MANUFACTURING OF NITRIC ACID

- DISHA DHADD (174015)

- KOMAL KANKANI (174029)
- SOHAIL KHAN (174030)
 INTRODUCTION
NITRIC ACID, ALSO KNOWN AS AQUA FORTIS AND SPIRIT OF NITER, IS A HIGHLY CORROSIVE MINERAL ACID.

• THE PURE COMPOUND IS COLOURLESS, BUT OLDER SAMPLES TEND TO ACQUIRE A YELLOW CAST DUE TO
DECOMPOSITION INTO OXIDES OF NITROGEN AND WATER. MOST COMMERCIALLY AVAILABLE NITRIC ACID HAS A
CONCENTRATION OF 68% IN WATER.

• WHEN THE SOLUTION CONTAINS MORE THAN 86% HNO3, IT IS REFERRED TO AS FUMING NITRIC ACID.

• NITRIC ACID IS THE PRIMARY REAGENT USED FOR NITRATION – THE ADDITION OF A NITRO GROUP, TYPICALLY TO
AN ORGANIC MOLECULE. WHILE SOME RESULTING NITRO COMPOUNDS ARE SHOCK- AND THERMALLY-
SENSITIVE EXPLOSIVES

• A FEW ARE STABLE ENOUGH TO BE USED IN MUNITIONS AND DEMOLITION, WHILE OTHERS ARE STILL MORE STABLE
AND USED AS PIGMENTS IN INKS AND DYES. NITRIC ACID IS ALSO COMMONLY USED AS A STRONG OXIDIZING
AGENT.
 STRUCTURE & FORMULA
• THE FORMULA OF NITRIC ACID IS HNO3
• THE STRUCTURE IS AS FOLLOWS :
 PHYSICAL PROPERTIES
Chemical Formula HNO3
Molar Mass 63.012

Appearance Colourless, yellow or red fuming liquid

Odour Acrid, Suffocating

Density 1.51 g cm−3, 1.41 g cm−3 [68% w/w]

Melting point −42 °C (−44 °F; 231 K)

Boiling point 83 °C (181 °F; 356 K) 68% solution boils at

121 °C (250 °F; 394 K)
Solubility in water Completely miscible

Vapour pressure 48 mmHg (20 °C)

Acidity (pKa) -1.4

Conjugate base Nitrate

 CHEMICAL PROPERTIES
• Commercially available nitric acid is an azeotrope with water at a concentration of 68% HNO3. This solution has
a boiling temperature of 120.5 °C at 1 atm. It is known as "concentrated nitric acid". Pure concentrated nitric
acid is a colourless liquid at room temperature.
• Two solid hydrates are known; the monohydrate (HNO3·H2O or [H3O]NO3) and the trihydrate (HNO3·3H2O).
• An older density scale is occasionally seen, with concentrated nitric acid specified as 42° Baumé.

ACID BASE PROPERTIES

Acid dissociation constant pKa value is reported less than −1. This means that the nitric acid in diluted solution is fully
dissociated except in extremely acidic solutions. The pKa value rises to 1 at a temperature of 250 °C.
7v Nitric acid can act as a base with respect to an acid such as sulfuric acid:

HNO3 +2 H2SO4 ⇌ NO+2 +H3O+ +2 HSO−4; Equilibrium constant: K ≈ 22

The nitroniumion, NO+2, is the active reagent in aromatic nitration reactions. Since nitric acid has both acidic and
basic properties, it can undergo an autoprotolysis reaction, similar to the self-ionization of water:

2HNO3 ⇌ NO+2 + NO−3 + H2O

REACTION WITH METALS
Nitric acid reacts with most metals, depending on the concentration of the acid and the nature of the metal.
Dilute nitric acid behaves as a typical acid in its reaction with most metals. Magnesium, manganese,
and zinc liberate H2:
Mg + 2 HNO3 → Mg(NO3)2 + H2 (Magnesium nitrate)
Mn + 2 HNO3 → Mn(NO3)2 + H2 (Manganese nitrate)
Nitric acid can oxidize non-active metals such as copper and silver. The products depend on temperature and
the acid concentration. For example, copper reacts with dilute nitric acid.
3Cu+8HNO3 →3Cu2+ +2NO+4H2O+6 NO−3
Nitric oxide reacts with atmospheric oxygen to give nitrogen dioxide. With more concentrated nitric acid,
nitrogen dioxide is produced directly.
Cu+4H+ +2 NO−3 → Cu2+ + 2 NO2 + 2 H2O
With nitric acid, most metals give the corresponding nitrates. Some metalloids and metals give the oxides; for
instance, Sn, As, Sb, and Ti are oxidized into SnO2, As2O5, Sb2O5, and TiO2 respectively.

Some precious metals, such as Au and Pt do not react with nitric acid, though pure gold does react with aqua
regia, a mixture of concentrated nitric acid and hydrochloric acid. However, some less noble metals (Ag, Cu) can
be easily oxidized and dissolved by nitric acid, leading to colour changes.
REACTIONS WITH NON-METALS
Nitric acid reacts violently with many organic materials and the reactions may be explosive. The hydroxyl group
will typically strip a hydrogen from the organic molecule to form water, and the remaining nitro group takes the
hydrogen's place. Nitration of organic compounds with nitric acid is the primary method of synthesis of many
common explosives, such as nitroglycerin and trinitrotoluene (TNT). The byproducts are less stable.

Reaction with non-metallic elements, with the exceptions of nitrogen, oxygen, noble gases, silicon,
and halogens other than iodine, usually oxidizes them to their highest oxidation states as acids with the
formation of nitrogen dioxide for concentrated acid and nitric oxide for dilute acid.

Cgraphite + 4 HNO3 → CO2 + 4 NO2 + 2 H2O

or
3 Cgraphite + 4 HNO3 → 3 CO2 + 4 NO + 2 H2O

Concentrated nitric acid oxidizes I2, P4, and S8 into HIO3, H3PO4, and H2SO4, respectively. Although it reacts
with graphite and amorphous carbon, it does not react with diamond; it can separate diamond from the
graphite that it oxidizes.
 AVAILABLE PROCESSES
The first mention of Nitric Acid was found in the Arabic Alchemists. Nitric acid was formed by
calcining a mixture of niter alum and blue vitriol (CuSO4.5H2O)
GLAUBER PROCESS
This process was found by Arabic Alchemists. Process to obtain Nitric Acid by Distilling Potassium
Nitrate with Sulfuric Acid.

BIRKELAND EYDE PROCESS

Oxidation of atmospheric nitrogen by atmospheric oxygen to give nitric oxide. Only 4-5% of Nitric
Oxide is formed at 3000 deg Cel. On further oxidation of nitric oxide Nitrogen dioxide is formed
which is followed by absorption in water to produce dilute Nitric Acid.

cOSTWALDS PROCESS
-DUAL PRESSURE PROCESS
-MONO PRESSURE PROCESS
 OSTWALDS MONO PRESSURE PROCESS
Factors Favouring the Single-Pressure Process

The single-pressure process uses a higher ammonia conversion pressure. This higher pressure provides
advantages in terms of equipment design, e.g. smaller converter dimensions and a single heat-exchanger-
train layout. The higher temperature and the favourable pressure both increase the energy recovery from the
process. The single-pressure process provides an extra 10% high-level recoverable heat energy.

Process Selection Conclusions

The single-pressure process appears to be preferred for a plant producing 280 tonne/day of 60% nitric
acid. The capital cost advantage of this process surpasses the benefits of the superior operating cost structure
of the dual-pressure process. Furthermore, the higher temperature and the favourable effect of pressure
enable a greater recovery of energy from the process. This choice, made on both economic and operational
grounds, is consistent with the conclusions.
 PROCESS DISCRIPTION

• The plant has a capacity of 1667 t/d N in the acid corresponding to 750 t/d HNO3 (100%).
• The produced acid is obtained with a concentration of 60% b.w. i.e. in total are produced 1250 t/d HNO3
60%. For this capacity the plant is designed as single - stream type.
• The plant operates according to the mono-medium pressure process, i.e. the plant operates in the combustion
and in the absorption section practically under the same pressure. The medium pressure of the plant is
approx. 5.5 at. Abs.
• Prior to the Ammonia combustion the air quantity required for the process is supplied by a turbo compressor.
The combustion of Ammonia to Nitric oxide is catalytically performed on Platinum gauzes with 10% b.w.
Rhodium. The heat obtained with this reaction
4 NH3 + 5O2 → 4 NO + 6H2O + 216000 kcal
is utilized in the waste heat boiler, La Mont type -, for steam generation.
• Part of this steam is utilized by means of a condensation steam turbine, for driving of the turbo compressor,
which is additionally driven by a tail gas expansion turbine.
• For starting of the plant the steam turbine is fed with foreign steam and after ignition of the burner the
steam generated in the plant with 420C and 40 abs. is used.
• Part of this steam is available as surplus steam and is delivered to the factory steam system.
• The separation of the water vapour contained in the combustion gas is effected in the gas cooler-condenser.
The main oxidation of Nitric oxide to Nitrogen dioxide is performed in the gas cooling train and in the lower
part of the absorption column.
• The upper part of the column serves for absorption. The absorption columns are provided with sieve plates
on which cooling coils are arranged for elimination of the reaction heat generated.
• The tail gas leaves the absorption columns with a residual NOx content of 1200 ppm. For further reducing
low NOx level in the tail gas to 250 ppm, the gas is reacted with ammonia in SCR to selectively give N2 as
reactant.
• The degassing of the product acid and the circulation acid from dissolved Nitrogen dioxide is effected in
separate degassing columns by mean of hot air, which is branched off after the air compressor.
• The water required (process water) for formation of the aqueous Nitric acid is charged on top of the
absorption column.
• The design of the plant is based on the assumption of a cooling water temperature of 33C and a rise of
8C. The Ammonia required for the process is made available in liquid condition.
• The cold obtained with evaporation of Ammonia is used for cooling in the absorption section. To have this
cold at low level the Ammonia is vaporized at 6 ata.
 THERMODYNAMIC FEASIBILITY

• 4 NH3 + 5 O2 → 4 NO + 6 H2O

Components ΔHf0 ΔG0 ΔS0 Cp

(kcal/mol) (kcal/mol) (kcal/mol.K) 493K(kcal/mol.

k)
Ammonia
-10.97 -4.12 -0.02 0.00998
Nitric oxide
-21.58 -6.57 -0.05
0.002
water -68.31 -56.66 -0.04
0.0189
• HEAT OF REACTION AT 298K :-
ΔHR0 = -452.3 KCAL/MOLE
• GIBB’S FREE ENERGY AT 298K :-
ΔGR0 = -349.8 KCAL/MOLE
• THE ENTHALPY CHANGE AT 493K :-
ΔHR = -436.38 KCAL/MOLE
• THE ENTROPY CHANGE AT 493K:-
ΔSR = -0.3694 KCAL/MOLE.K
• GIBB’S FREE ENERGY AT 493K :-
ΔGR = -254.26 KCAL/MOLE

SINCE, ΔGR IS NEGATIVE AT 493K THE REACTION IS FEASIBLE.

 MARKET DATA

• The Global Nitric Acid Market is primarily driven by the fertilizer industry and is expected to grow at
Compound Annual Growth Rate of 6.5% from 2016-2022.
• Use of ammonium nitrate and calcium ammonium nitrate in fertilizer is expected to be key driver of the nitric
acid market’s growth. Ammonium nitrate is derived from Nitric Acid which is extensively used in
manufacturing of explosives and fertilizers.
• Increasing demand from defence industry owing to use of explosives at cross border area has driven the
Nitric Acid Market’s growth.
• Other than fertilizer application, nitric acid is also used in production of adipic acid. Adipic acid produces
nylon 6.6 which is further used in textile, tire and automotive industry.
• Toluene di isocyanate (TDI) act as an intermediate, though using nitric acid for developing polyurethane
forms, which is used in furniture, transportation and automotive industry is also driving the growth of this
market. Thus, influencing nitric acid market’s demand over the forecasted period.
• Asia Pacific is largest market segment owing to increase in fertilizer and chemical industries in the region.
China forecasted fastest growth rate in the production and consumption of nitric acid owing to growing
chemical and explosive industries.
• North America and Europe witnessed a significant loss due to adverse environmental issues which will rise as
a result of usage of chemicals relating to nitric acid.
• Strict regulations government in Europe and North America regarding usage of ammonium nitrate in fertilizer
has shift the demand to emerging countries like China and India. Other application like adipic and TDI is
expected to drive the demand of nitric acid in North America.
• Other parts of the world are expected to witness strong growth due to increase in demand for nitrate based
fertilizer in agrochemical industry and lack of regulation in using chemicals.
• New uses have been found for ammonium nitrate-oil mixtures as a cheap open pit explosive for quarrying,
mining, construction. The market for other nitrate-based explosives is considered stable with very little
growth.
• Rocket propellant compositions may ultimately provide a small but increasing market for such products as
fuming red nitric acid (conc. HNO3 with N2O4 solubilized), N2O4 and monopropellants such as
tetranitromethane.
 INDUSTRIAL APPLICATIONS
• The main industrial use is production of fertilizers.
• Nitric acid is neutralized with ammonia to give ammonium nitrate. This application consumes 75–80% of the
26 million tonnes produced annually (1987).
• Production of explosives, nylon precursors, and specialty organic compounds.
• Use as an oxidant - The precursor to nylon, adipic acid, is produced on a large scale by oxidation of "KA
oil“- a mixture cyclohexanone and cyclohexanol with nitric acid.
• Rocket propellant - Nitric acid has been used in various forms as the oxidizer in liquid-fueled rockets. These
forms include red fuming nitric acid, white fuming nitric acid, mixtures with sulfuric acid, and these forms with
HF inhibitor.
• Analytical reagent - In elemental analysis by ICP-MS, ICP-AES, GFAA, and Flame AA, dilute nitric acid (0.5–
5.0%) is used as a matrix compound for determining metal traces in solutions. Ultrapure trace metal grade
acid is required for such determination, because small amounts of metal ions could affect the result of the
analysis. EG - turbid water samples, sludge samples, solid samples as well as other types of unique samples
which require elemental analysis. In electrochemistry, nitric acid is used as a chemical doping agent for
organic semiconductors, and in purification processes for raw carbon nanotubes.
• Woodworking - In a low concentration (approximately 10%), nitric acid is often used to artificially
age pine and maple. The colour produced is grey-gold similar to old wax or oil finished wood.