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The Chemical Engmeermg J ournal, 23 (1982) 211 - 221

0 Elsevler Sequoia S A , Lausanne - Prmted In The Netherlands


Absorption of N02/ N204 into Diluted and Concentrated Nitric Acid
J B LEFERS* and P J van den BERG
Laboratory of Chemwal Technology, Delft Unwerslty of Technology, Juhanalaan 136, 2628 BL Delft (The
Netherlands)
(Received 2 July 1981)
211
Abstract
The absorptron rate and mechanism of
N&-N204 gas mixtures drluted wrth mtrogen
mto nltrlc acrd solu trons were mvestrgated rn
a wetted wall column at 20 C and 30 C I t
was found that Nz04, whrch I S contrnuously
in equlllbrlum wrth NOP, B preferentially
absorbed into diluted nrtrrc acid as well as
rn to concen tmted nl truz acid The absorp tlon
of N204 rnto diluted acid I S accompanred by
a rapid pseudo-first order reaction with water
Values of HN,o,m were measured as a
functron of the acrd strength at 20 C
Above 63% nltrrc acid the absorption was
found to be purely physical The solubrllty
of N204 rn to concentrated nitric acrd (> 63%)
was derived from total vapour pressure data
concernmg the system NO,-N,O,-H,O-
HNO:, I t was found that Henrys law was
valid wl thin the condltron considered
INTRODUCTION
The absorption of NOp which 1s m equlhb-
num mth N204 mto water and mtnc acid
solutions IS very important for the production
of nitric acid
Moreover nitric acid can be used as a scrub-
bmg liquid to remove oxides of nitrogen from
tall gases of mtnc acid and nitration plants
Many mvestlgatlons can be found m the
literature concerning the absorption of NO,-
N,O, gas mixtures into water [l - 12, 14, 291
However, for industrial absorber and scrub-
ber design calculations the absorption rate
and mechanism of these gas mixtures mto
*Present address KEMA, Utrechtseweg 310.6800
ET Arnhem, The Netherlands
mtnc acid are much greater importance but
no reliable data can be found m the literature
In the present work the absorption mech-
anism of NO,-N,O, mto diluted and con-
centrated mtnc acid are mvestlgated m a
wetted wall column at 20 C and 30 C.
Furthermore, the solublhty of N,04 into con-
centrated mtnc acid 1s derived from total
vapour pressure data of the system N,04-
NO,-HNOs-H,O
ABSORPTION MECHANISM OF Nz04 INTO
WATER
Several mvestlgators [l - 12, 141, found
that if a NO,-N,O, gas murture 1s absorbed
mto water and diluted mtnc acid, Nz04 1s
the active species and physically dissolves m
the solution After dlssolutlon the N204
reacts with water to form mtnc acid and
nitrous acid The followmg reaction scheme
represents this
2NO2 (g) s N204 (8) (1)
N2O4 + Hz0 + HNO, + HNO2
(II)
Recently, Komlyama and Inoue [29] found
that this mechanism 1s not valid for very low
NO2 concentration m the gas phase (ppm
range) The nitrous acid produced by reaction
(II) may decompose according to
3HN0, -, HNOs + 2N0 + Hz0
(III)
Decomposltlon of nitrous acid does not take
place rapidly if its concentration 1s low [ 1, 5,
6, 7,614
The equlhbnum represented by reaction (I)
1s so rapidly estabhshed that it may be as-
sumed that NO:, and N2O4 are contmuously m
equlhbnum with each other [ 131 The equl-
hbnum constant can be described with
212
PNA, _
689161
K,=
Pco, exp
- 21
T
(1)
Applying the theory of mass transfer accom-
panied by a rapid pseudo-first order reaction
m the liquid phase the absorption rate per
unit of surface area can be written as
J
N 0, = HN20,
P
N20, L xfm (2)
Note that the value of k as defined m eqn (2)
mcorporates the molar concentration of
water Values of HNzo,a for water have
been measured by several authors using lab-
oratory absorbers Table 1 @ves a review of
these mvestlgatlons Hoftijzer and Kwanten
[ l] found the following equation for water
log &odm= - 0 53 - (760/T)
m the temperature range 276-348 K
(3)
TABLE 1
Comparison of literature data concernmg the absorp-
tlon of N204 Into water
References lo3 X HN,o, m (kmol m-2s-1 bar-l)
20 C 25 C 30 C
,;I
iI21
[71
[lOI
[81
[II
[141
1 09
0 57
1 09
0 76 0 88
0 56
0 68
0 92
0 49
EXPERIMENTAL
The expenments were carried out m a
wetted wall column, which 1s schematically
presented m Fig 1 Nltnc acid solutions
were introduced by gravity in the wetted
wall column through an annular slit The
lammar falling liquid film covering the inner
side of the inner tube (diameter 3 45 cm)
flowed down and was inclined to an annular
pool mth a small surface area, m which the
liquid level was kept on a constant height by
means of a level controller The film height
(h) was corrected for the end effect caused by
the stagnant liquid film above the annular
pool [19, 271 The effective film height (h)
m the NOz-expenments was 13 7 cm and
Fig 1 Sketch of the wetted wall column, dlmenslon
In mm
34.6 cm About 0 05% by weight of an alkyl
sulphonate was added to the liquid to ehm-
mate npples on the liquid f&n
Nitrogen dioxide, supphed from a cylinder,
was mixed mth a nitrogen gas stream and the
gas mixture was led m co-current flow
213
through the wetted wall column The flow
rate of the gas murture was chosen m such
a way that the average gas velocity was equal
to the surface velocity of the hquld film In
this way a lammar gas flow unth a flat velocl-
ty profile (plug flow) could be estabhshed
(see Fig 2)
llauld
I
h
Fig 2 Flow model and co-ordinate system
The m- and outgoing liquids were analysed
for their N,04 and HN02 content by mlectmg
a liquid sample (50 - 250 ~1) mto 10 cm3 of
0 8 M NaOH solution After reaction the
nitrite content was determined wth a colo-
nmetrlc method m an Auto-Analyzer [ 201.
Note that wth this method N,O1 and HN02
m the mtnc acid samples can not be dlstm-
gulshed The outgoing gases were analysed for
their NOz, Nz04 and NO content by means of
Infrared spectroscopy [ 271 The concentra-
tion of NO* and Nz04 in the mgomg gas
stream was calculated by estabhshmg a mass
balance around the wetted wall column
Prior to the NOz- absorption expenments
the liquid phase and the gas phase mass
transfer were investigated separately and were
compared wth the theoretically predicted
values
Llqurd phase mass transfer
The liquid-phase mass transfer was m-
vestlgated by absorbing pure CO2 mto water
at 20 C and 1 013 bar Under certain con-
ditions this physical absorption process can
be described by the theory of penetration
The amounts of CO2 absorbed by the liquid
with lmtlal zero gas concentration per unit of
surface area and after a contact time 7 can be
written as
(4)
A plot of #co, versus dr should @ve a straight
lme through the origin with a slope of 2CIqi X
m (Fig 3) From regression analysis the
slope was found to be 1 78 X 10m6 km01 m-*
s-l* which agrees very well with the value of
1 82 X lO-j kmol m-* s-l* found by Nysmg
1191
2 5
2c
15
E
z
E
* 1C
co
0
*
N
uo
8.05
I C
Fig 3 Absorption of CO2 mto water as a function
of the contact time (P, = 1 013 bar, T= 20C)
symbol h(cm)
0 15 9
7 34 9
* 51 9
Gas phase mass transfer
The gas phase mass transfer behavlour was
investigated by absorbing NH3 from a mtro-
gen gas steam into 2N sulfuric acid. If the
gas phase mass transfer takes place by molec-
ular diffusion only m radial direction the
fractional concentration change of NH,
m the gas phase can be described by
c,(h) - 1
- = 4 z a~ exp(-a,*n/Gz)
c
g.0
,x=1 n
m which the Graetz number 1s defined as
Gz= -!!-
pgDgf+
(5)
(6)
214
The values of u, can be found m the literature
[Zl] The experlmental results are @ven m
Fig 4 and from this figure It can be con-
cluded that the gas phase mass transfer 1s
well predicted by the Graetz-model At large
Graetz numbers the gas phase may be con-
sldered to be mfmltely deep and then the gas
phase mass transfer can be described by the
penetration theory More details have been
published elsewhere [ 271
0
lu
t
0
01
I I I I I
0 0 02 0 04 0 06 0 06 010
-A
== red
Fig 4 NH3 absorption experiments m a wetted wall
column mto 2N HzS04 at 20 C, comparison be-
tween experlmental results and theory
(-
theoretlcal hnes)
symbol h(cm)
0 14 9
34 9
A 51 9
RESULTS
Absorptron of NzO, rnto drluted mtrrc acrd
If NO,-N,O, gas murtures are absorbed
from an inert gas stream both are transferred,
m contmuous equlhbnum with each other,
from the gas phase to the gas-liquid mter-
face The diffusion of a NO,-N,O, gas
mixture m the gas phase was regarded as the
diffusion of one flctltlous component Q
defined as
cQ = CNO,,g + 2CN,0,.~ (7)
The gas phase mass transfer of the fictltlous
component Q can then be described by the
Graetz-model accordmg to
cc2 -cc?,, _ - 1
C,,o - Co.1
-4 z ,exp$$
( 1
n=1 an Q
(8)
The gas phase diffusion coefflclent of the
flctltlous component Q as a function of
D
NO, and DN,o,
was derived by Dekker [ 121
DQ = DN~o, +
2(DN0, - DN, o, )
dl + 8K,,FQ., + x/-K$~,,
(9)
D
No,
=136X 10L5m2s-
at 20 C and 1 0132 bar
DN,o,
= 096X10-5m2s-1
at 20 C and 1 0132 bar
m which Po,, 1s the partial pressure of NO2 +
2N204 at the gas-liquid interface and Poqo 1s
the partial pressure m the middle of the
wetted wall column. At the interface N,O,
dissolves m the liquid and reacts with water
according to reaction (II) The nitrous acid
produced does not decompose very rapidly
according to
3HN0, + HNOs + 2N0 + Hz0
(IV)
NO 1s very poorly soluble m aqueous solu-
tions and it can be easily diffuse mto the gas
phase Within our measured condltlons no NO
could be detected m the gas phase with
infrared spectroscopy [ 271 Therefore, we
assumed that the decomposltlon of HN02
could be neglected The absorption rate of
N204 mto the liquid phase can under un-
steady-state condltlons be described by eqn
(2), provided that hi >> 1 Within the exper-
imental circumstances this condltlon 1s ful-
filled The temperature nse near the mter-
face as a result of the heat evolved by ab-
sorption was calculated and found to be
small enough to be neglected (< 0 2 C) The
partial pressure of N204 on the gas-liquid
interface was calculated from eqns (8) and
(9) and known partial pressures of NOz and
N,04 of the in- and outgoing gas stream by
means of an iteration procedure The mea-
sured absorption rate as a function of PN,o,,I
was plotted for 25% nitric acid m Fig 5 and
for 40% nitric acid in Fig. 6 This should give
a straight line through the ongm urlth a slope
of &,o,a F
rom these figures it can be
concluded that N204 1s prefer&tlally ab-
sorbed mto the liquid phase Regression anal-
ysis gave the slope of the strrught lme and the
results are gwen in Table 2
From this table it can be seen that the
values of HN,04a decrease mth mcreasmg
215
N20A I
(0)
bar
Fig 5 The absorption rate of Ns04 mto 25% HNO3
at 20 C as a function of the partial pressure of the
active species on the Interface, h = 0 346 cm, 7 =
0 646 s, c, pNzO,.i + PN0,,,/2* ov PN20,,~
%*o, I 101
km
%+o. I I)%c+ I ,a,
Fig 6 The absorption rate of Nz04 mto 40% HN03
at 20 C as a function of the partial pressure of the
active species on the Interface h = 0 346 m, r =
0 722 s. 0. PN204~~, A, PN,O,.~ + pN01.,/2
TABLE 2
-
HN+JkD, values as a function of the nitric acid
strength at 20 C
Acid strength HN,o,~ x lo3 Reference
kmol me2 bar-l s-l
Water 0 76 [71. ill
25% HN03 0 49 f 0 03 this work
40% HN03 0 16 2 0 02 this work
acid strength This may be caused by the
decrease of HN,o, mth Increasing lomc
strength and the decrease of the pseudo-hrst
reaction rate constant k, smce the concentra-
tlon of the free water becomes relatively
small m more concentrated nitric acid [l]
The mfluence of the lomc strength on HN,o,
in diluted rntric acid is gwen by Hoftqzer
and Kwanten [l]
fHN,O,)rutnc aeld = (HN204)~ater exptmo 075 I)
(10)
where 11s the Ionic strength defined by
From Fig 7 it can be concluded that for
0 - 20% HN03 the decrease of HN,o,a
with increasing acid strength 1s mainly attn-
buted to the decrease of the Henry-coefhclent
(HN,o,) wth increasing ionic strength Above
20% nitric acid deviations occur
I
01
0 10 20 30 A0
- % HN03
Fig 7 HN~o~~ values as a function of the mtrlc
acid strength a, Kramers et al [ 71 and HoftiJzer and
Kwanten [ 11, 0, this work, - - - -, approxlmatlon pro-
posed by Hoftijzer and Kwanten [ 1 ]
Some authors [2, 5, 6, 121 observed mtrlc
acid mist durmg their expelnments concerning
the absorption of N,O, mto water, especially
at relatively high molar concentrations of
N,04 During the experiments presented here
no mtrlc acid mist was observed The nitric
acid formation m the gas phase does not seem
to be very important as was found by
Detournay and Jadot [ 271
216
A bsorptron of N204 I n to concentrated nr trlc
acad
The absorption of a NO,-N,O, gas mixture
from an inert gas stream mto concentrated
mtnc acid was considered as a physical
process, m which NO2 and NzO, diffuse m
contmuous equlhbrmm v&h each other from
the gas bulk to the gas-hquld interface At
the interface N,O1 1s preferentially dissolved
m the liquid phase The gas phase diffusion of
NOz and NtOd from the gas bulk to the mter-
face can be described by the Graetz-model
according to eqn (8) The physical absorption
of NzO, into the liquid phase can be described
by the penetration theory
JN,o, = ~(HN,o,PN,o,.I - CN,O,,l .O) -
(12)
Partial pressures of Nz04 on the gas-hquld
interface were calculated from eqns (8), (9)
and known partial pressures of NO2 and NzO,
of the m- and outgoing gas stream by means
of an iteration procedure The absorption rate
(J N,O,) as a function of the dnvmg force
WN,O,~N,O,.~ - CN,O,,I.O) should we a
straight hne through the orlgm (see Fig 8)
pN204 I
CW4
IO I N*04
lOI
tlor
PN*04 i pNo2 I CNZOq I o J NzO.,
IfI)
Fig 8 The absorption rate N,Oa mto 63% HNOs at
20 C as a function of the drtvmg force h = 0 346 m,
7 = 2 61 s, 0, PN,O,.~ - CN,O,,I.O~%,O,~ A, pN,O,,, +
PN0,.d2 - CN,O,.I.O~HN,O,
From this figure It can be concluded that
N,04 is the active species dunng the absorp-
tion The expenmental results are @ven m
Table 3 and Table 4 The theoretical absorp-
tion rates are calculated mth eqn (12)
and are compared with the measured absorp-
tion rates The dlffuslon coefficient of Nz04
mto concentrated mtrlc acid was calculated
from the relation of Wllke and Chang [ 281
D N,o,,, = 0 88 x lo- m2 s-l
(78% HNO, at 20 c)
D N,O,sl =0 77 x lo- m2 s-l
(63% HNO, at 20 C)
In the literature no values of the solublhty
of N,O, m concentrated mtnc acid can be
found Several authors measured the total
vapour pressure of the system NO,-N,O,-
HN03-H,O These results were interpreted
and Henry coefflclents (HN,O,) were derived
(see below) From Table 3 and Table 4 It can
be concluded that the proposed absorption
mechanism describes the expenmental results
fmly well
Solubrhty of N204 m concentrated nrtruz acrd
(63 - 80%)
In the previous part it was found that
gaseous N204, which 1s m equlllbnum mth
NO, 1s preferentially and physically absorbed
into concentrated mtnc acid (63 - 78%)
From this it can be concluded that N204 IS
much more soluble m concentrated mtrlc
acid than NO, If we may assume that mamly
N20, IS present m the liquid phase [ 24 - 261
and that Henrys law may be applied the
Henry coefficient can be written as
HV4
CV,.~ _
pN,O,
(13)
In the hter&uie no values of HN,~, can be
found Several authors [15 - 181 measured
the total vapour pressure (P& of the N,O,-
N02-HNOa-H20 system In ideal systems
the total vapour pressure can be written as
Ptot = PkINO, + PH,O + PNO, + pN20,
(14)
It should be noted that vapour pressures of
HN02, NO and N20B are very low above
concentrated mtnc acid solutions contammg
dissolved N,O, and therefore they were
neglected m eqn. (14). The vapour pressures
of HNOB and H20 were taken from the data
of the bmary system HNOs-HZ0 measured
by Vandom and Laudy [23] The vapour
pressures of HNOs and Hz0 are small com-
pared to the total vapour pressure (P,,,)
within the conditions considered and then no
large maccuracles are introduced The vapour
pressures of NO2 and N201 can then be cal-
culated from eqn (14) with aid of the equlhb-
num constant K, =PN,O,/PWO, of the equlhb-
rium
T
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219
2N02 f Nz04
(V)
Henry coefflclents (HNzO, ) were calculated
from the total vapour pressure data of
Klemenc and Rupp [ 161 and the results are
@ven m Fig 9 and Fig 10 From these figures
It can be concluded that the Henry coefficient
is independent of the amount of N,04 m the
liquid phase At small N,04 contents some
deviations occur
I 01 I I I
0 5 10 15
- % N200 by w eqht 1,~ HN03
I
20
Fig 9 HN,o, as a function of the N204 content m
16N HNOs Data from Klemenc and Rupp [ 161
-, 0 C, o, 12 5 C, A, 25 C
30
c
0 I I I I I
0 5 10 IS 20 25
- 7. N*04 by welphl an HNO)
Fig 10 HN 0 as a function of the N204 content m
19N HNO,* data from Klemenc and Rupp [ 161
y0C,o,1250C,~,25C
From the total vapour pressure data measured
by Wemrelch [ 151 and Karavaev and Yarko-
vaya [ 171 Henry coefflclents were calculated
as a function of the temperature and the acid
strength (see Fig 11) Some experiments were
carned out to investigate the Henry coefh-
clent more directly Nitric acid of 75% was
saturated mth nitrogen gas contammg 5 - 20
volume % of NO2 by means of a saturator at
a pressure of 1 04 bar The gas phase was
analysed for its N204 content mth infrared
spectroscopy The N,O,-content m the hquld
phase was determined by rnjectmg a hquld
sample of 50 ~1 mto 10 cm3 of a 0 8 M
NaOH solution. After reaction the nitrite
content was determined wth a colonmetnc
method [20] It was found that the mea-
sured Henry coefficient was mdependent of
the partial pressure of N204 m the gas phase.
The expenmental results are summarized m
Table 5
TABLE 5
HN,o, m 75% mtrlc acid as a function of the temper-
ature
Temperature HN,o, Measured range bar
C kmol mm3 bar-l &(O,
20 3 70 00106-00611
25 2 63 0008 -0 05
35 2 49 0 006 -0 04
45 3 34 0 003 -0 007
From Fig 11 it can be seen that there 1s a
rather good agreement with the results
derived from the vapour pressure data
CONCLUSIONS
The absorption of NO,-N,O, gas mixtures
from a nitrogen gas stream mto rntnc acid
was mvestlgated m a wetted wall column
From the experimental results it can be con-
cluded that NO2 and N,O, are transferred
in contmuous equlhbnum with each other
from the gas phase to the gas-liquid interface
In the liquid phase N201 IS preferentially
absorbed In the experiments with diluted
nitric acid (25% and 40%) the absorption
1s accompanied by a rapid pseudo-first order
reaction between N204 and water Values of
HN,oamwere measured at 20 C in 25%
220
NOMENCLATURE
Fig 11 HN,-,, as a fun&Ion of the temperature and
mtrlc acid strength O, Wemrelch [ 151, 25% by
weight of Nz04 m 75% HNOs, +, Wemrelch [ 151,
20% by weight of Nz04 In 75% HN03, q Wemrelch
[lb], 10% by weight of Nz04 m 75% HN03, A,
Klemenc and Rupp [ 16 J , V, Karavaec and Yarkovaya
[ 171, l , This work
and 40% mtrlc acid and were found to be
respectively 0 49 and 0 16
In the expenments wth concentrated nitric
acid (63% - 78%) it can be concluded that the
reaction of N,O, mth water can be neglected
and that N,04 dissolves physically m the
llquld phase Further it can be concluded
that the Nz04 1s much more soluble m con-
centrated mtnc acid than NO2 The solublhty
of N204 m concentrated nitric acid was
calculated from total vapour pressure data of
the system N,O,-NO2HNOs-H,O It can be
concluded that wthm the considered condl-
tlons Henrys law 1s valid The solublhty of
N204 m concentrated nitric acid decreases
strongly Mth increasing temperature This 1s
caused by the influence of the temperature
on the Henry coefficient and the influence of
the temperature on the gas phase equlhbrlum
2N02 $ N,O,
which shifts to the left side
ACKNOWLEDGEMENT
The authors express their gratitude to
Mr A A M Pnusken and co-workers for
their technical assistance and Miss Cindy
Jacobs for typing out the manuscript
an
c
D
GZ
h
h
H
I
J
k
KP
p
PC
Q
R
T
w
z
roots of Bessel Function
concentration, kmol me3
diffusion coefficient m2 s-l
3
Graetz number
film height, m
effective film height corrected for the
end effect, m
Henry coefficient, kmol m-3 bar-
lomc strength klon mm3
absorption rate per unit of surface area,
kmol m- 2 s- l
reaction rate constant, s-l
equlhbrlum constant of the reaction
2N0 2 N204, bar-
=C
N104,1~CN201,8 = HN~o,/ RT
partial pressure, bar
pressure m the wetted wall column, bar
flctltlous component defined as CB =
CNO, + 2cN 0
gas law co&t&t, J kmol-l K-
temperature, C, K
mass flow rate, kg s-l
valency of ion
Greek symbols
P
density, kg mm3
;
contact time, s-l
quantity of gas absorbed per unit kmol
m-2 of surface area after contact time 7
Su bscrrp ts
C wetted wall column
g
gas phase
1
gas-liquid interface
liquid phase
0 inlet
Q NO2 + 2N201
Superscrrp ts
bulk average or mlsmg up value
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