Nitric Acid

3
1. Problem Statement
In nitric acid manufacturing plant an absorber column uses a reaction gas mixture and 42% weak acid,at
5531 kg/hr as absorbent. The gas mixture enters the absorption column at 65
0
c and leaves at 10
0
c.The
reaction gas mixture and tail gas composition are follows:

Reaction gas Tail gas
Kg/hr Kmol/hr Kg/hr Kmol/hr
Nitrogen +inerts 27482 981.5 27482 981.5
Oxygen (O
2
) 1501 46.9 257 8.04
Nitric oxide (NO) 117 3.9 10 0.33
Nitrogen dioxide (NO
2
) 2099 45.6 25 0.55
Nitrogen tetroxide (N
2
O
4
) 1302 14.2 6 0.06

The operation is carried out at a pressure 950 KPa. The feed plate temperature is 50
0
c.60% wt acid is
withdrawn at 11784 kg/hr. (dissolved contents include 1.623 kg NO and 115.47 kg NO
2
).Make up water
required is 1532 kg/hr. The vapour and liquid densities are 10.1 and 1350 kg/m
3
respectively. Design the
sieve tray column.

4

2. Given Data
Operating Parameters

Operating pressure 950 kpa

Operating temperature 65
0
c to 10
0
c

Column Inputs

Reaction Gas Feed

Components Kg/hr Kmol/hr
N
2
+inerts 27482 981.5
O
2
1501 46.9
NO 117 3.9
NO
2
2099 45.6
N
2
O
4
1302 14.2
Total 32501 1902

Weak acid condensate (at 50 )
Nitric acid (42% wt)
5531 Kg/hr
Make up water 1532 Kg/hr

Output Requirements

Product acid (60% wt) 11784 Kg/hr
Dissolved NO
Dissolved NO
2
1.623 Kg
115.47Kg

Tail Gas

components Kg/hr Kmol/hr
N
2
+inerts 27482 981.5
O
2
257 8.04
NO 10 0.33
NO
2
25 0.55
N
2
O
4
6 0.06
Total 27780 990.48
5

3. Additional Data
3.1 Nitric acid absorption
The absorption column is required to absorb nitrous reaction gases thus producing 60% (wt.) nitric acid
product (dissolved contents include NO and NO
2
). This is achieved by the countercurrent absorption of
the nitrogen oxide components from the reaction gas into a water/weak acid media. The column
specification requires an operating pressure of 950 kPa and an absorption temperature in the range of
10C to 65C.
The design must consider three feed streams and two product streams. The three inlet feed streams are
reaction gases, weak nitric acid solution and make-up water. Two outlet streams flow from the column.
These are tail-gas stream and product acid. Absorption of nitrous oxides increases as the temperature is
reduced. This effect, together with the exothermic oxidation/absorption reactions, requires installation of
an internal cooling circuit.
Specific heat of the components
components Heat of formation (KJ/Kmol) Specific heat (KJ/KmolK)
H
2
O (V)
- 241830 34.34
H
2
O (L)
- 285840 75.4
NO
90370 29.75
NO
2
33800 37.8
N
2
O
4

9300 41.65
HNO
3

-206570 110.0
O
2
0 29.8
N
2
0
29.16

3.2 Analysis of the process chemistry
The main aspects are listed below.
(a) Formation of nitric acid occurs primarily by the reaction of nitrogen dioxide with water, although
some acid forms from the tetroxide. The major reaction is shown below.
SN0
2
(g) + E
2
0(l) 2EN0
3
(oq) + N0(g) 1
This is an exothermic reaction which is dependent on the partial Pressure (therefore total operating
pressure) of nitrogen dioxide.
(b) Additional reaction of nitric oxide and nitrogen tetroxide with water generates nitrous acid which
decomposes into nitric acid according to following reactions.

6

2N0
2
+E
2
0 EN0
2
+ EN0
3
. .2
N
2
0
4
+E
2
0 EN0
2
+EN0
3
. .S
SEN0
2
EN0
3
+2N0 +E
2
0. .4
(c) Secondary reactions concern the equilibrium of nitrogen dioxide with the tetroxide form, and the
oxidation of nitrogen monoxide (formed in the production of acid) to nitrogen dioxide.
2N0
2
(g) N
2
0
4
.S
2N0(g) +0
2
(g) 2N0
2
.6
Reaction 3 is relatively slow and is regarded as the rate-determining step in the entire process. Other key
reactions proceed virtually instantaneously. Both Reactions (2) and (3) are exothermic, and are dependent
on the various partial pressures (operating pressure) and temperature. Lower temperatures favor the
overall absorption chemistry. This factor, together with the exothermic nature of the reactions, determines
the need for a cooling circuit within the column.
(d) The dissolution of both nitrogen monoxide and nitrogen dioxide into aqueous nitric acid is inversely
proportional to their partial pressures. The amounts dissolved decrease with increasing temperature.
(e) In the mechanical considerations those factors of greatest significance are column diameter and plate
spacing. These factors determine the average residence time of the gases in the space between the plates,
and hence the degree of oxidation of nitrogen oxide (the rate-determining step).
(f) Tray design is also of critical importance. Tray area, weir height, and the size and spacing of tray
holes are all important variables. These factors and the gas velocity determine the tray efficiency. Tray
efficiency has a major effect on the overall column performance.
4. Process Design Methodology
Six component analysis model was used to design the absorption column. It accounts for N
2
, 0
2
, H
2
0, NO,
NO, and N
2
0
4
within the reaction gas stream. The operation of the column influences a number of key
stages; these stages are described as follows,
Stage 1: The reaction gas of known composition enters the column at 65C.
Stage 2: The number of moles of nitric acid formed as the gas passes through the liquid mixture on the
plate is calculated. This calculation includes a term that effectively describes the tray efficiency. The
moles of acid formed are given by: [Ref.1]
F
HN03
= _P
N0
+P
N0x
_
(K
3
E
3
+2E
3
)
(K
2
+ E)
__ (0
N0
+ 0
N0x
) C (P
N0
+P
N0x
)
-1
. . cq. 1
Where,
F
HNO3 =
moles of acid formed;
7

P
NO
= partial pressure of nitrogen monoxide (bar);
P
NOX
= partial pressure of nitrogen peroxide (dioxide + tetroxide) (bar);
G
NO
= flow rates of NO. (KMol/sec)
G
NOX
= flow rates of nitrogen peroxide (dioxide +tetroxide) (KMol/sec)
K
2
= dioxide/tetroxide equilibrium constant (Bodenstein); [Ref.2]
Where, logK
2
=
2993
1
9.226 And K
3
=
K
4
K
2
,
K
4
= equilibrium constant between nitrogen monoxide and nitrogen tetroxide as presented empirically by
the Carberry equation; [2]
logK
4
= 7.412 2u.28921w +S2.47S22w
2
Su.87w
3
. . cq. 2
W = concentration of acid present on the plate
E = equilibrium partial pressure of nitrogen dioxide as determined by solving the following equation:
SK
3
E
3
+(2E
2
K
2
) +E = SP
N0
+ P
N0x
. . cq. S [Ref.1]
C = degree of approach to equilibrium (tray efficiency).
Stage 3: The component mole balance is recalculated according to the moles of nitric acid formed. The
gaseous concentrations calculated after the formation of nitric acid, are used to calculate the degree of
oxidation of nitrogen oxide.
Stage 4: the oxidation of nitrogen monoxide takes place in the void area prior to the first sieve tray. The
degree of oxidation () is determined using the Fig 1.
Bodenstein equation for calculate the velocity constant K
1
is [Ref.4]
log K
1
=
641
I
u.72S
Assumes plug flow in the void area between plates calculate two dimensionless quantity Y and m,
where
=
K
1
tP
NO
2
2
And m =
2N
c2
N
NO

And from the nomograph the degree of oxidation () of nitrogen oxide is found out.
Where
P
NO
= partial pressure of NO (atm)
N
O2
=mole of oxygen.
N
NO
= moles of nitrogen monoxide.
t = residence time (sec)
T = temperature in kelvin
Stage 5: the equilibrium extends of dimerization () of nitrogen dioxide to nitrogen tetroxide is calculated
by using the equation [Ref.3]
8

K
P
=
2P0
N02
(1 [)
2
[(1 u.S 0
N02
)
. . cq. 4
Where
G
NO2
= flow rates of NO
2
. (KMol/sec)
P= total pressure (Mpa)
K
p
can be calculated by the given equations [Ref.3]
lnK
p
= 7.uSuS
6198
I
+ 1.7SlnI + u.u11I 1.64 1u
-5
I
2

Stage 6: The gas composition is revised. Inlet gas composition at i+1 plate can be calculated using
following equation. [Ref.3]
0
N0
+1
= (1 o)(0
N0
-1
+ u.SX
HN03
) cq. S
0
N02
+1
= (1 [)|0
N02
-1
(1.SX
HN03
) + o(0
N0
-1
+ u.SX
HN03
)| cq. 6
0
N204
+1
= 0
N204
-1
+ [|0
N02
-1
1.SX
HN03
+ o(0
N0
-1
+ u.SX
HN03
)| cq. 7
0
02
+1
= 0
02
-1
u.So(0
N0
-1
+ u.SX
HN03
) cq. 8
0
H20
+1
= 0
H20
-1
u.SX
HN03
. cq. 9
Stage 7: The computation proceeds to the next tray; this constitutes a return to Stage 2 whereby the
fraction of nitrogen dioxide convert into nitric acid and remains monoxide oxidized in the void space
above the tray. The steps proceed as indicated in Stages 2 to 6.
The calculation is terminated when the number of moles of nitric acid required from the next tray is
found to be less than or equal to zero
This model is considered the following assumption,
Oxidation of nitric oxide proceed in void space between trays and HNO3 formation due to absorption is
found in liquid pool.
The tray temperatures are set by the known values of feed and output temperatures. The bottom tray
was given the value of 65C corresponding to the inlet gas temperature. The weak-acid feed tray was set
at 50C (the temperature of this feed condensate) and the top tray was set to 10 C. Temperatures for all
other trays in the column were set by linear interpolation between these points.
Gas and liquid are ideally mixed in the pool of liquid over the plates.
There has no concentration and temperature gradient in the pool of liquid.
HNO
2
completely decomposes into HNO
3
NO and H
2
O.
Heat loss to the environment is negligible and reaction heat is exchanged with heat transfer coil.
.The nomograph for finding the degree of oxidation of NO is given below,
9

Fig 1
10

5. Process design Computation
5.1 Overall Material Balance:

Overall material balance:
(reaction gas in + make up water in + weak acid in) (tail gas out + strong acid withdrawn)
=32501+5531+1531-27780-11784
= 0
5.2 Tray by tray calculation
Operating pressure: 950 KPa.
Column diameter: 1.8 m
Hole diameter: 5 mm
Residence time: 1.4 sec
Liquid density: 1350 kg/m
3

Vapor density: 10.1 Kg/m
3
Tray efficiency: 50 %
Process water
1531 kg/hr
Weak acid (42%)
5531 Kg/hr
Acid withdrawn (60%)
11784 kg/hr
Inlet gas
32501 kg/hr
Tail gas
27780 kg/hr
Cooling water in
Cooling water out
11

Calculation for stage 1:
Tray temp: 65
Concentration of nitric acid on the plate, w: 0.6
Value of equilibrium constant of NO and N
2
O
4
, K4: 1.8239
Value of equilibrium constant of NO
2
and N
2
O
4
, K
2
: 0.4256
Value of K
3
: 4.2859
Value of K
P
: 2.1127
Value of velocity constant K
1
:14.8476
Value of degree of oxidation : 0.9
Value of extend of dimerization : 0.005
Equilibrium partial pressure of NO, E: 0.2259 bar
Value of dimensionless group Y: 1.71
Value of dimensionless group, m: 6.40
Inlet composition of stage 1
Component kg/hr kmol/hr kmol/sec mol frac
Partial pressure
KPa bar atm Mpa
N2 27482 981.5 0.272639 0.893367 848.6989988 8.378075 8.270558 0.848699
O2 1501 46.9 0.013028 0.042689 40.55423642 0.400338 0.3952 0.040554
NO 117 3.9 0.001083 0.00355 3.372313902 0.03329 0.032863 0.003372
NO2 2399 52.15217 0.014487 0.047469 45.09576952 0.44517 0.439458 0.045096
N2O4 1302 14.2 0.003944 0.012925 12.27868139 0.121211 0.119656 0.012279
total 32801 1098.652 0.305181 1 950 9.378085 9.257734 0.95
By solving eq. 1 the moles of nitric acid formed in the 1
st
stage is 2.9 mol/sec.
The revised composition for oxidation of nitric acid in the void space is,

Component Kmol/sec mol frac
Partial pressure
KPa MPa bar atm
N2 0.272639 0.901939 856.8416 0.856842 8.458456357 8.349908
O2 0.013028 0.043098 40.94332 0.040943 0.404178913 0.398992
NO 0.002533 0.008381 7.961687 0.007962 0.078595132 0.077587
NO2 0.010137 0.033534 31.85738 0.031857 0.314485441 0.31045
N2O4 0.003944 0.013049 12.39649 0.012396 0.122373999 0.120804
total 0.302281 1.000001 950.0005 0.950001 9.378089842 9.257739
12

By using the value of dimensionless group Y and m, from nomograph the degree of oxidation of nitric
acid is to be found 0.9.
By solving eq. 4, the extend of dimerization of NO
2
to N
2
O
4
is found 0.005.
Again the composition of the gas phase is revised as eq.5 to eq. 9, which is considered as the inlet
composition of stage 2.
Calculation of stage 2:
Tray temp: 63.75
2
O
4
, K4: 6.49
2
and N
2
O
4
, K
2
: 0.4590
Value of K
3
: 14.15
Value of K
P
: 1.9610
1
:15.09043
Inlet composition of stage 2:
Component kmol/sec mol frac
Partial Pressure
KPa Mpa Bar atm
N2 0.272639 0.905353 860.0853 0.86008529 8.490477 8.381516986
O2 0.011888 0.039476 37.502 0.037501997 0.370207 0.365456343
NO 0.000253 0.000841 0.799183 0.000799183 0.007889 0.007788022
NO2 0.012355 0.041026 38.97477 0.038974765 0.384746 0.379808447
N2O4 0.004007 0.013304 12.63927 0.012639267 0.124771 0.123169452
total 0.301141 1.000001 950.0005 0.950000503 9.37809 9.257739251

st

13

2
to N
2
O
4
is found 0.005.
Calculation of stage 3:
Tray temp: 62.50
2
O
4
, K4: 15.30
2
and N
2
O
4
, K
2
: 0.4954
Value of K
3
: 30.89
Value of K
P
: 1.8193
1
:15.3389

Partial Pressure
KPa Mpa Bar atm
N2 0.272639 0.910219 864.7083 0.864708309 8.536114 8.426568224
O2 0.011888 0.039688 37.70357 0.037703573 0.372197 0.367420697
NO 0.001058 0.003533 3.356636 0.003356636 0.033136 0.032710367
NO2 0.00994 0.033184 31.52478 0.031524783 0.311202 0.307208493
N2O4 0.004007 0.013376 12.7072 0.012707204 0.125441 0.123831497
total 0.299531 1.000001 950.0005 0.950000506 9.37809 9.257739277
14

Inlet gas composition of stage 3:
Partial Pressure
KPa Mpa Bar atm
N2 0.272639 0.932287 885.6725 0.885672476 8.743065 8.630863684
O2 0.011438 0.039112 37.15651 0.03715651 0.366797 0.362089573
NO 0.000159 0.000543 0.515702 0.000515702 0.005091 0.005025511
NO2 0.010785 0.036879 35.03533 0.035035333 0.345857 0.34141874
N2O4 0.004061 0.013886 13.19134 0.013191337 0.130221 0.128549365
total 0.299081 1 971.5714 0.971571358 9.59103 9.467946874

st
Partial Pressure
KPa Mpa Bar atm
N2 0.272639 0.916646 870.8135 0.870813548 8.596383 8.486063681
O2 0.011438 0.038456 36.53313 0.036533135 0.360643 0.356014796
NO 0.000984 0.003307 3.142115 0.003142115 0.031018 0.030619862
NO2 0.00831 0.027939 26.54235 0.02654235 0.262017 0.258654764
N2O4 0.004061 0.013653 12.97003 0.012970026 0.128036 0.126392692
total 0.297431 1.000001 950.0012 0.950001175 9.378096 9.257745796

2
to N
2
O
4
is found 0.005.
In this way tray by tray calculation was done and the total no of trays was found 56.

15

Table 1: Concentration of nitric acid in different stage
Tray no
HNO
3
formed
(mol/sec)
Acid conc. in tray
(weight fraction)

Tray no
HNO
3
formed
(mol/sec)
Acid conc. in tray
(weight fraction)
1 0.0029 0.6 29 0.00023 0.121847
2 0.00161 0.581263 30 0.00019 0.111265
3 0.00165 0.569715 31 0.00018 0.102296
4 0.00167 0.556899 32 0.00017 0.093604
5 0.00165 0.542783 33 0.00016 0.085212
6 0.00158 0.527549 34 0.00011 0.077148
7 0.00146 0.511592 35 0.00011 0.071507
8 0.0013 0.495486 36 0.00011 0.065787
9 0.00118 0.479894 37 0.0001 0.059984
10 0.00102 0.46459 38 0.00009 0.054636
11 0.00088 0.450372 39 0.000096 0.049763
12 0.00077 0.437289 40 0.000075 0.0445
13 0.00115 0.425163 41 0.00007 0.040342
14 0.00145 0.405746 42 0.00007 0.036423
15 0.00125 0.378738 43 0.00006 0.032467
16 0.0011 0.352829 44 0.000055 0.029047
17 0.00095 0.327684 45 0.000056 0.025887
18 0.00082 0.303935 46 0.00005 0.022645
19 0.000708 0.281713 47 0.000048 0.019729
20 0.000615 0.261087 48 0.000045 0.016912
21 0.00053 0.24197 49 0.00004 0.014253
22 0.00048 0.224514 50 0.000038 0.011876
23 0.00042 0.207853 51 0.000036 0.009606
24 0.00045 0.192558 52 0.000032 0.007444
25 0.0004 0.175373 53 0.000032 0.005513
26 0.00033 0.159354 54 0.00003 0.003574
27 0.0003 0.145575 55 0.000029 0.001748
28 0.00024 0.132581 56 -2.4E-05

16

5.3 Heat duty calculation
The required flow rate through each set of cooling coils is calculated with the known value of heat duty.
Using the heat capacity data and enthalpy data, the energy balance is performed.

Heat duty = net enthalpy out-net enthalpy in
= n
out
E
out
n
n
E
n

Contributing compound Heat duty (KJ/hr.)
Nitrogen 981.S 29.16 (1u 6S) = 1S741Su
Oxygen 8.u4 29.8 (1u 6S) = 1S177.S6
Nitric oxide u.S8 29.7S (1u 6S) = 621.77S
Nitrogen dioxide S.u6 S7.8 (1u 6S) = 6S61.74
Nitrogen tetroxide u.u6 41.6S (1u 6S) = 1S7.44S
Nitric acid |{S6.87 11u (6S Su)] +{7S.S6 (2u6S7u)]
+ {7S.SS 11u (6S Su)]] = 1SS79887
Water |{47.44 7S.4 (Su 1u)] + {178.22 7S.4 (6S Su)]
+ {S7.67 28S84u]] = 111122S9
Nitric oxide deformation {S.S2 (9uS7u)] = S181u2.4
Nitrogen dioxide deformation {42.S4 (SS8uu)] = 14S78S2
Nitrogen tetroxide deformation {14.14 (9Suu)] = 1S1Su2
Total 7749SS2

.
So the cooling coil must remove 7.75 *10
6
KJ heat in each hour.
Required flow rate of cooling water,
Consider, the design inlet temperature of the coil is 7
And the design outlet temperature is 25
So required flow rates of water in cooling coil is
= cot Juty{spcciic cot o wotcr (I
out
I
n
)]
= 7749532/(4.2*(25-7))
= 102507 kg/hr.
= 102.507 cubic meter/hr.

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