1.
Introduction
Energy is required for every process to get desired products. There are some processes in
inorganic chemical industries where raw material itself acts as a source of energy. Nitric
acid production is that kind of process due to highly exothermic reactions involved in it.
Irreversibility in the reaction is the major cause for the exergy loss. Using exergy analysis,
we can pinpoint true losses of available energy in this process. Chemical industries can
increase their profit margins with the help of exergy analysis combined with other
techniques [1]. Various studies have been carried out for the exergy analysis of inorganic
chemical process industries. Commercially nitric acid plants are operated by two methods -
mono pressure and dual pressure. In the present work, an attempt has been made to carry
out exergy analysis of mono high-pressure nitric acid process and suggestions have been
proposed to reduce exergy losses. First time attempt has been made for the recovery of
heat from cooler condenser in the nitric acid plant.
2. Process Description
Ammonia is oxidized to produce nitric oxide. The heat generated by this reaction is
recovered in heat exchangers and used to produce work. Oxidation of nitric oxide and
subsequent absorption is carried out in an absorber where heat is removed by cooling
tower water and chilled water. A PFD of the mono high-pressure process of nitric acid
manufacturing is shown in Fig.1. Air at 308.15 K with a flow rate of 5054.48 kg/t of 100%
acid is compressed up to 1.3 MPa (470.15 K) and send to the mixer (M). A Part of
compressed air is sent to the absorber. Ammonia at 240.15 K with a flow rate of 281.11
kg/t of 100% acid is vaporized (AV), superheated (AS) and send to the mixer. A mixture
of ammonia and air (1: 9.7) is fed to the ammonia oxidation reactor (AOR) where
reactions no. 1 to 3 take place in the presence of a platinum catalyst.
1. 4NH3 + 5O2 = 4NO + 6H2O ΔHR,298 = -226.60 kJ/mol
2. 4NH3 + 4O2 = 2N2O +6H2O ΔHR,298 = -275 kJ/mol
3. 4NH3 + 3O2 = 2N2+ 6H2O ΔHR,298 = -318 kJ/mol
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Fig. 1 Process flow diagram of nitric acid production (T: steam turbine, C: compressor, E:
expander, HE-1-HE-7: heat exchanger, CC: cooler/condenser, AV: ammonia vaporizer,
AS: ammonia superheater, AB: absorber, AOR: reactor, M: static mixer).
At high pressure, 96% ammonia is converted into NO and reaming 4% is converted into N 2
and N2O [2]. The reaction temperature reaches up to 1189.15 K due to highly exothermic
nature. A train of heat exchangers is used to recover the heat. Steam of 4.2 MPa is
generated in waste heat boiler (WHB). Part of it is fed to steam turbine after superheating.
Large oxidation spools are included in the heat exchanger train to promote reaction 4 and
allow recovery of the reaction heat in the heat exchangers (HE-1 to HE-4).
4. 2NO + O2 = 2NO2 ΔHR,298 = -57.11 kJ/mol
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After the energy recovery, nitrous gases are passed through a cooler condenser (CC) where
it is further cooled to 325.15 K at 1.2 MPa. In the nitric acid plant, the design of condenser
is crucial for obtaining the desired concentration of product acid from the absorption
section [3] .Water is condensed due to lower temperature with the simultaneous absorption
of nitrogen oxides. The nitric oxide reacts with residual oxygen to form nitrogen dioxide
and its liquid dimer, nitrogen tetroxide.
5. 2NO2 = N2O4 ΔHR,298 = -57.32 kJ/mol
Weak nitric acid and nitrous gases in cooler condenser are separated and fed to the
absorber (AB). Water is fed from the top and air is from the bottom of the tower through
the bleaching section.
6. 3NO2 + H2O = 2HNO3 + NO ΔHR,298 = -20.53 kJ/mol
Reaction no. 6 is exothermic and continuous removal of heat is required. Upper trays of
the column are provided with chilled water coils and lower trays are provided with cooling
water coils. From reaction 5 & 6, every three moles of NO 2 reacts with water to form two
moles of nitric acid and gives back one mole of NO. This NO should be reoxidized with
additional O2 from the air. Every time one-third of the oxidized nitrogen has to be re-
oxidized with oxygen during formation of nitric acid. Nitric acid (60%) and tail gas
(almost 97% N2) are going out form the column at 339.15 K and 287.15 K respectively.
Product acid is sent for storage. Tail gas is passed through various heat exchangers and
finally expanded to the gas turbine (E) which is part of turbo-compressor as shown in Fig.
1. Mass balance of overall process is shown in Table 1.
Table 1 Material balance of nitric acid plant
Flow (kg/t of
Input Temperature (K) Pressure (MPa)
100% acid)
Air
5054.48 308.15 0.101
N2 (74.40%)
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O2 (22.60%)
Water (3.01%)
Ammonia 281.11 240.15 1.376
Process water 300 313.15 1.96
Flow (kg/t of
Output Temperature (K) Pressure (MPa)
100% acid)
Nitric acid
Nitric acid (60%) 1634.84 319.15 1.213
Water (40%)
Tail Gas
N2 (97.01%)
O2 (2.86%) 3885.3 320.15 0.101
H2O (0.1%)
NO (0.018%)
Water from Inter stage
115.45 310.15
compressor pressure
Due to stringent environmental regulations, nitrous gas concentration in tail gas must be
within the limit before going to the atmosphere. Nitric acid (15-35 wt %) may be
effectively used to scrub tail gas for reduction of nitrous gases [5]. Mowla and Razavi
(2004) studied the use of activated carbon in a fluidized bed for adsorption of nitrous
gases. Traces of nitrogen oxides are present in the tail gas due to reaction cycle (Reaction
no. 5 & 6). The cycle can be broken if NO formed in reaction 6 is reacted with nitric acid
to form N2O3. It will be ultimately converted to nitric acid after reacting with O 2 and water.
There will not be any nitrogen oxide coming out of absorber [4]. But practically in the
plants all over the world tail gas is treated by either use of a catalyst [5] (selective catalytic
reduction and non-selective catalytic reduction) or limiting its content in absorber itself
(Extended absorption) [6]. In this process, extended absorption method is used for
reduction of Nitrous gases in tail gas.
3. Energy Balance
Three forms of energy are used in the process 1) Mechanical (Shaft work) 2) Thermal and
3) Electrical. Ammonia itself acts as a source of energy. The energy balance of the process
is shown in Table 2. Enthalpy values are calculated at 298.15 K reference temperature.
Half of input energy is provided by oxidation of ammonia. Electricity is required to
operate various pumps in the plant. Though nitric acid formation from NO 2 and its dilution
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gives 21% heat, it does not contribute for any useful work production. The heat of outlet
gas from the reactor is initially recovered in expander gas heater (HE-1) followed by waste
heat boiler (WHB) and steam superheater (HE-2). Hot tail gas enters gas expander at
894.15 K and 1.1 MPa while steam enters a turbine at 589.15 K and 4.22 MPa. Excess
steam is exported after providing sufficient quantity to steam turbine. The energy input to
the compressor is 1857 MJ/t through the turbine and expander out of which only 30 % is
converted into work. Turbine contributes 70% and expander contributes 30% power to run
the compressor.
Table 2 Energy balance of nitric acid process
MJ/t of MJ/t of
Input % Output %
100% acid 100% acid
Air 562.39 6.99 Nitric Acid 180.75 2.25
Water 22.18 0.28 Tail Gas 90.06 1.12
Heat to
Electricity 126.72 1.58 5457.21 67.86
Cooling Tower
Makeup Water 690.22 8.58 Steam Export 2314.10 28.77
NH3 Heating 89.72 1.12
Heat of NH3 Oxidation 3806.70 47.33
Heat of NO Oxidation 906.59 11.27
Heat of HNO3
1035.43 12.52
Formation
Heat of HNO3 Dilution 224.85 2.80
Heat of Reoxidation of
454.69 5.65
NO
Heat of NO2 to N2O4
122.63 1.88
Formation
Total 8042.13 100.00 Total 8042.13 100.00
Energy flow including sensible heat and heat of reaction in heat exchanger train is shown
in Fig.2. Heat generated in absorber due to oxidation, absorption, acid formation and
dilution is taken away by cooling coils provided on the trays. Top trays are chilled with
chilled water of 274.85 K and bottom trays (except bleacher) are cooled with cooling water
of 307.15 K.
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6000
Energy
5000 Total Exergy
Physical Exergy
Chemical Exergy
4000
MJ/t
3000
2000
1000
0
HE-1 WHB HE-2 HE-3 HE-4 CC
Fig. 2 Energy and Exergy flow in heat exchanger train including heat of reaction.
About 68 % of input energy is lost in the cooling tower. Cooling tower circuit is shown in
Fig.2. Compressor and cooler condenser are the major candidates contributing large
amount of heat. Outlet cooling water from the cooler condenser (CC) is used to heat
ammonia in ammonia vaporizer (AV). Total 5457 MJ/t heat is discarded into the
atmosphere from the cooling tower. Energy balance shows a large quantity of heat is being
wasted but does not give any idea about its usefulness. It is possible by carrying out exergy
analysis.
4. Exergy Analysis
The energy balance of the system shows input energy is the sum of output energy and
accumulation. The case is not true for exergy balance because some part of exergy is lost
in the system due to irreversibilities present in the process. The Exergy balance of the
system can be written as
Exergy in = useful process work (product) + external exergy loss with waste stream +
exergy destruction (4.1)
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Calculations for exergy analysis are carried according to equations explained in chapter-2.
Values of chemical exergy are shown in Appendix-I. Exergy balances of individual
equipments are as follows (Fig. 4.4 to 4.10)
5. Conclusion
The nitric acid plant is a net exporter of energy. Ammonia oxidation is a major source of
energy. Plants energy efficiency is 31% and exergy efficiency is 20.83 %. Heat energy
discarded through cooling tower water is 67.86 % of the total energy. Reaction
irreversibility is a major cause of exergy loss. The Exergy efficiency of the plant can be
increased by reducing exergy losses. It is concluded that
By reducing the inlet air temperature in the compressor, exergy efficiency of the
plant can be increased up to 21.33%.
By using heat given by cooler condenser in Organic Rankine Cycle power plant,
exergy efficiency can be increased up to 24.15%. ORC plant is economically viable
if unit cost of electricity above 4 Rs./kWh.
The additional available energy of 254.26 MJ/t from both measures will increase
exergy efficiency of the nitric acid plant from 20.83 % to 24.65%.
Apart from above benefits, reduction of CO2 emission is an added advantage. Above
savings can reduce 57.56 kg of CO2 per ton of acid (100%) Carbon credits will help to
reduce expenditure required for above improvements.
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