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Nitric Acid Production - Mass and

Energy Balances
kedi (63) (/@kedi)in #science (/created/science) • 7 years ago (edited)

The purpose of this process is to produce nitric acid by anhydrous

ammonia. Drawing of the flow chart for the process and mass and energy
balances are required. Constitutively nitric acid production is that the
nitrogen monoxide in the gases formed by the oxidation of ammonia is
converted into nitric acid by absorbing it with water. Three different
processes are proposed for nitric acid production at the sources. These
are,

1. Oxidation and absorption at atmospheric pressure

2. Oxidation and absorption at high pressure (approximately 8 atm)
3. Oxidation at atmospheric pressure and absorption at high pressure
In this work we will use second option.

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Theoretical Knowledge
Nitric acid, which is very common in use, is a
clear yellowish liquid. It contains nitrogen,
hydrogen and oxygen atoms. The formula is
HNO3. Nitric acid can be produced in three
ways. These are, reacting the Chilean saltpeter
with sulfuric acid, catalytic burning of
ammonia and the burning of the air
components. Catalytic burning (Ostnvald
prodecure) is the most commonly used way of production nowadays.
Nitric acid technical (spesific) properties are,

Chemical Name Nitric Acid

Formula HNO3

Molecular Weight 63.02 g/mol

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Color / Form Yellowish / Liquid
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Chemical Name Nitric Acid

Density 1,339 ( % 55 ) - 1,1150 ( % 20 ) - 1,3667 ( % 60 ) g/cm³

Freezing Point 17 ° C ( % 20 ) - 22,4 ° C ( % 60 )

Boiling Point 103,4 °C ( % 20 ) - 120,4 °C ( % 60 )

Areas of Usage - Nitric acid is used in fertilizer production, metal industry,

paint industry, explosive materials industry, pH balancing,
electropolishing etc.

Mass Balances for The Production of Nitric Acid

Let’s suppose that,

Annual operating time is 8000 hours

Process yield is %94 over ammonia
Reactor yield is %96
The nitric acid concentration to be produced is 58% by weight
There is 0.2% NO by volume in the exhaust gases
The risk of explosion may be high if the ammonia being transported is
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more than 12%. The concentration of ammonia in the inlet should be
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above 11%
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As (/trending) (/login.html)
a basis for mass balances, ammonia (/login.html)
entering the reactor is taken as 100
kmol.

Oxidation Unit

The yield of the reaction no 1 that by

%96,

NH3(g) + 5/4 O2(g) -» NO(g) + 3/2

H2O(g)

Formed NO 100*(96/100) = 96 kmol

Required Oxygen 96x(5/4) = 120 kmol

Formed water 96x(3/2) = 144 kmol

4% of the ammonia is consumed in the input for nitrogen by reaction No. 2

formation.

NH3(g) + 3/4 O2(g) --» 1/2 N2(g) + 3/2 H2O(g)

Amount of nitrogen produced 4/2 = 2 kmol

Amount of oxygen required 2x3/2 = 3 kmol

Amount of water produced 3x2 = 6 kmol

Total amount of water produced Login

144 + 6 = 150 kmol
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Amount of nitrogen produced 4/2 = 2 kmol

Stoichiometric amount of oxygen 120 + 3 = 123 kmol

NO oxidises to NO2 by courtesty of the excess air in the input

NO(g) + 12 O2(g) --» NO2(g)

If the input ammonia concentration is taken as 11% by volume,

Amount of air in the inlet 100x(100/11) = 909 kmol

Amount of oxygen 909x(79/100) = 718 kmol

Amount of oxygen that does not react 191 - 123 = 68 kmol

Amount of nitrogen in the product stream 718 + 2 = 720 kmol

The amounts of the currents in the oxidation unit:

Mass Balance for The Condenser

The oxidation is completed until it exits

in the condenser and the whole of NO
is converted into NO2. The water in the
gas stream entering the condenser also
condenses to form a dilute nitric acid solution containing 40-50% HNO3 by
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weight. Let’s suppose that, (/login.html) Sign
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45% of the stream exiting the(/login.html)
condenser is nitric acid (/login.html)

Let's basically assume that there is 100 kmol HNO3 in the liquid stream
(condensate) leaving the condenser

3NO2 + H2O --» 2HNO3 + NO

Amount of water
required to form 50 kmol = 900 kg
100 kmol HNO3

Mass of 100 kmol

100x63 = 630 kg
HNO3

Amount of water
required to dilute (6300x55) / 45 = 7700 kg
630 kg acid as 45%

Total amount of
water required to 900 + 7700 = 8600 kg
obtain dilute acid

(Amount of water preduced per 100 kmoles of

NH3 in the inlet) / ( Amount of water required to
Formed HNO3
make 100 kmol of HNO3 to 45% solution) =
100x(2700/8600) = 31,4 kmol

Amount of NO2
consumed in the 31,4x(3/2) = 47,1 kmol
No.5 reaction

Amount of NO
31,4x(1+2) = 15,7 kmol
reacted

Amount of water
15,7 kmol
reacted
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The(/trending) (/login.html)
amount of water that is condensing (/login.html)
but not reacting with NO2 = 150
-15,7 = 134,3 kmol

The amount of NO in the gas stream from the condenser can be equal to
the amount of NO2 that forms HNO3 by absorbing it in the condensate.
Therefore, the amount of NO in the gas stream from the condenser = 15.7
kmol

Mass Balance for Nitrogen Oxides

The total amount of NO + NO2 entering the unit = No.4 = 96 kmol

31.4 kmol , leaves the unit as HNO3. For this reason, the total amount of
NO + NO2 in the gas stream = 96 -31,4 = 64,6 kmol

Assuming this is 15.7 kmol of NO, the amount of NO2 in the outgoing gas
stream = 64,6-15,7 = 48,9 kmol

Mass Balance for Oxygen

Let’s suppose that,

The amount of oxygen not reacted is x moles

The amount of oxygen resulting from the unit = The amount of

oxygen in stream 6 + The amount of oxygen in stream 4

= [NO/2 + NO2 + x ] + [3/2 *HNO3 +H2O/2] = (171 + x) kmol

= [15,7/2 + 48,9 + x ] + [3/2 *31,4 +134,3/2] = (171 + x) kmol

Amount of oxygen entering the unit = Amount of oxygen in stream 5

= [NO/2 + O2 + H2O] = [96/2 + 68 + 150/2] = 191 kmol

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191= 171 + x x=20kmol (it is the amount leaving the unit without
entering the reaction)

To calculate how much of the water vapor in the condenser input stream is
concentrated and how much remains in the vapor phase, as a preliminary
experiment, suppose that the entire water vapor is concentrated.

Amount of water in the condenser Water mole fraction x Total

leaving stream flow rate

Total flow rate of this stream (except

804,6 kmol
water vapor)

The mole fraction in this stream of

4,77x10^3
water

Amount of water vapor 4,77x10^3x804,6 = 3,8 kmol

The condensed water vapor content 134,3 - 3,8 = 130,5 kmol

Amount of water in stream 6 3,8 kmol = 68,4 kg

134,3 - 3,8 = 130,5 kmol = 2349

Amount of water in stream 7
kg

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Total flow rate of 6 and(/login.html) (/login.html)
7 = 23588,4 + 4327,2 = 27915,6 kg

Total flow rate of incoming stream = 27915 kg

Absorption Unit

Let’s suppose that,

NO2 in the gas stream entering the absorption unit is absorbed by water
and a %60 by weight nitric acid solution is formed. The amount of oxygen
in the incoming stream should be the amount that will increase NO to
NO2. The amount of oxygen in the waste gases leaving the absorption unit
should be kept at around %3

By taking advantage of the combination of 6 currents, the amount of NO in

the current entering the unit = 15.7 kmol of oxygen = 20 kmol

The amount of oxygen needed to oxidize NO2 in the input stream = 15,7 / 2
= 7,85 kmol

The amount of free oxygen in the incoming stream = 20 -7,85 = 12,15 kmol

Amount of oxygen required = (48,9 + 15,7)x(1/4) = 16,15 kmol

16,15-12,15 = 4 mol oxygen should be sent

If y mol of secondary air stream is sent to the absorption unit, 0.21 kmol of
oxygen will be in this stream. This oxygen will be consumed for 4 kmol NO
oxidation and the amount of oxygen in the waste gases will be 0,21y - 4
kmol.

Nitrogen will not undergo any change in the absorption unit. Therefore,
amount of nitrogen in exhaust gases; equal to the sum of the amount of
nitrogen in the stream coming from the condenser to the absorption unit
plus the amount of nitrogen in the secondary air.
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The amount(/)of nitrogen in the waste gas = 720 + 0,79y kmol Sign
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If we (/login.html)
assume that there is only oxygen (/login.html)
and nitrogen in the flue gas stream,
and that the amount of other gases is negligible, the percentage of oxygen
in this stream is %3. y = 141,6 kmol

The amount of oxygen in the waste gas stream = (141,6x0,21) - 4 = 25,7

kmol

The amount of nitrogen in the waste gas stream = (141,6x0,79)+ 720 = 831,8
kmol

If we assume that the amount of NO in the waste gas stream is 0.2%, the
amount of NO in the waste gas stream = total flow rate x 0,002 = (831,8 +
25,7)x0,002 = 1,7 kmol

The amount of oxygen in the waste gas stream = 25,7 + 1,7x(1/4 + 1/2) = 27,0
kmol

Absorbed nitrogen oxides = 48,9 +15,7) - 1,7 = 62,9 kmol = 3962,7 kg

Using the 6-way reaction method, the necessary stoichiometric amount of

water = (62,9/4)x2 = 31,5 kmol

If the concentration of acid stream from the absorption unit is 60% by

weight, amount of water required for dilution = = (3962,7 / 0,6)x0,4 = 2641,8
kg = 146,8 kmol

The amount of acid formed is based on the reaction of 6,

31,5 kmol H2O x 4kmolHNO3/2kmolH2O = 63 kmol HNO3

Energy Balances of Nitric Acid Production

Ammonia Vaporizer
Ammonia will be collected under pressure as liquid. The saturation
temperature at 8 atm is 20 °C. Let's assume that the feed is done at 15 ° C, at
the evaporator ambient temperature.
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Specific heat at 8 bar 4,5 kJ/kgK

Covert heat at 8 bar 1186 kJ/kg

Vaporizer inlet velocity 731 kg/st

The inlet temperature required to raise the 731x[4,5x(20-15) + 1186]

temperature to 20 ° C and evaporate; = 883413,5 kJ/st

With the addition of 10% excess for heat 1,1x883413,5 = 971754,9

losses kJ/st ≈972 MJ/st

Mixing Point

For Air ---------

Feed rate 11272,9 kg/st

Feed temperature 230 °C

Cp Air 1 kJ/kgK

For NH3 Vapor ---------

Feed rate 731 kg/st

Feed temperature 20 °C

Cp NH3 Vapor 2,2 kJ/kgK

The energy balance around the confluence point,

11272,9x1(230 - t3 )+731x2,2x(20 - t3) = 0

t3 = 204 °C

Energy Balance in The Absorption Tower Login

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Heat (/login.html)
source in the absorption column (/login.html)
will be the same as the condenser
and the same calculation method will be used.

Tower ---------

Heat in the secondary air 1754,8x1(40-25) = 0,018 GJ/st

Heat in tail gases (at 25 ° C) 0 °C

Heat in the feed water (at 25 ° C) 0 °C

Oxidized NO (202,5-21,9)/30 = 6,02 kmol/st

Produced heat 6,02x57120 = 0,34 GJ/st

Formed HNO3 1704/63 = 27,05 kmol/st

Produced heat 2 27,05x63640 = 1,72 GJ/st

Dilution temperature of %60 at 25 ° C 27,05x14207 = 0,38 GJ/st

Condensed water 29,4 - 26,3 = 3,1 kg/st

Latent heat at 40 ° C 2405 kJ/st

Heat at reference temperature 4,18x(40 - 25) = 63 kJ/kg

Heat released out 3,1x(2405 + 63) = 7,6x10-3 GJ/st

Heat in the ascending acid 0,64x(40 - 25 ) = 0,11 GJ/st

References:

Keleti, C. (1085), Nitric Acid and Fertilizer Nitrates ( Fertilizer Science

& Technology Series), CRC Press
http://www.essentialchemicalindustry.org/chemicals/nitric-acid.html
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R.M. Harrison and H.A. McCartney, (1979) Some Measurements of
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Ambient(/)Air Pollution Arising from the Manufacture of Nitric Acid and
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Ammonium Nitrate Fertilizer, Atmos (/login.html)

#chemistry (/trending/chemistry) #education (/trending/education)

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7 years ago in #science (/created/science) by kedi (63) (/@kedi) Reply 5

$ 21.50 152 votes (/science/@kedi/nitric-acid-

production-mass-and-energy-

balances)

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melih (51) (/@melih) 7 years ago (/science/@melih/re-kedi-20171020t131211383z#@melih/re-kedi- [-]

20171020t131211383z)
I don't know why, but that post reminds me the movie Fight Club.

$ 0.23 5 votes Reply

steemiteducation (72) (/@steemiteducation) 7 years ago (/science/@steemiteducation/re-kedi-nitric- [ - ]

acid-production-mass-and-energy-balances-20171019t170333695z#@steemiteducation/re-kedi-nitric-acid-
production-mass-and-energy-balances-20171019t170333695z)

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benimhayatim (/@benimhayatim) 7(/login.html) (/login.html)
years ago (/science/@benimhayatim/re-kedi- [-]
20171020t224955293z#@benimhayatim/re-kedi-20171020t224955293z)
Makale çok güzel teşekkürler

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usama25 (25) (/@usama25) 4 years ago (/science/@usama25/qlc5np#@usama25/qlc5np) [-]

Can you please elaborate the above step, how you used 6300 kg instead of 630 kg?

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mary2345 (25) (/@mary2345) 2 years ago (/science/@mary2345/rm6lr9#@mary2345/rm6lr9) [-]

If we assume that there is only oxygen and nitrogen in the flue gas stream, and that the amount of other gases is
negligible, the percentage of oxygen in this stream is %3. y = 141,6 kmol. How do you get 141,6 kmol? From
what stream do you get 3% of?

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