PRODUCTION FOR 100 MTPD OF NITRIC ACID

BY OSTWALD’S AMMONIA OXIDATION

PROCESS

Under the guidance of

Dr. B.VENKATA RAMANAIAH

By
S.CHANDRA SEKHAR (20331A0839)
CH.SANDHYA (20331A0807)
P.SRAVANI (20331A0836)
S.SAI SUMANTH (21335A0815)

Department of Chemical Engineering

CONTENTS
1. Process flow sheet
2. Process description
3.Material Balances
4.Energy Balances
5.Design of heat exchanger,absorption column
5.References
Fig: Nitric acid by Ammonia oxidation process
 Process Flow Sheet

.
 Description
• Compressed air is mixed with anhydrous ammonia; fed to a shell and tube
converter designed so that the preheater and a steam heat recovery boiler-
superheater are within the same reactor shell. The converter section consists of 10-
30 sheets of Pt-Rh alloy in the form of 60-80 mesh wire gage packed in layers
inside the tube. The gas passes downward with a velocity designed to give a
contact time of about 2.5 x 10- sec in the catalyst zone at 800°C.
• Product gases from the reactor, containing 10-12% NO, are sent through heat
recovery units, a quench unit for rapid cooling to remove a large fraction of the
product heat, and into the oxidizer-absorber system. Air is added to convert NO to
NO, at the more favorable low temperature (40-50°C) environment of the
absorption system.
• The equipment in the absorption train may be a series of packed or sieve tray
vertical towers or a series of horizontal cascade absorbers. The product from this
water absorption system is 57-60% HNO, a solution that can be sold as is or
concentrated
Nitric acid synthesis

• Exothermic
• Catalyst = Platinum-Rhodium (Pt-Rh)
• Temp. 800 °C
• Pressure: 3.5 atm
(i) Ammonia oxidation process
4NH3+502→ 4NO + 3H2O + Heat
(ii) Nitric oxide oxidation and absorption
2NO+02 → 2NO2 + Heat
3NO2(g) + H2O(1) → 2HNO3 (Aq) + NO + Heat
NO produced in the above step will be reoxidized.
MATERIAL BALANCE FOR EACH EQUIPMENT
BASIS:
One hour of operation.
Ratio of air and ammonia = 10.6 : 1
Air flow to the process = 12200 NM3/Hr.
= 12200 ×1.22528.96 = 536.8 Kmol/Hr.
Oxygen flow (21%) = 112.72 Kmol/Hr.
N2 flow (79%) = 424.0720 Kmol/Hr.
Let x moles of ammonia enter in the ratio of 10.6%.
10.6/100 = x/x+536.8

∴ NH3 required = 63.6474Kmol/Hr.

Then x = 63.6474Kmoles
1.REACTOR
The reaction occurring in the reactor
4 + 5 → 4NO + 6 (98%) Reaction 2:
4 + 3 → 2 + 6 (2%)
is the limiting reactant consumed = 63.647 0.02
Reaction 1: =1.272 Kmol.
consumed = 63.6474 0.98 consumed = 1.591 Kmol.
= 62.37 Kmol. produced = 0.636 Kmol.

∴ Total consumed
consumed = 77.96 Kmol. Water produced = 1.908 Kmol.
NO produced = 62.37 Kmol.
produced = 93.55 Kmol. = 77.96 + 1.591
= 78.8738 Kmol.
Unreacted = 112.72 – 78.8738
= 33.8464 Kmol.
leaving = 424.07 + 0.636
= 424.706 Kmol.
NO leaving = 62.37 Kmol.
leaving = 95.4592 Kmol.
2.WASTE HEAT BOILER

Reaction :
2NO + (96%)

NO consumed = 62.37 0.96

= 59.87 Kmole.

consumed = 30.4338 Kmole.

produced = 60.8675 Kmole.

Reaction :
3N + 2HN + NO
In the cooler condenser diluted HN of 35% strength is produced, but we don’t
know how much is produced.
Let us assume 100 Kmole of HN is formed in the cooler condenser.
Water consumed =50 Kmole.
Mass of 50 Kmole of = 50 18 = 900 Kg.
Mass of 100 Kmole of HN = 6300 Kg.
Water required to dilute 35% strength acid = 6300 = 11700 Kg.
Total water required for dilution = 11700 + 900 =12600Kg.
Formed nitric acid = 100 = 13.637 Kmole.
consumed = 13.637 = 20.455 Kmole.
NO leaving = 6.8185 Kmole.
4.OXIDATION TOWER
Reaction :
2NO + 2 (99%).
NO consumed = 9.3655 0.99
= 9.2723.
Secondary air supplied to the oxidation chamber
= 2228 /Hr = 98.0320 Kmol/Hr.
flow = 20.5867 Kmol.
flow = 77.4453 Kmol.
consumed = 4.6362 Kmol.
produced = 9.2723 Kmol.
unreacted = 19.3631 Kmol.
leaving = 424.706 + 77.4453
=502.1513 Kmol.
Reaction : Inlet = 88.6492 Kmol.
2 + 2HN + NO (99%) be required for dilution and reaction to occur
N consumed = 50.6855 0.99 = 148.8697 - 88.6492
=50.1786 Kmol. = 60.2205 Kmol.
consumed = 25.0893 Kmol.
HN consumed = 50.1786 Kmol.
Total HN produced = 50.1786 + 13.6370 =
63.8150 Kmol.
= 4020345 Kg/Hr.
NO leaving = 25.0893
leaving = 88.6492 – 25.0893 = 63.5599
Total nitric acid produced = 4020.345 Kg/Hr.
Nitric acid (60%) = = 6700 Kg/Hr.
∴ water required = 2679.655 = 160.0813
MT/Day.
∴ in the outlet = 148.8697 Kmoles.
ENERGY BALANCE FOR EACH EQUIPMENT
REACTOR:
4 + 4NO + 6 ∆ = -54.1 Kcal/mol.
4NH3 +3 O2 → 2 N2 +6 H2O ΔH 298 K = -75.7 kcal / mol.
Heat of reaction for Reaction-1
Heat of formation of reactions and products
NH3 = -46.19 kJ/mol
NO = 90.374 kJ/mol
H2O = -241.826 kJ/mole
Heat of reaction 1 =(ΔHf.p - ΔHfr)
ΔHfp = (62.37 * 1000 * 90.374) + (93.55 * 1000 * -241.826)
= -16986195.92 kJ/hr
ΔHfr = (62.37 * 1000 * - 46.19)
= -2880870.3 kJ/hr
ΔH r*n 1 = - 16986195.92 + 2880870.3
= - 14105325.62 kJ/hr
For Reaction 2
ΔHf.p = 1.908 * 1000 * - 241.826
= - 46145.834 kJ/hr
ΔHf.r = 1.2728 * 1000 * - 46.19
= - 58790.632 kJ/hr
ΔH r*n2 = - 46145.834 + 58790.632 = -402855.202
= - 402855.202 kJ/hr
Now
Total Heat Of Reaction = - 14105325.62 – 402855.202
= - 14508180.82 kJ/hr
Cp of the inlet at 190 ̊C
Cp of NH3 = - 41.68 kJ / Kg kmol.K
Cp of O2 = 29.88 kJ / Kg kmol.K
Cp of N2 = 30.960 kJ / Kg kmol.K
Cp at 840 ̊C
Cp of NO = 34.1501 kJ / Kg kmol.K
Cp of H2O = 42.952 kJ / Kg kmol.K
Cp of O2 = 37.14 kJ / Kg kmol.K
Cp of N2 = 33.509 kJ / Kg kmol.K
Enthalpy of reactants at 190 ̊C
Σ Hr = [m Cp) NH3 + (m Cp )O2 + ( m Cp)N2 ] ΔT
= [(63.6474 * 41.68) + (112.72 * 30.96) + (424.0702 * 29.88) ] (463 – 298 )
= 3104285.642 KJ / Hr

Enthalpy of reactants at 840 ̊C

Σ Hp = [ (m Cp ) NO + (m Cp) H2O + (m Cp ) O2 + (m Cp ) N2 ] ΔT
= [ (424.706 * 31.79) + (33.8464 * 33.509 ) + (62.37 * 34.1501) + (95.4592 *
42.952) ] (1413 – 298)
= 17005519.46 KJ / Hr

Total heat q = Σ Hp + Σ ΔH at 25 ̊C - Σ Hr
= - 14508180.82 +17005519.46 – 3104285.647
= - 606947.2 KJ / Hr
2.WASTE HEAT BOILER
CP of gases entering at 840 ̊C
Cp of NO = 34.149 kJ / Kg kmol.K
Cp of H2O = 42.952 kJ / Kg kmol.K
Cp of O2 = 37.144 kJ / Kg kmol.K
Cp of N2 = 31.709 kJ / Kg kmol.K
Cp of NO2 = 53.13 kJ / Kg kmol.K
Enthalpy of gases entering are
= [(62.37 * 34.179) + (95.4592 * 42.952) + (33.8464 * 33.144) ] (424.706 * 31.7098) (813 –
298 )
= 16968908.69 KJ / Hr
Enthalpy of gases outlet
= [(60.8675 * 43.48) + (2.545 * 31.96) + (3.4126 * 30.03) + (95.4592 * 36.19) +
(424.706 * 28.13) (608 – 298 )
= 5650435.951 KJ / Hr
Enthalpy changes = 16968908.69 – 5650435.951 = 11318472.74 KJ/Hr
Mass flow of water to waste heat boiler =7000Kg/Hr
CP of water =4.2 KJ/Kg.K
Inlet temperature of water in shell side =190 ̊C
Outlet temperature of steam =2 ̊C
Q= ṁ CpΔT
3144.02 = 1.9 * 4.2 (Tsteam – 190)
Tsteam = 583.98 ̊C
LMTD = = 195.59 ̊C
Mass flow rate of steam from waste heat boiler = Q= ṁ λ
Latent heat of vaporization = 2260 KJ/Kg
Mass flow rate of steam = = 1.39 Kg/Sec
= 5004 Kg/Hr
3.COMPRESSOR
Heat output from the compressor
Q= n*ΔH =
Specific heat capacity of N2 and O2 are 1.04 & 0.918 KJ/Kg.K
Enthalpy of N2 = 104 * (405 – 313) = 95.68 KJ/Kg
Enthalpy of O2 = 0.918 * (405 – 313) = 83.548 KJ/Kg
Heat output = Q = n*ΔH
= (424.02 * 28) * (95.68) + 3607 * (84.548)
=1440984.758 KJ/Hr
COOLER CONDENSER
AT 335 ̊C (Inlet)

NO2 = 60.8675 Kmol CP = 43.48 KJ/Kmol

H2O = 95.4592 Kmol CP = 38.140 KJ/Kmol
NO = 2.545 Kmol CP = 31.96 KJ/Kmol
N2 = 424.706 Kmol CP = 29.13 KJ/Kmol
O2 = 3.4126 Kmol CP = 30.03 KJ/Kmol
AT 50 ̊C (outlet)

NO2 = 40.4125 Kmol CP = 37.517 KJ/Kmol

H2O = 88.492 Kmol CP = 37.14 KJ/Kmol
NO = 9.3635 Kmol CP = 29.913 KJ/Kmol
N2 = 424.706 Kmol CP = 28.09 KJ/Kmol
O2 = 3.4126 Kmol CP = 29.3 KJ/Kmol
HNO3 = 13.637 Kmol CP = 54.51 KJ/Kmol
Enthalpy of reactants
= (60.8675 * 43.48) + (95.4592 * 38.140) + (2.545 * 31.96) + (424.706 * 29.13) + (3.4126
* 30.03) + (633 -298)
= 697326.254 KJ.
Enthalpy of products
= (9.36 * 29.91) + (424.70 * 28.09) + (29.3* 3.412) + (40.412 * 37.517) + (13.637 * 54.51)
+(88.64 * 37.14) + (50 -25)
= 446339.73 KJ.
Enthalpy of reaction = - 641.6 KJ/mol
Heat of reaction at 25 ̊C = - 641.6 * (13.637 + 9.3635)
= - 14757.12 KJ.
Q = -265743.64 KJ.
OXIDATION TOWER
Inlet temperature = 50 ̊C CP of H20 = 9.25* 4.186 = 38.7205 KJ/Kmol.K
Outlet temperature = 47 ̊C CP of NO2= 8.9625 * 4.186 = 37.517 KJ/Kmol.K
Moles of reactants CP of O2 = 7.03 * 4.186 = 29.427 KJ/Kmol.K
NO = 9.3635 Kmol
N2 = 502.2513 Kmol
O2 = 23.9 Kmol
NO2 = 40.4125 Kmol
Moles of products
NO2 = 50.6855
NO = 0.0912
O2 = 19.3631
N2 = 502.2513
CP of NO = 7.146 * 4.186 = 29.913 KJ/Kmol.K
CP of N2 = 6.95 * 4.186 = 29.0927 KJ/Kmol.K
Enthalpy Of Reactants
= (9.3635 * 29.913) + (502.2513 * 29.0927) + (23.9 * 29.427) + (40.412 * 37.517) + (50 -
25)
= 427751.04 KJ.

Enthalpy Of Products
= (50.6855 * 37.517) + (0.0912 * 29.913) + (19.3631 * 29.427) + (502.213 * 29.097) + (47
-25)
= 375879.53 KJ.

Reaction :
2NO + O2 2NO2 ΔH 298 = - 113 KJ/mol

∴ reaction enthalpy = -113 * 50.6855

Formed NO2 moles = 50.6855

= - 5727.4615 KJ
TOTAL HEAT = Hp + Hreactant at 25 ̊C – Hr
= 375879.53 – 5727.4615 – 427051.04
Design of heat exchanger
Design a suitable heat exchanger to cool secondary air of Ostwald’s ammonia
oxidation process from 140oC to 80oC. Flow-rate of secondary air is 78 kg/s. Water is
used as the cold fluid, with a temperature rise from 27oC to 65oC. Use Kern method.

Solution procedure:
Step-1: Shell size and number of tubes.
 Assume overall heat transfer coefficient
 Determine LMTD correction factor
 Calculate corrected LMTD
 Calculate heat load
 Select layout and tube size
 Find required heat transfer surface
 Determine number of tubes
 Determine Shell size
Step-2: Overall heat transfer coefficient
 Determine equivalent diameter on shell side
 Determine tube-side and shell-side heat transfer coefficient
 Determine overall heat transfer coefficient
 Check the value of calculated overall heat transfer coefficient is
at least 30% higher than the assumed value.
 If not, repeat the step-1 and step-2 taking the calculated overall
heat transfer coefficient as the initial value.
Parameter 1-1 Shell and Tube 1-2 Shell and Tube

Heat load 4740.84 kW 4740.84kW

LMTD 63.36 oC 63.36 oC

Tube OD 25mm 25mm

Tube ID 20mm 20mm
Tube length 4.88mm 4.88mm
Tube sheet thickness 25mm 25mm
Number of tubes per pass 774 387
Tube pitch 31.25mm(Triangular) 31.25mm(Triangular)

Shell diameter 1055.8mm 1055.8mm

Baffle spacing 0.5Ds 0.5Ds
No.of baffles 9 9
Tube side HTC 1029 W/m2 - 0 C 1029 W/m2 - 0 C

Shell side HTC 837.37 W/m2 - 0 C 837.37 W/m2 - 0 C

2 0 2 0
Design of absorption column
Gm Lm

Y2 X2

Y+DY X+DX
d
Y x ↕ X X

Gm1 Lm
Y1 X1
• BED HEIGHT
y1 x1

Z= Gm/Kgap ∫ dx/y-Ye = Lm/Klac1 ∫ dx/xe-x

y2 x2

Z=Hog*NTU
NTU= 1/1-(mGm/Lm)ln[(1-mGm/Lm)y1/y2 + mGm/Lm)]
The optimum value for the term mGm/Lm will lie between 0.7 to 0.8.
Hog = Hg + mGm/Lm Hl
Hol = Hl + Lm/Gmm Hg
m = slope of the equillibrium line
Gm /Lm = slope of operating line
Hg = 0.011Ψh(sc)L^0.5*(DC/0.305)^1.1(Z/3.05)]/(Lw*f1f2f3)^0.5
Hl = 0.305 dh (sc)L^0.5*K3*(Z/3.05)^0.15
Column Diameter : 2.509m
Z = HTU*NTU
HTU = 0.5m
NTU = 12m
Z = 6m
REFERENCES

1) Bhargava, R., & Agrawal, R. (2018). Pinch analysis-based energy optimization of

an ammonia plant. Journal of Cleaner Production, 184, 685-697.

2) Farsi, M., & Shariati, A. (2016). Energy integration in nitric acid production
plants. Applied Thermal Engineering, 108, 476-485.

3) Kalakul, S., & Arpornwichanop, A. (2020). Heat integration of nitric acid plant
using pinch analysis and mathematical optimization. Chemical Engineering
Transactions, 78, 343-348.