. These are:
Table 8. Comparison between Model Predictions and I. Variations in the rates of absorption of NO,. :'-.I,
Experimental Observations N:!04 with respect [0 concentration of nitric acid
2. Heterogeneous equilibria between NO. :'-.1,0], :'-.I:
Total gas flow=2.5x 10-3 kmol/s
NO, flow=3.5 x 10-4 kmolls nitric acid concentration
NO"/N" =0.107 3. Formation of nitric acid in the gas phase
Air flow = 1.74 x 10-3 kmolls 4. Complete energy balance
Column I Column 2 Total The new model is capable of incorporating the effects C
imum permissible concemration of nitric acid on N
Actual Removal of NOn % sorption.
Simulation 55.9 21.9 77.8
56.3 20.7 77.0 Specific rates of absorption of N:!OJ in water and mix
Experiment
Actual NO" /N" at outlet solutions of sulfuric and nitric acids were measured in 8
Simulation 0.318 0.239 cell with tlat interface. The observed rares of absor~
Experiment 0.331 0.226
water were found to agree with the published literal
Equilib. Removal of :"'10" 070 mixed acid solutions. the specific rates of absorptie
Simulation 58 23.3 81.3
Average cone., 070 found to decrease with an increase in the nitric acid
:O;itricacid 6.0 2.5 tration. The following correlation was found to holt
Sulfuric acid 42.0 43.0 range of 0-20 wr. 1)10HNO, in 40 wr. 070sulfuric acid
Atm. Atm.
Pressure 18-19 kN/m:! panial pressure of tetravalent nitrogen
Liquid Temp., C
At Inlet 31 31
<>263.-
Hr(l-1.616x 10
At outlet [H(kD)i :!IN,()4=3.66x lO 'e
Simulation 37.3 31.7
Experiment 36.0 32.0 [,267 X II
-

~
.\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 ).

,~al AIChE Journal March 1991 Vol, 37, ~o, 3 335


i (
"-';::., , ,~.;.,.,...~,."",.~.
.""":'-".~'

Counce, R. M., and J. J. Perona, "Gas-Liquid Interfacial Area of where


a Sieve Plate with Down Comers and 0.6070 Perforations," Ind.
Eng. Chern. Proc. Des. Develop., 18,562 (l979a).
Counce, R. M., and 1. J. Perona, "Gaseous Nitrogen Oxide Ab- YNZ04 = Kz( YNOZ)zPTIYT u
sorption in a Sieve Plate Column," Ind. Eng. Chern. Fundarn., 18,
400 (l979b)..
Counce, R. M., and J. 1. Perona, "A Mathematical Model for Ni-
YNZ ] =K]YNOYNO, PTIYT
- u

trogen Oxide Absorption in a Sieve Plate Column," Ind. Eng. Chern. (l
Proc. Des. Develop., 19, 426 (1980). YHNOZ= (K4YNOYNOzYHZOPTIYT)1/Z
Counce, R. M., and 1. J. Perona, "Scrubbing of Gaseous Nitrogen
Oxides in Packed Towers," AIChE J., 29,26 (1983). I/Z
Ks( YNOZ)3yHzO PT
Danckwerts, P. V., Gas-Liquid Reactions, McGraw-HilI, New York - (f
YHN03-
(1970). [ Y NO Y TJ
Emig, G., K. Wohlfahrt, and U.. Hoffmann, "Absorption with Si-
multaneous Complex Reactions in Both Phases, Demonstrated by In computing gas phase equilibria, we assume that then
the Modeling and Calculation of Counter-Current Flow Columns
no formation or removal of reactive nitrogen. Hence Y
for the Production of Nitric Acid," Cornput. Chern. Eng., 3, 143
(1979). total reactive nitrogen per mole of inert, is expressed as:
Holma, H., and J. Sohlo, "A Mathematical Model for an Absorption
Tower of Nitrogen Oxides in Nitric Acid Production," Cornput.
YN' = YNO + YNOZ + 2( YNZ04)
Chern. Eng., 3, 135 (1979).
Hoftizer, P. J., and F. J. G. Kwanten, "Absorption of Nitrous Gases,"
+ 2
(
YNZ03) + Y HN03 + Y HNOZ
(i
G. Honhabel, Gas Purification Processes for Air Pollution Control,
Butterworths, London (1972).
Joshi, 1. B., V. V. Mahajani, and V. A. Juvekar, "Absorption of
NO, Gases," Chern. Eng. Cornrnun., 33, I (1985). whereas the extent of oxidation at any moment is expres
Kameoka, V., and R. L. Pigford, "Absorption of Nitrogen Dioxide in the form of YNO', moles of divalent nitrogen per mole
into Water, Sulfuric Acid, Sodium Hydroxide, and Alkaline Sodium inert:
Sulfite Aqueous Solutions," Ind. Eng. Chern. Fundarn., 16, 163
(1977) . (,
( YHN03)
Kirk and Othmer, Encyclopedia of Chernical Technology, 3rd ed., YNO' = YNO + YNZ03 + 0.5(YHNOZ) - 0.5
Wiley, New York, 16,623 (1981).
Koukolik, M., and J. Marek, Proc. 4th Eur. Syrnp. Chern. React.
Eng. (sup pI. Chern. Eng. Sci.), Pergamon, Oxford, 347 (1968). YHZO' is moles of water in the form of oxyacids and I
Koval, E. J., and M. S. Peters, "Reaction of Aqueous Nitrogen Diox- water vapor per mole of inert. It is expressed as:
ide," Ind. Eng. Chern., 52, 1011 (1960).
Lefers, J. B., and P. J. Van der Berg, "Absorption of N02/N204 into ( YHN03) + 0.5( YHNOZ) (,
YHZO" = YHZO + 0.5
Diluted and Concentrated Nitric Acid," Chern. Eng. J., 23, 211
(1982).
Mahajani, V. V., "Figuring Packed-Tower Diameter," Chern. Eng., Equations A2 to A5 express YNZ04, YNZ03,YHNO~'and YH
Sept. 20, 132 (1982). in terms of YNO, YNO" YH,o, and YT. When these are sub
Mahajani, V. V., and J. B. Joshi, "Mass Transfer in Packed Column: tuted in Eqs. AI, A6, A7: and A8. four equations in Y
A Quick Look," (in preparation, 1990).
\lakhotkin, A. F., and A. M. Shamsutdinov, Khirn. Khirn. Tekhnol., Y'IO" YH,o, and YT are obtained. They are:
19(9),1411 (1976).
Matasa, C., and E. Tonca, Basi!: Nitrogen Cornpounds, Chemical yj.- YT( 1)
Y'IO + Y"o~ -+-YH:o + Yo: +
Pub. Co., New York (1973).
Niranjan. K., V. G. Pangarkar, and J. B. Joshi. "Estimate Tower
Pressure Drop;" Chern. Eng., June 27,67 (1983). - YV~ {[K,Pr( Y'IO~)3 YH~O'Y'lO]li~ + (K.jPT Y:-ooY"oz YH~o
Onda. K.. E. Sada. T. Kobayashi, S. Kita, and K. Ita, "Salting Out
Parameters of Gas Solubility in Aqueous Salt Solutions," J. Chern. -[K,PT Y"o~ Y"o...K:PT (Y'IO~)~]=O
Eng. Japan, 3. 18 (1970).
Sada. E., H. Kumazawa. N. Hayakawa, I. Kudo, and T. Kondo. L:
"Absorption of NO in Aqueous Solutions or KMnO,," Chern. Eng. YT( Y,,* - Y'IO- Y"o:) - Y~~ I (K.jPT Y'IOY'Io:YH:o)
Sci., 32. 1171 (1977).
Sherwood, T. K., R. L. Pigford, and C. R. Wilke. .Vfass Transfer, :
+ [KSPT( YNO/ YH~oIY'lo]1 I - 2PT[K~( Y"o~):
\1cGraw-Hill. New York (1975).
Selby, G. W., and R. \1. Counce, "Aqueous Scrubbing' of Dilute
- K] YNo YNo:] =0 (P
Nitrogen Oxide Gas Mixtures," Ind. Eng. Chern. Res., 27. 1917
( 1988).

YT( YNO* - YNO) -1/2 Y~~ [(K.jPTY'IOY';!.O~YH~O)I/Z


Appendix A. Estimation of Partial Pressures of 3 I!2 ]
Various Gaseous Components on the Basis of - [KSPT( YNOZ) YHZOi ' Y'\Io] - K]PT YNO YNoz =0 (A
Gas Phase Equilibria
I/Z
The total number of moles in the gas per mole of inert is YT( YH~O" - YHZO) - 1/2 Y~~ I (K4PTYNO Y"o~ YHZO)
obtained by adding ratios of all gaseous species to mole '01' 3 i/2
+ [K,PT (Y'\I0z) YH~oIYNo] =0 (A
inert.

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]

+ As[P~~oz - Az (p{.;O)4/3] + A7[ (PNO) 112(p~OZ) IIZ


~re IS
Appendix C. Estimation of Design Parameters
Y~*, . .. .
2/3 112
.
IIZ and Physical Properties
- AS(PNO) ] + A9(PNO) (PNOZ)+AlO(PNO) (PNOZ)
The column diameter was estimated on the basis of flooding
+ A I iPNO + A 12 = 0 (Bl) calculations. The correlation (Mahajani, 1982) used to deter-
mine flooding conditions is:
(A6) where
In Y=- 3.3861- 1.0814 In X- 0.1273 (In X)2 (CI)
AI = I~ (HNOZ)3/Z[(2/3 kD)NOZ]1/2)/3
~ssed
where
Ie of Az= I/K~/ZK6113
(O*)2p J1.~.1
A3 = (2K2 ~ HNZ04 [(kD)N20/12) 13 -
Y=
(A7) PL PG
A4= I/(Kz K~/3)

free As= (K3 ~HNZOJ [(Dk)NZO/I2J/3 X =~: ~:r/2


IIZ
A7 = (K4 pkzo) KL'!.HHNO/6
I/Z Packing factor P was calculated from the equation,
.(A8) As = 1/ (K~I2K~/3)

A9 =- K3 (kG~)NZOJ P=Z(dp)-S (C2)


.flNO)
bsti- AIO= - (K4 pkzo)112 (kG'!.)HNO/2 The correlation employed for computing the effective in-
Y"Q,
All = - (kG'!.)NO terfacial area (Joshi et aI., 1985) in packed column is

A,z= (kG~)NOP~O+ (kG'!.)HNO:PHNO/2+(kG~)N20~Ri203 Ct VL(3(dp)r


'!.
, (C3)
E'

,.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

'nal AIChE Journal March 1991 Vol. 37, No.3 337


'""
",".',.'.'
.,
" """,~h"'~'
..' . ~

Table AI. Values of Constants in Eqs. CI-Cll


f a {3 Z s 10-2
Pac kings m n=-y "X
Raschig rings 3.76 4.53 -1.015 0.5dp 8.0 0.403 27,800 1.533 2.1
843 0.913 4.4
Pall rings 2.17 3.96 -1.07 O.ldp
0.25dp
28.4
19.6
0.5
0.478 7,091 1.337
. 2.7
Intalox saddles 2.03 6.74 - 1.0

contribution of the solute gas. Oanckwerts (1970) and One


where the Reynolds number is given by
et a!. (1970) have reported the values of salting-out paramete
dp VL PL
for various cations, anions, and gases. The value of ig for N
ReL= (C7) gas was reported by Sada et al. (1977). The value of ig f(
ILL E HNO) was estimated from the vapor press un: of HNO) OV
nitric acid. The value of ig for HN02 was assumed to be t1
The specific surface area is calculated from the packing same as that of HNO).
diameter as

ap=m(dp)n (C8) Appendix D. Heat Changes


Gas phase heat changes
Values of m and n for different packings are given in Table Contribution to the heat changes from the gas phase are d\
AI. to the following steps.
Liquid-side mass transfer coefficient kL has been estimated I. The rate of formation of N20) from NO and N02 in tl
from the following correlation: differential element is given by:
0.5 (0
(kd/Dd =1/ReL ( ) P:~L
(C9) (NzO)j= (NZO)e - (NZO)i + (NZO)a

(NzO)j= G ( Y"zo),e - Y"Z0Jol) + Ra"ZO).LSdh (0


Values of coefficient 1/ are listed in Table AI.
Pressure drop in the packed column was estimated by the The rate of heat generation due to NzO) formation is:
following correlation (Niranjan et a!., 1983)
Q, = (NzOJ)j ilii4 (0
f( G* )2a p
(M'/h) (ClO)
= [6 PC(E-Ed]
2. The rate of formation of NZ04 from N02 in the diff(
ential element is given by;
Oiffusivities of gases vary with temperatUre and pressure.
For this purpose, the following correction was used. (0
(N204)j= (N204)h - (N204)i + (N204)a
(T/298.2)L75(101.33/ ?T) (CII)
Dx=DdS'C (0
(N204)j= G( Y"204.e- YN204.i) + Ra"204.LSdh

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:

roglo (101.33 x H"o) =- 1,463.32IT + 2.178 (CI2)


3. The rate of formation of HNO) in the differential elem(
is given by:
The solubility of NO and HNOc in the presence of electrolytes
like HzSO~ and HNOJ was estimated by using the fullowing (HNO)j= (HNOJ)e - (HNO)i + (HNO)a ([
equation;
(HNO)j=G( YHNO).e- YHN0Jol)+ RaHNO).cSdh ([
10glO(He/Hw) = -f.K,l (CI3)
-
where The rate of heat liberated due to HNOJ formation is;

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

338 March 1991 Vol. 37. :"/0.3 AIChE Jourr


(
(HN02)f= G( YHN02.e- YHN02.;) + RaHN02.LSdh (Dll) Q6 = (H20)u Lw (DI8)
2
:) ~

The total heat change in the gas phase is given by:


The rate of heat liberated due to HN02 formation is:

QG=QI +Q2+Q3+Q4+QS+ Q6 (D 19)


Q4= (HN02)fMl7 (DI2)

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)

(3) N203(g) + H20(/) -2 HN02(l) (022)


= G( YNO,i- YNO,e- YN203.e+ YN203,i

~ due (4) 3 HN02(l)-HN03(l)+2 NO(g)+H20(/) (D23)


-112 YHN02.e+ 112 YHN02,i+ 112 YHN03,e-l12 YHN03,;)

n the (5) HN03(g)-HN03(/) (D24)


- (RaN203.L + 112 RaHN02.L - 112 RaHN03,G) S dh) (DI4)
(6) HN02(g)-HN02(/) (025)
. (01) The rate of heat generation due to NO oxidation is given by:
Heats of reaction are summarized in Table 2.
(02) Qs = (NO)o Mil (D 15) Heat liberated due to absorption with chemical reaction in
the liquid phase is expressed as:

Heat changes due to water evaporation


QL = (RaNo2,LMls + RaN204,LMl9 + RaN203,LMlIO

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)

+ 1/2 YHN02,e-1I2 YHN02,;) + (112 RaHNO),G Qr= QG -+ QL (D27)


ID5)

+ 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)

--"al -\IChE Journal March 1991 Vol. 37, No.3 339

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