Computers them. Engng, Vol. 16, No. 1, pp. 11-25, 1992 0098-1354/92 55.00 + 0.

00
Printedin Great Britain PergamonPressplc

MODELING AND SIMULATION OF A SPRAY COLUMN

FOR NO, ABSORPTION
K. R. JETHANI, N. J. SUCHAK and J. B. JOSHI?
Department of Chemical Technology, University of Bombay, Matunga, Bombay 400 019, India

(Received 24 October 199O;Jinal revision received 3 July 1991; received for publication II July 1991)

Ahstraet-Absorption of nitrogen oxides was studied in a spray column of 1.25 m id. and 11.5 m height.
Mixed-acid solutions of nitric and sulfuric acid were used as absorbents. Specific rates of absorption were
measured using a stirred cell with a flat interface.
The mathematical model for the adiabatic absorption included: the gas phase reaction and equilibria,
gas phase mass transfer, equilibria at interface, liquid phase reactions and associated heat effects. The
following outstanding features were also incorporated: heterogeneous equilibria and its role in computing
the volumetric absorption rates, formation of HNO,, HNO, in the gas phase and their mass transfer to/
from liquid phase, dependence of H(kD)“z on the concentration of HNO, with/without other electrolytes
and complete energy balance.
The spray column has been modeled as a countercurrently operating mass transfer equipment with
known initial conditions. Concentrations and Aow of the gas stream at the inlet (bottom) of the column
were known. Values of the concentrationand the temperatureof the liquidphase beingwithdrawnfrom
the bottom of the column were also specified.To begin computing a temperatureand concentration
profile,a differentialelementalong the heightof the columnis considered.Equilibriumin the bulk of the
gas phaseof thisdifferentialvolumewerecomputedby the Newton-Raphsoniterativemethod. Interfacial
partialpressures of water and nitric acid were interpreted from a database by a NewtonGregory forward-
backward difference method. Volumetric mass transfer rates in the gas and the liquid phases were
computed by solving two film theory model equations. These rates are used in evaluating derivatives
with respect to height and then integrated numerically by using a fourth-order Runge-Kutta method,
establishing mass balance across the differential height. Heat changes due to equilibria in the gas phase,
absorption and desorption of nitrogen oxides and evaporation of water were computed to estimate the
temperature of the incoming liquid phase. Gas phase equilibria are computed for the next element. These
computations were repeated for subsequent differential elements until they added up to the desired height.
A favorable agreement has been shown between the model predictions and the experimental
observations.

1. INTRODUCTION components. Sherwood ef al. (1975) and Joshi et al.

Absorption of NO, gas is an important step in the
manufacturing of nitric acid. The removal of NO,
from the off-gases/flue gases has received considerable
attention due to stringent statutory regulations for a
clean environment.
Absorption of NO, gas is probably the most
complex when compared with other absorption oper-
ations. The reasons are: (i) the NO, gas is a mixture
of several components consisting of N,O, NO, NO,,
N,O,, N,O,, N,O, etc. and the absorption of NO, gas
in water results into two oxyacids, namely nitric acid
and nitrous acid; (ii) several reversible and irrevers-
ible reactions occur in both the gas and liquid phases;
(iii) simultaneous absorption of many gases occurs
followed by a chemical reaction. Also simultaneous
desorption of many gases occurs preceded by chemical
reaction. For example, the absorption of NO,, N,03
and N,O., is accompanied by a chemical reaction
whereas the desorption of NO, NO, and HNO, is
preceded by a chemical reaction; (iv) heterogeneous
equilibria prevail between the gas and liquid phase
tTo whom all correspondenceshould be addressed.
(1985) have reviewed these aspects of NO, absorption.
Spray columns are used for contacting a dispersed
phase (a liquid or a solid-laden liquid) with a con-
tinuous phase (gas). Spray columns find extensive
applications in the industry for absorption and spray
drying. The main advantages of spray columns com-
pared with packed columns are: (1) high treatment
capacity of the gas phase; (2) low pressure drop for
the gas phase. However, a substantial pressure drop
is needed for a good spray; (3) low fixed capital
investment; (4) in cases where oxidation is the rate-
controlling step (e.g. absorption of NO,), the values
of the mass transfer coefficient are unimportant. The
spray column provides a greater oxidation volume at
a lower fixed capital investment; and (5) the liquid
circulation rate in the case of packed columns is
decided by the minimum wetting rate. This restriction
does not exist for spray columns.
However, the extent of gas-phase mixing is large
in spray columns. This can be overcome by using
intermediate sieve trays.
For the process design of NO, absorption towers,
it is necessary to understand the combined effects
of several equilibria, the rates of mass transfer and

11
12 K. R. JETHAN I et al.

chemical reaction. Further, substantial heat effects
are associated with the NO, absorption and tempera-
ture variations need to be taken into account in the
process design. There have been outstanding attempts
in this direction. For instance, Koval and Peters
(1960), Andrew and Hanson (1961), Koukolik and
Marek (1968), Carleton and Valentin (1968), Hoftizer
and Kwanten (1972), Makhotkin and Shamsutdinov
(1976), Holma and Sohlo (1979), Emig et al. (1979)
and Hoshi et al. (1985) have reported various aspects
of the process design of packed columns, plate
columns and packed bubble columns used for the
manufacture of nitric acid. However, there have been
no modeling and experimental studies using spray
columns. Further, the following additional points
have been considered while modeling spray columns:
Simulation of large size absorbers increases the
confidence in the model development. In the published
literature, although some experimental data have
been collected on pilot scale absorbers, the absorbent
was water in most cases. There is scant inform-
ation available in the published literature regarding
large-scale simulation. Furthermore, there has been
no study when the nitric acid contains some
electrolyte. Therefore, it was thought desirable to
simulate a large-scale spray column absorber.
Mixed-acid solutions (nitric and sulfuric) were used
as solvents. A comparison has been presented be-
tween the model predictions and the experimental
observations.

(0 the rates of absorption of NO,, N,O, and 2. MATHEMATICAL MODEL

Nz04 in nitric acid are different from those in
2.1. Model for overall rate of absorption
water. The rates decrease with an increase in
the concentration of nitric acid; 2.1.1. Gas phase reactions and equilibria. The NO,
(ii) it is known that, for a given set of partial constitutes of mixture of various nitrogen oxides
pressures of NO, NO2 and N2 0, , there exists NO, NO,, N, 0, , N204 and N, 0,. In the presence of
a certain limiting concentration of nitric acid water vapor, which is generally the case in most
beyond which no absorption of N204 and NO2 industrial absorbers, there exist oxyacids HNO, and
occurs (Carberry, 1958). This heterogeneous HNOJ. All the components of NO, are in equilibria
equilibrium substantially reduces (even 3-4 with each other. Nitric oxide undergoes irreversible
times) the rates of absorption of N02, N203 oxidation with oxygen in the gas phase. The oxidation
and N204 and the extent of reduction increases reaction is expressed as:
as the nitric acid concentration approaches
the equilibrium value. This aspect needs to be 2NO(,, + O,,,, A 2NO,, . (1)
included in the mathematical models reported
so far; Joshi et al. (1985) have reviewed the published
(iii) a substantial quantity of nitric acid is formed literature on NO oxidation. It is believed that NO
in the gas phase, particularly at high tem- oxidation proceeds by dimerization of NO followed
peratures and high partial pressures of NO,. by oxidation by oxygen to form N, 0,. The oxidation
Therefore, the HNO, formation needs to be reaction is second-order with respect to NO and
included in the mathematical model; first-order with respect to oxygen.
(iv) mass transfer of HNO,, HNO, and H20. It is Complex equilibria prevail in the gas phase which
known that the transfer of HNO, contributes can be described by following equations:
substantially to the overall absorption of NO,
gases (Hoftizer and Kwanten, 1972). Further- 2NO,, K1_
- N20W, (2)
more, the transfer of water is very important
while taking the energy balance;
a detailed energy balance also needs to be NOW + NOW L
- N,Oy,,, (3)
(v)
incorporated in the model.
NO, + NO,, + H,O, _-% 2HNO,, , (4)
Most of the above features have not been included
in the models published in the literature. Table 1
summarizes the previous work. 3N0, + H2 0, --% 2HNO,, + NO,. (5)

Table 1
Mass transfer of
Role of H,O, HNO, and/
Dependma of heterogeneous Formation of or HNO, from/to
N(kD)‘~ on equilibria on the HNO, in the gas phase to/from Complete energy
HNO, concentration rate of absorption BasPb liquid phase balance
Emin er al. 11979) NC NC NC NC C
Holka and ‘Sohi; (1979) NC NC NC NC
Miller (1987) C NC NC NC
Wicgand et al. (1990) C NC NC NC C
C = considered: NC = not considered.
 Modeling and simulationof a spray column 13
Table 2. Gas phase reactions
yTty%O - yNO)
Equilibrium and rate constants
Equations @mm’) - 1/2yY2[tK4pTYNOy,, yH,0)“2
log,, K, =652.1/T - 0.7356
: log,, K2 = 2993/T - 9.226 - ~K,p,~yN~~3yH,0/yNO~“~
3 log,, K3 =2072/T - 7.234
4 log,, K+ = 2051.17/T - 6.7328 - K3 PT YNG yNOl = 0, (16)
5 log,o KS =2003.8/T - 8.757
yT(y$,O - yH,O)

- 1 /2 yy2 [tK4 pT yNO yN@ yH,0)“2

The reaction rate constant K1 and the gas-phase
equilibria constants K2 . . . KS were reported by Joshi + tK,p,~yNO~~3yH,0/~NO~“~ = 0. (17)
ef al. (1985) and are summarized in Table 2.
For known molar concentrations of inerts, oxygen,
The total number of moles in the gas per mole of
total NO, and the NO*-to-(N*) ratio, equilibrium
inert is obtained by adding ratios of all gaseous
partial pressures of all the gaseous species can be
species to moles of inert:
known by solving (14-17) simultaneously for Yr,
YT = Y,, + Y,o, + Y&O, + Y,,,, yNO 7 YNOI and yHIO. Compositions of HNO,, HNO,,
N,O, and N204 are availed from equilibria relations
+ yHNO, + yHN, + yHIO + yO, + I, (6)
(7-10).
where 2.1.2. Rates of gas-phase mass transfer. The
concentration profiles for the gas film are shown in
YNzO. = K2 t yNOz >2pT / yT P (7) Fig. 1. The volumetric rates of gas phase mass
YNzOj = KS yNG yNG~pTf yT* (8) transfer are given by the following equations:

YHN02 = cK4 yNO yNOz y”,0pT/yT)“2, (9) Ra,o,o = &3a)NObk,0 -dOI, (18)

KSt yNOl 1’yH,O pT “2 (19)

Y HNo, =
r, > .
(kGa)NOsbtiOz -pk~O~l’
(10) R~No,,G =
YNO
R%o&i = (kGa)N~0rb~~04 -Pk+Oab (20)
In computing gas phase equilibria, we assume that
there is no formation or removal of reactive nitrogen. 1PaNz03,G = (kGa)Nz% [P&O3 -&031’ 01)

Hence, Y$, total reactive nitrogen per mole of inert

RaHN03,G = qkG a)HN03 b%NOj - P~INO~I~ tw
is expressed as:
RanNoZ ,G = tRGa)HNOz b&NO, - P&Ozlr (23)
yl: = yNO + yNOz + 2( yN+,,>

RauIO,o = (ba)H20[Ph20 --PO,,,% (24)

+ 2(yN,0,) + Y”NOl + YHNO~, (I11

whereas the extent of oxidation at any moment is 2.1.3. Interface equilibria. At the interface, NO,
expressed in the form of Ygo, moles of divalent NO,, N,09, N,O, and HNO, are assumed to always
nitrogen per mole of inert: be in equilibrium with each other. Thus, at the
interface, gas equilibria is defined by the following
YZ, = YNO •I- YN~o~ + ~.~(YHNo,) -~.~‘(YHNo,). (12) equations:
Y&, is moles of water in the form of oxyacids and PLO.
(25)
K =

free. water vapor per mole of inert. It is expressed as: 2 G&7’

Y&o = yH,O + O-5( yHNO, ) + o-5( YHNOl )- (13)
Equations (7-10) express YNzo,, YNzo3, YuN%
and YHNO~ in terms of UN,, YNol, YHlo and Yr . (P itN_ I2
(27)
When these are substituted in (6) and (1 l-l 3), four K4 = (Pi.lo)(Pk,)(Pt,o> *
equations in Y,, , Y,,,, YHzo and Yr are obtained.
The equations are: HNO, and H,O are at their saturation concentrations
at the interface. The vapor pressure of H,O or HN03
Y: - yT(yNO + YNO, + y”,O + yG, + l) over an aqueous sulfuric acid solution is a function
of temperature and nitric acid concentration:
- y?2 [tK5 pT( yNOl 1’ yHzO / yNO)1’2

+ cK4 pT yNO yNO, y”,0)“21

ph20 =fK concWNOd1, (28)

- 14 pT yNO, yNO + K2pT(yN,)2] = O. cl41 &,O, =f[T, concWNOd1. (2%

yT(y?i - yNO - yNOz)

2.1.4. Liquid-phase reactions. Nitrogen oxides
when absorbed in an aqueous sulfuric acid solution
-
yyz tcK4 pT yNO yNO, yH,O )I” form nitrous and nitric acid. The following reactions
+ ~K,p,~y,,,~3yH10/y~O~“2]
occur in the liquid phase:

- 2%(K2(yN0,)2 - & YNO YN,) = O, (15) 2NO,,,, + H, O(,, - HNOX,, + HNO,, , (30)
 K. R. J~~~uNIet ol.

P
HO
2NO l O,-ZNO,- PM0
f
ZNO, T- Nz04+P
” 2%

NO. NO,& NtO,-P

“2%

3WOt* Hz0 d ZHNO,- P

NHO,
*NO
NO+ N4+Hz0 c- 2HNOL--m PMMo
c

~YEJ&~ BULK LIQUID

Fig. 1. Mechanismof NO, absorptioninto water.

N,%, + Hz%, - 2HNO,<,, 3 (31) Hence limiting partial pressures of NO,, N,03 and
HNO, based on heterogeneous equilibria would be:
N, 0,~ + H2 O,,, - HN02m + HN%, . (32)
Pho, = (PFi,o.l~2P. (37)
HN02 in the bulk of the liquid phase is considered to
be decomposing to form nitric acid: P&O) = K,PLoP:o~. (38)
P~HN~ = [&~~o~k~o,~!t,oI’~. (39)
3HNO,,,) - HNO,,, + 2NO0, + H2 O,, . (33)
No absorption takes place when:
Z-1.5. Mass transfer with chemical reaction in the
liquid firm. The concentration profiles for different P&,0. = Ph*o,.
species in the liquid film are given in Fig. 1. It has The net driving force is thus the difference between
been illustrated by Joshi ef al. (1985) that the absorp- interfacial and limiting partial pressures of N02,
tion of N02, N203 and N204 is accompanied by a N201, N,O, and HN02.
chemical reaction within the liquid film. However, Volumetric absorption rates of different species are
absorption of NO, is also limited by the nitric acid (Joshi et al., 1985)
concentration in the bulk of the liquid phase and
partial pressure of NO at the interface. Carberry R%o,,L = n(HNo,)3’2[2/3(~D)No.$‘2
(1958) made a plot of maximum attainable concen- x <P&o* - Pkoz>3n* WI
tration of nitric acid as a function of parameter K,
defined as: R%,o,,L = aH,,o,[(kD)N,o,11’2
Pi-+* x (P&o. - Pk*cl,h (41)
K6= (PR,04)“2 ’
(34)
Ra NzO3.L = ~HN20,[(kD)~20~l”z

The empirical equation (Matassa and Tonca, 1973) x CP~~~ -PLEA (42)
obtained from various plots is of the form:
R%No,,, = kL a&ma (P&NO2 - P !-lNOdr (43)
In Kn = 2.188 x 10’ Te2.”
Nitrous acid in bulk decomposes to form HNO, and
-4.571 x 10” T-‘.4=’ W, (35) NO in the liquid phase. Since the latter has limited
solubility, it desorbs. The rate of desorption of NO
where
is given as:
Kn ==pNo/p&s = K:‘2&(101.33)2 (36)
RaN0.L= $ RaN,O,,L + f IPaN20..L

and W is the maximum attainable HN03 concen- (49

+ 4 RaNO,.L + 3 IpcIHN02.L *
tration in the weight fraction. The method for deter-
mining & in the presence of sulfuric acid shall be 2.1.6. Overull volumetric rates of __
absorption.
_.
discussed later. Overall rates of absorption are computed by solving
 Modeling and simulationof a spray column 15

equations (18-29) and (34-44). There are 23 equa-

tions whereby unknowns are namely: (i) volumetric
rates of gas phase mass transfer: RaNo,o, RaNo2,0,
AI, = -(K,P~,o)‘“(k,a),,,,/2,
RaN,o,.o 9 KaN2q.o 3 RanNo+ K%No~.o 3 Kan,o,o; A,, = -VwONo,
(ii) partial pressures of NO, NO,, Nz04, N,O,,
A,2 = @Ga)NOpkO + (ko&mzPoHIuoJ2
HNO,, H,O and HNOB at the interface; pNO, pkol,
p&,o,, phlo3, P lHNq, P Lzo, P hNol ; (iii) heterogeneous + (h’)w~P;;zo,
equilibrium parameter &, limiting partial pressures
and
I&,~,. p&oI, p&03, phNq; (iv) rates of mass transfer
with chemical reaction in the liquid film, Ra,*,,, B, [PLZI, - B2(P~oo>“313’2
RaNro3,L, RaNlor.L, RaHNo+; and W rate of desorp-
+ B,P&,, + B&P~& - Bs(~&oo)“~l
tion of NO from the liquid to gas phase RaNo,L.
Two more equations are needed to make the model + B,(P~o,)~ + B,[P!~P& - B~(P~.,o)“~I

consistent. These are provided by the material balance

+ B&~~o~im~o2)“2 - B,~(P~~o)~‘~I
of divalent and tetravalent nitrogen oxides across the
interface. + B,(PLo)(P&oJ
The NO, balance at the interface gives:
+ Bd~k,~b>“‘+ B,, = 0,
(K%oz,o - RaNO,,L.) where
=2(R%G,,L - RaN,04,G) B, = 3A,,

+ V%,O,,L - RaN,o,,G) 4 = A,,

+ l12WaHNG2,L - RaHNo,,G). (45) B3 = (kc a)Nog 3
NO balance at the interface gives: 8, = 3A3,

RaNo,, - K%o.o B,=A,,

= (RaNzol.L - R%,o,,o ) Be = 2K2&9)N9.349

+ l/2(Ra,,~,L - RaHNq,o). (46) B, = 3A,,
Equations (28-29) and (35-36) are solved inde- B, = -Ag.
pendently while equations (18-27), (34) and (37-46)
B9 = 3A,,
are coupled algebraic equations. In order to attain
convergence under varied parametric conditions, it B,,= --Alo,
was found necessary to reduce them to a set of two
equations in terms of p& and p&. The following B1I = - (kG a)NO~p~ol - (kc a)HNOtpoHNq/2

two equations are obtained by substituting equations - (kci&g,P&o~ - 2(k&,,oJ’&o,.

(1%27), (34) and (37-44) into equations (45-46):
B,,=A,.
Al[PLO> - A,(pNo)“y
2.2. Model for the column performance
+ Ad(P&o,)* - A,(Pw’31
2.2.1. Model equations. The spray column has
+ A5[PNOPb* - A2(P~o)4’31 been modeled for simulation studies. The following
assumptions were made:
+ A7KPLoY’2(P~o*)“2 - A,(Pho)2’31
(i) gas and liquid phases flow in a countercurrent
+ A9(P+.10)(PL02) + A,0(PLDY’2(Pk40,)1’2 plug flow manner;
+ AuP& + An (ii) liquid hold-up is uniform throughout the
= 0,
column;
(47) (iii) gases follow ideal gas behavior;
where (iv) the column is operating at steady-state.

AL = Ea(H~0,)3’2((2/3kD)NG~)“*1/3, 2.2.2. Mass balance. Mass balance across a cliffer-

entiai height dh at height h (Fig. 2) from the bottom
A2 = l/Kj’2 K:“,
results in the following differential equations:
-43 = [2K,a%,o, ((kD),,o.)“%3, Component balance in the gas phase:
A., = l/(K, KY3),
(a) divalent nitrogen balance:
AS = [~3a~~,o,((Dk)N,0,)‘~21/3,
4 = (K,P~~*)‘~‘K‘~H,,,,/~.
d YRo
-=
dh
-2 {h(pko)2P&% - RaNO.G

A8 = l/(Ky2 K;‘3)1’2, + hNsOs.0 + 0.5(RaHNq,o - K&t,,,,)}; (49)

16 K. R. JETHAM
CI al.

6AS OUT LlOlJlD IN Table 3. Heats of reaction

standard bc4u of
reaction (25°C)
Reactions kc4 x lo-’
(A) Reactions in the gas phase:
ZNOw + O,, + ZNO, an, = -13.64
kmol-’ of NO oxidized
2NO%, - NzO+j AH, = - 13.49
kmol-’ of N,O, formed
NO, + NO, * N,Ow AH,= -9.55
kmol-’ of N,O, formed
3NOw + HZOW -+ 2HNOw + NOW A&~,-;;.=, formed

NO, + NO, + H,Ow - ZHNO&> AH, = -4.905 ’

km01- ’of HNO, formed
dh (B) Reactions in the liauid uhhase:
. Equations: _ _
(74) kmol-’ of NO, absorbed AH, = - 12.82
(75) kmol-’ of N,O, absorbed AHs= -12.04
(76) kmol-’ of N,O, absorbed AH,, = - 9.55
(77) kmol - ’of HNO, decomposed AH,, = + 5.71
7 (78) kmol - ’of HNO, absorbed AH,, = -9.36
h
(79) kmol - ’of HNO, absorbed AHI = -9.9

librium constants, solubilities, vapor pressures and

I diffusivities depend upon temperature. Heat liberated
6AS iN- L WLI(LUID OUT because of various reactions in the gas and liquid
VD- phases have been included in Table 3. It will be
Fig. 2. Differential element for the mass and energy assumed that the heat liberated is taken up by the
balances. liquid phase and the interface is always saturated with
water vapor.
(b) balance for total reactive nitrogen: If Qr is the total heat change per unit time in
the differential element then the temperature change
dY3 under adiabatic conditions is given by:
-= -g I- RaN0,O + RaNO, ,O + zRaN,% ,O
dh
AT = Q,/mVp”, (54)
+ 2RaN,0.,O + RaHNOa,G + RaHNOz,O 1; c50)
where AT is the temperature change across the
(c) water vapor balance: differential element.

dYB,o
-= - $ (%IsO.o + 1 fZRaHN03 $3 (a) Contribntion to the heat changes from the gas
dh
phase are he to the following step
+ 1/2RaHNO&Oh c51)

(d) oxygen balance: 0) the rate of formation of N203 from NO and

NO, in the differential element is given by:
dYo,_ 1s
-
dh
- -zjz &tP”,o)2(P8,)~Gl- (52) (N2°3)r= (N2O3)e - (N2O3)i + (N2°3hY
(55)
Component balance in the liquid phase:
CN203)r=G(y~~qC- YN~~,~)

(e) balance for nitric acid: S dh. (56)

+ m.l,O,,L

dxmo The rate of heat generation due to N,O,

3 dh = -; i4/3RaN20.,L + 2/3RaN203,L
formation is:
+ RaHNo,,O + wfi~,.L -t w%NO& ). (53) Q,=(N,W,A%; (57)
Equations (49-53) are coupled linear differential (ii) the rate of formation of N204 from NO, in
equations. Total mass balance is established across the differential element is given by:
the differential height on solving these equations
W204h= cN2°4)e - W2O4)i + (N204h*
simultaneously.
(58)
2.2.3. Heat balance. Oxidation of NO, formation
(N204)r= G(YN,o,, - YN~o.+~)
of N20, and N,O, in the gas phase, absorption of
N02, N,O,, N104 and the liquid phase reactions are + RaN,o,,Ls d. (59)
exothermic. The decomposition of HNO,, however,
The of heat generation due to N,O,
rate
is endothermic. Because of these reactions significant
formation is:
heat changes occur. The values of physico-chemical
parameters such as reaction rate constants, equl- Qz=G%WfA.n3; (60)
 Modeling and simulationof a spray column 17

(iii) the rate of formation of HNOl in the a = w2oww- (72)

differential element is given by:
The total heat change in the gas phase is given by:
(HNO3 )f = (HNOA - (HNO, )i + (HNO, )a
Qci=Q,+Q,+Q,+Qe,+Q,+Q,; (73)
(61) Heat changes due to absorption with chemical
= ‘XYm,o~s - Y,,o,,,) reaction:
+ R%a,,o s dh. (62) In the absence of information on heats of dis-
The rate of heat liberated due to HNOS solution of gases the information on heats of
formation is: formation of reactants and products was used to
compute the heats of reactions.
Qs = (HNO, h AH,; (63) Reactions under consideration for the heat
(iv) The rate of formation of HNO, in the balance are:
differential element is given by:
(1) 2NO,@, + H,O(,, -* HNO, + HNO,, (74)
(HNO, )C= (HNO, ). - (HNO, )i
(2) Nz O,,, + Hz% + HNO,<,, + HN%, , (75)
+ (HNO,),, (64) (76)
(3) N, 03uj + H, 0, -* 2HNO,, 3
= G(YHNo,.~-YHN,.~)
(77)
(4) 3HNO,,, + HNO,(l, f 2N0, + H,O, ,
+ hzNo2.L Sdh. (65)
(5) HNO,, + HNOX,,, (78)
The rate of heat liberated due to HNOz
(6) HNO, --t HNO,,,. (7%
formation is:
Heats of reaction are summarized in Table 3.
Q4 = W-JO1 If AH, ; (66) Hence heat liberated due to absorption with
(v) The rate of heat liberated due to the oxida- chemical reaction in the liquid phase is expressed
tion of NO is estimated from the knowledge as
of the rate of NO oxidation. It may be noted
QL = @aNo,,AH, + RaN,o.,AH,
that NO is used in the N,O, and HNOz
formation and it is liberated during HNO, + RaN,o,LaHIo + IpnHNO~,G AHI,
formation.
+bmoz.~ AH,, + &.so,,. AH&S dh. (80)
The mass balance for NO across the
Total heat change in the differential volume is
differential element is given by:
summation of all the heat changes:
NO,, = cN0z.i - NO,.) - N103.f
QT=QG+QL. (81)
- l/2HN0,,f + 1/2HN0,,f, (67)
3. FSI-IMATION OF MODEL PARAMETERS
= G(YN0.i - Y~o,e - Y~,o,,e
Diffusivities of gases vary with temperature and
+ yN203j - 1/2yHN02,c + ~/~YHNo,~
pressure. For this purpose, the following correction
+ ~/~YHNo,,~ - l/2YHN03,i) was used:
- (%+o3,L + 1/2%i,~,, 0, = Drts.=c(T/298.2)‘-75(101.33/P,). (82)
- 1/2R%,o,,o)S dh) (68) The solubility of HNOa and HN02 in water is 2090
and 0.484 km01 me3 (kN me2)-‘, respectively (Joshi
The rate of heat generation due to NO
et al., 1985). The solubility of NO in water is given
oxidation is given by:
by the following equation:
Qs=(N'%AH,. (6% log(101.33 x HNo) = - 1463.32/T + 2.178. (83)
@) Heat changes due to water evaporation:
The solubility of NO and HNO, in the presence of
The rate of water evaporation in the differen- electrolytes like H2S04 and HNOp was estimated by
tial element was obtained by material balance: using the following equation:

(H,O), = (HzO,, - HzO,i) + 1/2HNO,, logW,,lK,.) = -c KL (84)

+ 1/2HNO,,, (70) where

= G(YH,o,, - YH2o.i + 1Dy~~q.e H, = solubility in water, km01 mW3 (kN m-z)-‘,

- 1 /2 YHN03,i + l/2 yHN9.c & = solubility in electrolyte solution, km01 mm3
- 1 /2 YHNOz ,i ) + ( 1 /2RaHN03 $3
(kN m--2)-1 9

+ 1 /2RaHNQ., )S dh, (71) KS 3 salting out parameter = i+ + i- + i,,

18
i+ and i- are contributions of cations and anions
of the electrolyte, respectively, to the salting out
parameter and i8 is the contribution of the solute
gas. Danckwerts (1970) and Onda et al. (1970) have
reported the values of salting out parameters for
various cations, anions and gases. The value of ie for
NO gas was reported by Sada er al. (1977). The value
of ig for HNO, was estimated from the vapor pressure
of HN03 over nitric acid. The value of i,, for HN02
was assumed to be the same as that of HNO,.
Specific rates of absorption of N,O, were measured
experimentally to estimate W(kD)*‘* values. It is
discussed in a later section.
Mass transfer rates in gas-liquid contacting equip-
ment are determined by the gas holdup, interfacial
area and mass transfer coefficients. Pinilla et al.
(1984) have studied mass transfer coefficients for the
gas and liquid phase, interfacial areas and axial
dispersion parameters in a spray column using a solid
cone nozzle. They have presented their results in the
form of graphs. The gas-phase mass transfer co-
efficient (&a), liquid phase mass transfer coefficient
(&) and interfacial area (a) are given as a function
of superficial gas velocity (Vo) and mass velocity of
liquid (L*). The mass transfer coefficients used in the
present simulation work were obtained from the data
reported by Pinilla et al. (1984).
4. SOLUTION OF MATHEMATICAL
The method of solution involved the following
steps:
4.1. Estimation of gas -phase composition
Equations (14-17) form a set of four simultaneous
nonlinear algebraic equations where the four un-
knowns are (moles per mole of inert of) NO, NO*,
H,O and total moles in the gas phase. These four
equations are solved numerically by the Newton-
Raphson matrix method for nonlinear equations.
This method is described below:
The four equations are in the form of:
A(Z) = 0, where i=1,...,4,
2 =(X,,-%,XJ,X,).
and
x1 = YNO. x2 = YNOl 3 x3 = yH20,
Partial derivatives [f&Z) = &(a)/ax,] of these four
equations with respect to the four variables are
derived analytically.
Matrix
&(2) = [&(*)I, 1 < i c n, 1 <i
and
F(Z) = [fi(.Q,fiW **.hW19
where the (k + 1)th estimate of W is:
g’+‘=z”+;ak,
K. R. Jarn,+utet nl.
b is the solution vector for a set of simultaneous
linear equations and is computed as:
b = --F(?) - [r#D(?)]-‘.
The initial value (or guess value) vector is chosen as
a bulk partial pressure from the previous differential
element. Convergence limits are based on either of the
following strategies:
(1) for k < minimum number of convergence
counts a: -z ~~ where e2 is a small numerical
value;
(2) for k > minimum number of convergence
counts @lx: < L) where + is the numerical
error tolerance value.
Values of these four variables are substituted in
equilibria relationships equations (7-10) to establish
gas-phase equilibria.
4.2. Estimation of interface composition and volumet-
ric mass tratufer rates
For the estimation of interface composition, we
need to solve 21 equations simultaneously (l&27),
(34) and (37-46). The intricate algebraic reductions
of these 21 equations into two polynomial equations
(47), (48) has obviated the need for the scaling
algorithm. Equations (45) and (46) are NO and NO2
MODEL balance equations at the gas-liquid interface. The
interfacial partial pressures of NO and NO, are
always present in greater magnitude than other
components of NO,, and hence have been selected as
variables for the solution of equations (47) and (48).
The Newton-Raphson method described earlier in
conjunction with the Gauss-Jordan method has been
employed. The objective behind using this composite
technique of algebraic and analytical in nature was to
achieve a single positive finite solution with minimum
numerical iterations. Substituting these values in equa-
tions (25-27), (34) and (37-39) results in interfacial
and limiting partial pressure values of N204, N203
and HN02.
HNOa and H20 are always at their saturation
concentrations at the gas-liquid interface. The equi-
librium vapor pressures over sulfuric acid and nitric
acid solutions are available from the literature. For a
given temperature and concentration, vapor pressures
x,= Yr. of HNO, and Hz0 are required in computing the
volumetric mass transfer rates. Estimation procedure
for vapor pressures of HNO, and H2 0 from available
data forms a system of one dependent and two
independent variables. The simplest and most reliable
method is to interpolate first with respect to one
< n, variable and then with respect to the other variable.
Standard Newtomgory forward/backward interp-
olation formulas have been used for interpolation.
Volumetric mass transfer rates are computed by
using estimated values of mass transfer coefficients of
gas and liquid phase, physico-chemical parameters
[like W(kD)“T and known values of partial pressures
 Modeling and simulationof a spray column
of various components in the bulk of gas phase and
at the interface.
4.3. Solution of ordinary differential equations
Equations (49-53) are five coupled ordinary differ-
ential equations. A standard fourth-order Runge-
Kutta method is used to solve these equations. Initial
conditions, i.e. gas-phase and liquid-phase concen-
trations and temperature at the bottom of the spray
column are known. Calculations are started from the
bottom of the column. A few dummy variables such
as the concentrations in the liquid phase are also
integrated over the height. These dummy variables
are used for computing contributions of different
components of NO, in the formation of HNO, and
HNO, in the liquid phase.
4.4. Solution of heat balance equations
From the solution procedure described earlier,
concentrations of all the components are known
at inlet and exit of the differential height. Rates of
MODEL SOLVER
pzi&
Fig. 3. Flowsheetof NOXA package.
19
chemical reaction and mass transfer are known from
their contributions within the differential element.
Assuming that all the sensible heat is taken up by the
liquid phase, the change in temperature across the
differential height is estimated by using equations
(54-8 1).
5. PROGRAM STRUCTURE
We have developed a design and simulation pack-
age for NO, absorption (NOXA) in countercurrently
operating mass transfer equipment like spray
columns, packed columns, etc. The package NOXA
is modular and built around the main program
ABSORB. The software has been developed for
general applicability to various absorbents. In the
present illustration, the software has been tailored for
simulating a NO, absorber operating with dilute
solutions of sulfuric and nitric acid as the absorbent
system in a spray column. Different modules of the
NOXA package are shown in Fig. 3. Bidirectional
ROUTlNES
20 K. R. JETHANI et al.
arrows indicate exchange of information and uni-
directional arrows indicate transmission of inform-
ation. The names of the variables used are based on
their physical meaning. Most of the information trans-
fer between the main program and the subroutines is
via COMMON blocks. All the programs are coded in
ANSI FORTRAN 77 on a micro VMS O.S. operat-
ing on a Micro Vax-II computer. Special efforts have
been made in mathematical modeling to improve the
computational economy and speed of execution.
Most of the key components chosen for solution of
the model have a sufficiently large numerical value
which causes early convergence in iterative calcula-
tions with minimum rounding-off errors. The pack-
age was tested for varied parametric conditions and
was found to operate error free in most cases. Careful
program design has insured against logical errors
in most of the subroutines. Options have been pro-
vided for adiabatic as well as isothermal operation.
Section-wise information on the program is given
below.
5.1. Main program ABSORB
ABSORB is the main program module of the
NOXA package. The overall flow logic of ABSORB
is as follows:
1. Read all data files for obtaining initial con-
ditions, properties and physical data.
2. Call subroutines (OXY and WATER) to
obtain initial conditions at the bottom of the
spray column.
3. Call subroutine GASEQ to establish gas equi-
libria in the bulk of the gas phase.
4. Call subroutine WATER to recompute vapor
pressures of water and HN03 at the gas-liquid
interface.
5. Call subroutine FILMOD to compute volu-
metric mass transfer rates in gas and liquid
films and estimate the interfacial composition
of various NO, species.
6. Evaluate derivatives of components with respect
to the column height and integrate numerically
the ordinary differential equations by using a
fourth-order RungeICutta method.
7. Re-establish equilibrium composition in the
bulk of the gas phase (call GASEQ).
8. Estimate temperature changes in the liquid
phase.
9. Check the boundary conditions for concen-
trations of key components in the gas and
liquid phase, temperature and height of the
column.
10. Print the height, temperature and concen-
tration profiles of gas- and liquid-phase
components.
5.2. Subroutine GASEQ
GASEQ is a subroutine subprogram which employs
a Newton-Raphson method for solving coupled non-
linear algebraic equations (14-17) in Y,, , YNoz, Y,,o
and Yr . The flow logic of GASEQ is explained below:
1. Obtain values of P, T, Yg, Y&,:,,, Y&, and Yo,
from the main program.
2. Estimate gas-phase equilibrium constants.
3. Compute the augmented Jacobian matrix con-
taining the nonlinear equations and their partial
derivatives (obtained by calling DERIVI).
4. Compute the increment vector for all four vari-
ables by inverting the matrix (call MATINV).
5. Test each element of the increment vector for
significant values.
6. Re-establish new estimates of the four variables
and limits for significance.
7. Check the consistency of the four variables
before returning to the main program.
5.3. Subroutine WATER
The gas-liquid interface is assumed always to be
saturated with water vapor and nitric acid. Estimated
vapor pressure data at various temperatures and
concentrations of nitric and sulfuric acid are available
from the main program. This forms a system of one
dependent and two independent variables. Double
interpolation by Newton-Gregory single interpolation
was employed to obtain vapor pressures of HNO,
and HrO at the interface. Subroutine WATER is
called from the main program ABSORB and also
from the subroutine FILMOD. The steps in this
subroutine are as follows:
Obtain vapor pressure data at various tempera-
tures and concentrations from the main program.
Choose pivot point and. forward/backward
interpolation techniques depending on tempcra-
ture.
Compute (interpolate) vapor pressures at a given
temperature for all liquid phase concentrations
(by calling NEWGRE).
Choose pivot point and forward/backward
interpolation grid and compute vapor pressures
of HNO, and Hz0 at the desired concentration.
5.4. Subroutine EILMOD
FILMOD is a subroutine which computes volu-
metric mass transfer rates within the gas-liquid film.
It employs modules for estimating gas and liquid
phase mass transfer coefficients and physico-chemical
parameters [H(kD)“g. It assumes equilibria between
components of NO, at the interface. The flow logic
of FILMOD is presented below:
Obtain values of partial pressures, pressure,
temperature and liquid concentrations from
the main program.
Estimate H(kD)“’ (call HKD) and mass
transfer coefficients (call KGA).
Obtain interfacial partial pressures of Hz0 and
HN03 over aqueous solutions (call WATER).
Compute constants of equations (47-48).
 Modeling and simulationof a spray cohann
5. Compute augmented Jacobian matrix contain-
ing nonlinear algebraic equations [equations
(47-48)] and their partial derivatives (call
DERIV2).
6. Compute the increment vector for both vari-
ables by inverting the matrix (call MATINV).
7. Test the numerical values of each element of
the increment vector for significance.
8. Obtain new estimates of partial pressures of
NO and NO, at the interface and limits of
significance.
9. Establish equilibrium partial pressures of all
other components of NO, at the interface,
compute volumetric rates of mass transfer and
absorption with chemical reaction.
10. Check the consistency of component mass
balance at the interface before returning to the
main program.
6. EXPERIMENTAL WORK
6.1. Measuretnent of specific rates of absorption
Absorption of NO,, N,O, and N,O, in water has
been extensively studied in the literature. Joshi et al.
(1985) have critically reviewed the previous work.
Kameoka and Pigford (1977) have shown that the
rates of absorption of N,04 in water and an aqueous
sulfuric acid solution were practically the same. They
carried out experiments with 0.09 N H, SO, solutions.
At higher concentrations of sulfuric acid, the rates are
likely to decrease. Furthermore, in the present work,
the absorbent is a mixture of sulfuric and nitric acid
at different concentrations. The kinetics of absorption
of NO, in mixed-acid solutions have not been studied
in the past. Therefore, it was thought desirable to
undertake a systematic investigation.
For the estimation of rates of absorption, it is
desirable to know the values of diffusivity, rate
constant and orders with respect to different species.
WATER
IN
Fig. 4. Schematicdiagram of the experimentalset-up in a stirredcell.
21
The measurement of these individual parameters is
extremely difficult. Fortunately, the rates of absorp-
tion can be determined if we know the value of
combined parameter Hx(kD)y2 as described by
equations (40), (41) and (42).
Experiments for determining H,(kD):p values for
NO, and N204 in water and mixed-acid solutions of
nitric and sulfuric acid were conducted in a stirred cell
with an i.d. of 95 mm. Temperature was maintained
by using a constant temperature bath. The schematic
diagram of the experimental set up is shown in Fig. 4.
The effect of mass transfer was eliminated by varying
the stirrer speed. It was found that the speed of
agitation does not have any effect on the rate of
absorption when the speed exceeds 40 revmin-‘.
Therefore, all the experiments were performed at the
speed of 40 rev min-I. Furthermore, at this speed, the
liquid surface was found to be flat without any vortex
formation.
A gas stream constituting 19-20% NO, was
obtained as a product gas from the pilot plant of
oxalic acid. The gas stream was analyzed for divalent
and tetravalent nitrogen oxides. Over 96% of NO,
was in the form of NOT. For all the experiments
120ml of absorbent was contacted with the NO,
flowing in the stirred cell for a period of 5 min. The
total volumetric flowrate of gases was measured by
using a calibrated rotameter. It was set at 250 ml s-i_
Water, 40% sulfuric acid and mixed-acid solutions
containing nitric acid and 40% sulfuric acid were
used as absorbents. A few experiments were also
conducted to evaluate the effect of temperature on the
values of the absorption parameter Hx(kD)ij2.
Tetravalent nitrogen oxides (NO:) constituted
more than 96% of the NO, gas used in the exper-
iments. Under these conditions the partial pressure
of divalent nitrogen oxides (pi0 and phzo3) was
negligible. It is expected that the values of
[H3’2(2/3kD)1’2]No, and [H(kD)‘/2]N20, in H,SO, will
TEMPERATURE TRANSMETER
f CONTACT THERMOMETER1
@ TEMPERATURE CONTROLLER
HEATINB PAD
ROTAMETER
20 Y. NO. (96 Y. NO*)
22 K. R. JETHANI et al.

be lower than those in water due to the presence of Table 5. Nitric acid concentration equivalent to mixed acid
concentration
the electrolyte. It was assumed that:
Wt% HNO, w(km’2lN,or Equivalent wt%
in 40% H,SO, at 30°C HNO, in water
W3’2W3kD>"zl~o, ,watcr W(kD)‘“l~,o,wer
[H3’2(2/3kD)1’21~o,,,,,, = [WkDP21~~o~.~~so,. (85) 5
10
15
2.70
2.168
1.44
x
x
x
10-e
lO-6
10-e
36.36
38.55
41.93
The specific rate of formation of HN03 by the 20 0.519 x 10-6 47.97

absorption of NO, gas is given by the following

equation:
(ii) for water and nitric acid (Lefers and Van der
R HNOl = 413~~~o, + 213~~~~ Berg, 1982):
,o[-3.21551.424W’/(l - w))l.=] ,-1285.3/T
[H&D )“2]N20,= . (89)
= 4/3[H(kD)“21N204.H2SOIPNt0,
WtkD )“z]Ny,, values in the presence of 40% sulfuric
+ 2/3[~S’z(2/3~D)“21~~~.~~~~.(~N~~)3’2,
(86) acid were found to be much lower than those found
The interfacial partial pressures of NO2 and N204 are in water. This is because the activity of water
decreases in the presence of sulfuric acid. The values
related by equation (25). The following equation is
obtained by substituting equations (25) and (85) in of [H(kD)“z] given by equations (88-89) were used
equation (86): for the estimation of &-values for mixed acids. The
equivalent nitric acid concentration was estimated on
the bases of the same [II(kD values. Table 5 gives
R HNO~= [HW)“21,,,,,,,o, 413 K,QJL,,)~
the values for nitric acid concentration equivalent to
mixed-acid concentration. These values were used for
+ 2 W3’2W3 kD)“21N02,woter
cpi )3,2 determining KG from equation (36).
NO2 3 (87)
3 [H(kD )“21~mvater The values of [H(kD)“2]Nzo, and [H3/2(2/3kD)“~No2
The value of [H(kD)‘12],,0,,,,,,,, was obtained from were assumed to vary (with respect to concentration
equation (87) by using the experimental values of the of acids and temperature) in an identical manner to
specific rate of formation of HNO,. that of [H(kD)“2]N,0,.
The value of [H(kD)1’2]N,0, for water was found 6.2. Absorption of NO, in spray column
to be 7.6 x lop6 kmol m-’ 3SC’* (kN m-2)-’ at 30°C.
This value is in agreement with those reported in the Experiments were conducted in a countercurrently
literature (Sherwood et al., 1975; Joshi et al., 1985). operated spray column. Details pertaining to column
The values of H(kD) ‘P for N,04 at various acid dimensions and internals are given in Table 6. The
concentrations are given in Table 4. It can be seen spray column was of 1.25 m Ld., 11.5 m total height
that the value decreases with an increase in the con- and 10 m spray height. The schematic diagram of the
centration of nitric acid. Furthermore, [H(kD)“Z],,, experimental set up is shown in Fig. 5. The details of
was found to increase with an increase in tempera- the spray column are shown in Fig. 6.
ture. It was thought desirable to develop a correlation The spray column was used for the recovery of
NO, gases generated in the manufacture of oxalic
for [H(~D)“‘IN~o, in the range of temperature and
concentration covered in this work. The following acid. The process consists of oxidation of mono-
correlations were found to hold:
Table 6. Details of experimental set-up
(i) for mixed-acid solutions: Snrav column
Diameter (m) I .25
W(kD Yl N20, = 3.66 x ]Oe5 e-6263.7/RT Total height (HI) 11.5
Spray height (m) 10.0
x (1 - 1.16 x 10-2W, - 1.267 x IO-‘W$,), (88) Material of construction S.S. 316
Liauid distributors Straight pipe header type, 50 NB.
2 Nos
Spray naz.zles per distributor 12
Table 4. Experimental values of [I+(kD)1’2],,, for 40% sulfuric Volumetric flowrate per noule 6lmin-’ at4Opsia
acid (% of NO, = 19; temperature = 30°C; ccmcn of sulfuric acid = Type of spray nozzle- l/4” NPT male-threaded flat
40% w/w) cone type, cone angle = 65”
% w/w Nitric acid [H(kD)‘p]N ,[kmol mm3 s(kN II-I-‘)] x lo6 Fully-developed flow within 1 m
Total flowrate (m3 h-‘) 12-15
0.0 2.95 Temuerature of ooeration (“0 33
5.0 2.60 PI& heat exchao~r (m’) . ’ 12
10.0 2.29
bP
15.0 1.12 C+acity(m3h-‘) 15
20.0 0.60 Heat (m of water) 45
Nitric acid = 0% w/w Material S.S. 316
Sulfuric acid = 40% w/w Bxperimental conditions:
Temperature [H(kD)l’z],,,,, [km01 m-* . s@N m-‘)I x 10s
V,(mm s-y 2-3
IO-12
40 3.3 1380
20 2.8 0.08-0.1
IHWPI Nl,,,, 30°C for water = 7.6 x 10-s km01 HI-~. s(kN m-3
Nld, at the inlet (%) 19-23
 Modeling and simulation of a spray column 23

l-
GAS OUTLET 6hS OUTLET

SPRAT NOZZLES LIQUID SPRAY

(12 Nor1
(12 NOZZLES)

SIEVE TRAY

GAS 1NLET -

LlOUlD INLET-
PHE

so NClO
LIQUID SPRAY
CP (12 NOLZLtS)

Fig. 5. Schematic diagram of the spray column absorption

system: CP = centrifugal pump; LLI = liquid level indi-
cator; Rl = rotameter 1; R2 = rotameter 2; R3 = rotameter
3; ST1 = sieve tray 1; ST2 = sieve tray 2; ST3 = sieve tray 3;
and T = temperature indicator. SIEVE TRAY

sachharides using mixed-acid (40% w/w sulfuric

acid and 14-15% w/w nitric acid). The oxidation
reactions are as follows (Kirk and Othmer, 1981):

(4 C,H,,O, + 12HN0,
+ 3C,H,O,. 2H,O + 3H,O + 3N0 + 9N0,;

@I 4CsH,*0, + 18HNOS + 3H,O

+ 12C,H,O,. 2H,O + 9N,O;

(cl C6 H,, 0s + 6HNOj

+ 3C2 H, 0, .2H, 0 + 6NO;

(4 CsHn06 + 12HN09
---*6C0, + 12H,O + 6N0 + 6N0,.
These reactions were carried out in stirred tank
reactors operated in series. The off gases consist
mainly of NO, and COz (some CO2 is generated due
to complete oxidation). The volumetric flowrate of
this stream was measured by using a pre-calibrated
orifice meter. A centrifugal blower was used to
provide the required measured quantity of air
continuously. This pre-mixed gaseous mixture was
introduced at the bottom of the spray column. The
spray column is divided into four sections of 2.5 m
each, separated by perforated sieve plates to reduce
backmixing and channeling in the gas phase. Spray
nozzle assemblies are placed at 6 and 11 m from the
bottom of the spray column. The spray nozzles are
LlOUlD OUTLET
Fig. 6. Details of spray column.
l/4“ NPT male-threaded, flat cone types with cone
angles of 65”, and height 37 mm. The spray nozzles
have a discharge rate of 6 1rain-’ nozzle-’ at 40 psia
pressure and they achieve fully-developed flow within
1 m. Each spray nozzle assembly consists of 12 spray
nozzles placed on a 50 NB straight pipe header. In the
absence of any data, we have used the correlations for
solid cone nozzles for the estimation of a, k,u and kou.
The liquid product from the reactors consisted
of sulfuric acid (40% w/w), product oxalic acid
(ll-12% w/w) and unreacted nitric acid (0.5% w/w).
Oxalic acid was separated by cooling crystallization.
24 K. R. JP~UNI et al.

The mother liquor was used for the recovery of NO, These are: (a) variations in the rates of absorption of
gases and enters the liquid circulation loop of the NO*, N,Os, N,04 with respect to concentration of
spray column. The average composition of the liquid nitric acid; (b) heterogeneous equilibria between NO,
phase for the spray column is given in Table 6. The N,03, N,O, and nitric acid concentration; (c) form-
liquid overflow stream from the spray column was ation of nitric acid in the gas phase; (d) complete
cooled in a plate heat exchanger and part of it was energy balance. The new model is capable of
recycled to the stirred tank reactors along with a make- incorporating the effects of maximum permissible
up stream of mixed-acid (nitric and sulfuric acid). concentration of nitric acid on NO, absorption.
Composition of the gas and temperatures were 2. Specific rates of absorption of N20, in water
measured at the inlet and outlet of the spray column. and mixed-acid solutions of sulfuric and nitric acids
The liquid-phase concentrations and the flowrates were measured in a stirred cell with a flat interface.
were also measured. Liquid-phase concentration was The observed rates of absorption were found to agree
measured by fixing the acid mixture in an excess with the published literature. In mixed-acid solu-
quantity of sodium hydroxide. The concentrations of tions, the specific rates of absorption were found to
sodium nitrate and sodium sulfate were measured decrease with an increase in nitric acid concentration.
using an ion chromatograph (Dionex HPIC model The following correlation was found to hold good
2010 i). Calibration charts were constructed by in the range of O-20% w/w HNO, in 40% w/w
using the standard samples of NaNO, and Na*SO.,. sulfuric acid, and at 18-19 kN me2 partial pressure of
The liquid-phase flowrate was measured by using a tetravalent nitrogen oxides:
pre-calibrated rotameter.
[N(/cO)‘/z]N,o, = 3.66 x lo-* e-6263.7/Rr
6.3. ResuIts and discussion
x (1 - 1.616 x lo-*Wu - 1.267 x lo-‘W&).
Details pertaining to the superficial gas velocity,
superficial liquid velocity, temperature of operation 3. Absorption of NO, gases was carried out in
and the concentrations of various species are given a 1.25 m i.d. spray column. A favorable agreement
Table 6. The percentage removal of NO, in the spray was observed between the model predictions and
column is summarized in Table 7. For the purpose experimental observations.
of comparison, results of model predictions are also
given in Table 7. A favorable comparison can be seen NOMENCLATURE
between the predicted and experimental values of
* = Interfacialarea,in2m-’
conversion with respect to NO,. C,O=Average specific heat of liquid phase, kcal
It may be noted that most of the liquid phase was Ckmol K-l)-’
recycled in the spray column, as shown in Fig. 5. As d/r=
Differential height of column
a result, the HNO, concentration in the liquid phase D, =
Diffusivity of component x, m2s-’
Do =
Diffusivity in the gas phase, mr s-’
attains a constant composition This was indeed
D, =
Diffusivity in the liquid phase, m* SC’
found to be true in the present set of experiments. G =
Flowrate of inerts, kmol s-I
Therefore, the contributions of HNO, formation and G* =
Mass flowrate of gas stream, kg m-* s-’
decomposition to the extent of NO, absorption were U(kD)‘j2 =
Absorption factor for fast pseudo-first-order
not considered in the present model. reaction, kmol [m*(kN m-*)s]-’
Hx(kD), ‘P = Absorption factor for fast pseudo-first-order
reaction for component x, km01 [mr(kN
7. CONCLUSIONS
m-%I-’
1. A
mathematical model has been developed AH = Standard heat of reaction, kcal kmol-’
U, = Solubjljty in electrolyte, kmol m-r (kN f-r)-’
in which four new features have been included. H No = E!ytuy m NO in water, kmolm- (kN
)
Table 7. Total flow of gas = 2.495 x IO-’ H, = Solubility in water, kmol me3 (kN m-‘)-I
kmols-‘;flowofNO,-6x IO-*kmols-I; H = Total height of spray column, m
NO*/N* = 0.60; flow of air = 1.84 x lo-’ h = Height, from bottom of the spray column, m
kmol s-’
k, = Liquid-side mass transfer coefficient, m s-’
spray column k, = Forward reaction rate constant for reaction n
Removal of NO_ C%) k _ = Backward reaction rate constant for reaction n
Simulation ^ . 48.2 z” = Equilibrium constant for reaction n
Experimental 47.7 X;, = Heterogeneous equilibrium constant defined
NO*/N* at outlet by equ&ions (34) and (36)
Simulation 0.65 kc = Gas-side mass transfer coefficient. kmol [m* s
Exoerimental 0.57
(kN m-*)1-’
Aver&e concn (%)
KH = Heterogeneous equilibrium constant defined
Nitric acid 12.0
Sulfuric 40.0 by equations (35-36)
Pressure atm L = Flowrate of liouid. kmol s-’
Temperature of liquid (“C) L l = Mass velocity bf liquid, kg m-* s- ’
At inlet 31 I;,= Latent heat of vaporization of water, kcal
At outlet kmol- ’
Simulation 32.5
m” - Mass flowrate of liquid, kmol s-r
33.0
N* = Total moles of NO,
 Modeling and simulation of a spray column
NO* = Total moles of divalent nitrogen oxides
NO: = Total moles of tetravalent nitrogen oxides
PI: = Limiting partial pressure of component x at
the gas-liquid interface
p: = Partial pressure of component x at the gas-
liquid interface
p: = Partial pressure of component x in bulk of gas
phase
Pr = Total pressure of gas, kN rn-’
Q, = Heat changes due to formation of N,03 in
bulk gas, kcal s-’
Qs = Heat changes due to formation of N,O, in
bulk gas, kcal s-i
Q, = Heat changes due to formation of HN03 in
bulk gas, kcal s-I
Q4 = Heat changes due to formation of HNO, in
bulk gas, kcal s-i
Q, = Heat changes due to oxidation of NO in bulk
of gas, kcal s-l
Qs = Heat changes due to water evaporation in bulk
gas, kcal s-’
Q, = Total heat changes in gas phase, kcal s-’
Q,_ = Total heat changes in liquid phase, kcal s-’
Qr = Total heat changes, kcal s-’
R = Universal gas constant, (m3 kN m-‘) (kmol
K)-L
fiX*l. = Rate of absorption of component X, kmol
(m3 s)-’
fi,.o = Rate of gas phase mass transfer of component
X, kmol (m” s)-’
Re, = Reynolds number for liquid
S = Cross-sectional area of the column, mz
SC, = Schmidt number for gas
T = Temperature, K
AT = Temperature difference, K
V,_ = Superficial liquid velocity, m s-’
Vo = Superficial gas velocity, m s-’
W= Weight fraction of HNO, in aqueous nitric
acid solution
W, = Weight percentage of HNO, in mixed acid
X, = kmol of x ions kmol-’ of water
(X), = Component X at the exit of the differential
volume
(X) = Component X at the inlet of the differential
volume
(X), = Component X formed in the differential volume
(X), = Component X oxidized in the differential
volt&e
(X), = Component X vaporised in the differential
volume
X(s) = Component X in the gas phase
X,,, = Component X in the aqueous phase
Yr = Total moles of gas mol-* of inert
Y, = Moles of gaseous component x mol-’ of inert
(Y,), = Y, at the exit of the differential height
( YX)i = Y, at the inlet of the differential height
Y,: = kmol of reactive nitrogen kmol-’ of inerts
Yg, = kmol of divalent nitrogen kmol-’ of inerts
Y&o = kmol of water in form of oxyacids and free
water in gas phase kmol-’ of inerts
Greek symbols
co = Fractional gas hold-up
Lo = Fractional liquid hold-up
Subscripts
a = Absorption
e = Exit condition
f = Formation
25
G = Gas phase
i = Inlet condition
L = Liquid phase
T = Total
v = Vapor
REFERENCES
Andrew S. P. S. and D. Hanson, The dynamics of nitrous
gas absorption. Chem. Engng Sci. 14, 105 (1961).
Carberry J., Some remarks on chemical equilibrium and
kinetics in the nitrogen dioxide-water system. Chem. Engng
Sci. 9, 189 (1958).
Carleton A. J. and F. H. Valentin, Proc. Fourth European
Symp. on Chem. Reaction Engng (suppl. Chem. Engng
Sci.). p. 361. Pergamon Press, Oxford (1968).
Carta G. and R. L. Pigford, Absorption of nitric oxide in
nitric acid and water. Ind. Engng Chem. Fundam. 22, 329
(1983).
Danckwerts P. V., Gas-Liquid Reactions. McGraw-Hill,
New York (1970).
Emig G., K. Wohlfahrt and U. Hoffmann. Absorption with
simultaneous complex reactions in both phases demon-
strated by the modeling and calculation of countercurrent
flow columns for the production of nitric acid. Computers
them. Engng 3, 143 (1979).
Hoftixer P. J. and F. J. G. Kwanten, Absorption of nitrous
gases. Gar Purification Processes for Air Poiltrtion Control
(G. Nonhabel, Ed.). Newnes Butterworths, London
(1972).
Holma H. and J. Sohlo, A mathematical model for an
absorption tower of nitrogen oxides in nitric acid
production. Computers them. Engng 3, 135 (1979).
Joshi J. B., V. V. Mahajani and V. A.. Juvekar, Absorption
of NO, gases. Chem. Engng Commun. 33, 1 (1985).
Kameoka V. and R. L. Pigford, Absorption of nitrogen
dioxide into water, sulfuric acid, sodium hydroxide, and
alkaline sodium sulfite aqueous solutions. Ind. Engng
Chem. Fun&m. 16, 163 (1977).
Kirk and Othmer, Encyclopedia of Chemical Technology,
Vol. 16, p. 623, 3rd Edn. Wiley, New York (1981).
Koukolik M. and J. Marek, Proc. Fourth European Symp.
on Chem. Reaction Engng (suppl. Chem. Engng Sci.),
p_ 347. Pergamon Press, Oxford (1968).
Koval E. J. and M. S. Peters, Reaction of aqueous nitrogen
dioxide. Ind. Engng Chem. 52, 1011 (1960).
Lefers J. B. and P. J. Van der Berg, Absorption of NO,/
N,O, into diluted and concentrated nitric acid. Chem.
Engng J. 23, 211 (1982).
Makhotkin A. F. and A. M. Shamsutdinov. Khim. Khim.
Tekhnof. 19, 1411 (1976).
Matassa C. and E. Tonca, Basic Nifrogen Compounds.
Chemical Publishing Co., New York (1973).
Miller D. N.. Mass transfer in nitric acid absorption. AIChE
JI 33, 1351 (1987).
Onda K., E. Sada, T. Kobayashi, S. Kito and K. Ito, Salting
out parameters of gas solubility in aqueous salt solutions.
J. Chem. Engng Jpn 3, 18 (1970).
Pinilla E. A., J. M. Diaz and J. Coca, Mass transfer
and axial dispersion in a spray tower for gas-liquid
contacting. Can. J. Chem. Engng 62, 617 (1984).
Sada E., H. Kumaxawa, N. Hayakawa, I. Kudo and
T. Kondo, Absorption of NO in aqueous solutions of
KMnO,. Chem. Engng Sci. 32, 1171 (1977).
Sherwood T. K., R. L. Pigford and C. R. Wilkc, Mars
Transfer. McGraw-Hill, New York (1975).
Wiegand K. H., E. Scheibler and M. Thiemann, Computa-
tion of plate columns for NO, absorption by a stage-to-
stage method. Chem. Engng Technol. 13, 289 (1990).