ACID NITRIC (HNO3) PRODUCTION

López Rosaira. [1], Begambre Juan. [1], Osorio Taher. [1], Mercado Oswaldo. [1], Diaz Adrian. [1],
Baldiris Idelfonso. [2]

[1]
3rd Semester Students of Chemical Engineering Program, [2] Inorganic Chemistry Professor
Delivered: 17/06/2019

OBJECTIVES

GENERAL OBJECTIVE
Analyze the Acid Nitric Production on a Laboratory and Industrial Scale

SPECIFIC OBJECTIVES
 Learn about obtentions methods of Nitric Acid.
 Understand the involved chemistry in Nitric Acid Production processes.
 Learn about the uses of Nitric Acid

INTRODUCTION
This text mainly covers the subject of nitric acid production, which, as a chemical engineers, it is
our responsibility to know, know and understand since it is a very important compound in the
chemical industry and with a very extensive global demand, which must be supplied on a large
scale.
Before starting to talk about nitric acid production, it is very important to know what nitric acid is
because we are interested in what it is used for and to know some history to contextualize the
subject described below.
It is known as Hydrogen Nitrate, Nitrile Hydroxide, Nital, Aqua fortis, Azoic Acid, WFNA for
White Fuming Nitric Acid, RFNA for Red Fuming Nitric Acid, "Spirit of Nitre".
Formula: HNO3 CAS: 7697-37-2 UN Number: 2031 Main Hazard Class UN: 8
CHEMISTRY OF NITRIC ACID
Nitric Acid is a strong acid, corrosive and suffocating vapors; its common form in nature
corresponds to salts of type (X(NO3)n) and not to its acid form due to the high reactivity it
exhibits in front of many substances. It is a colorless or yellowish liquid, but it may turn reddish
if it contains enough dissolved Nitrogen Dioxide. It has a very strong irritating odor in high
concentrations. It is completely soluble in water forming an azeotropic at 69.2% of acid content
and the rest of H20.
When the concentration of nitric acid in the solution is above to 86%, the fuming "surname" is
attached to the acid. A distinction is made between red and white fuming nitric acid, depending
on the amount of nitrogen dioxide in the solution. It is called red fuming nitric acid when it
contains a minimum of 10% in NO2, and white fuming acid when it contains 0.5% NO2 and no
more than 2% of water content. The physical properties of the solution vary according to its
composition.
Nitric acid is a colorless liquid under environmental conditions (in the absence of water) that
decomposes slowly by the action of light, adopting a yellow coloring due to the NO2 produced in
the reaction:
4HNO3 → 4HNO2 + 2H2O + O2
Anhydrous nitric acid has a density of 1.522 kg/m3, a molecular weight of 63.0 g/mole and its
structural formula is as follows:

Nitric Acid decomposes by heating forming water, oxygen and Nitrogen Dioxide; this behavior
makes difficult the determination of many of its properties at temperatures above 50 ºC. It also
decomposes in the presence of alcohols.
Nitric acid is one of the strongest acids from the ionic point of view but what really characterizes
it chemically is its oxidizing capacity, which is manifested on almost all metals except in the case
of gold and platinum, this is somewhat curious because in the presence of hydrochloric acid if it
is able to dissolve them.
The main emissions generated by the manufacture of nitric acid consist of nitrogen oxides, traces
of ammonia and nitric acid, with NO2 being the most toxic compound generated in production.
NITRIC ACID USES
Nitric acid is of interest to us because it serves as a nitrating agent in the manufacture of
explosives, as well as in the manufacture of fertilizers. Ammonium nitro sulfate is a simple
nitrogen fertilizer obtained chemically in the reaction of nitric and sulphuric acid with ammonia.
It is also used in certain cases in the passivation process. It is widely used in the electronics
industry, in the elaboration of printed circuit boards (PCBs) and in artistic engraving as "etching";
it is also used as an agent to test gold and platinum. It is currently one of the most widely used
acids both at industrial and laboratory level; its annual production in recent years amounts to 60
million tons. The most common industrial process for the production of nitric acid is based on the
catalytic oxidation of ammonia, a process first patented by the German chemist Wilhelm Ostwald
in 1902.

NITRIC ACID PRODUCTION

The first mention of nitric acid is found in Pseudo-Geber's De Inventione Veritatis, in which it is
obtained by calcining a mixture of alum, nitrogen and blue vitriol. Albert the Great described it
again in the 13th century and by Ramon Llull who prepared it by heating nitro and clay and
called it "Fortis Water".
Glauber devised a process to obtain it by distilling potassium nitrate with sulfuric acid. In 1776
Lavoisier demonstrated that it contained oxygen and in 1785 Henry Cavendish determined its
precise composition and demonstrated that it could be synthesized by passing through a current
of electric humid air sparks.
Several routes of synthesis have been proposed throughout recent history; among them is the
Birkeland-Eyde process (invented at the beginning of the 20th century), which consists of the
direct combination of atmospheric oxygen and nitrogen in an electric arc. The implication of this
technology was unsuccessful due to its high energy costs.
Although the basic chemistry of the nitric acid process has not changed in the last hundred years,
the development of the technology has resulted in more efficient, compact and environmentally
friendly plants. At the laboratory level, nitric acid can be prepared by heating potassium nitrate
with concentrated sulfuric acid in a glass vessel, following the reaction below:
KNO3 + H2SO4 → KHSO4 + HNO3
Nitric acid vapors are condensed in a receiver, which is cooled by water.
The process used for the generation of nitric acid is based on the oxidation of ammonia in the
presence of a catalyst and subsequent absorption into the water of the nitrogen oxides generated
to produce the product in question. This process was first carried out in 1838 by C. F. Kuhlmann,
however, this discovery was not commercialized due to the high cost of ammonia compared to
Chilean saltpeter (composed of sodium nitrate). However, advances in the synthesis of ammonia
from the Haber-Bosch process gave the process an important boost, lowering raw material costs
and favoring the implementation of this technology in the early decades of the twentieth century.
At present, weak nitric acid can be produced, with a concentration between 30-70%, and nitric
acid with concentrations higher than 90%. In the following article, we will focus on obtaining
weak nitric acid, placing emphasis on the different stages involved in its production as well as on
the different technologies that are used or have been used to obtain it.
Having said this, the process for obtaining weak nitric acid consists of the following stages:
1. Oxidation of anhydrous ammonia with air to nitric oxide.
2. Oxidation of nitric oxide to form nitrogen dioxide.
3. Absorption of nitrogen dioxide in water to give a solution of nitric acid.
From a balance of the different reactions that occur in the process, the production of nitric acid is
summarized by the following global reaction:
NH3(g) + 2O2(g) → HNO3(aq) + H2O(l)

In practice, these three process steps can be carried out in different ways, resulting in several
different production processes. Modern nitric acid plants are designed according to mono-
pressure and dual-pressure processes. The peculiarities of one system and another will be
discussed and analyzed in a later article.
 Catalytic oxidation of ammonia
The first stage of the synthesis route consists of the oxidation of ammonia whose efficiency is a
key factor.
The procedure consists of reacting in the catalytic reactor a mixture of ammonia and oxygen-
enriched air to selectively obtain nitric oxide, following the following reaction:
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
Before the reaction takes place in the catalytic reactor, a number of steps are necessary.
The ammonia, once vaporized and filtered, joins the air stream, which has also been previously
filtered and compressed (taking advantage of the power generated in the gas and steam turbine).
When the ammonia/air mixture contains 10.2% ammonia (ratio suitable for maximizing NO
formation) it comes into contact with the catalyst, resulting in a very fast (with a space velocity of
60,000-600,000h-1) and exothermic (-226 kJ/mol) reaction.
Generally, an excess amount of air is provided relative to the stoichiometric amount in order to
control the flammability of the reaction mixture and to provide an additional amount of oxygen
for subsequent oxidation reactions.
The adsorption of ammonia is followed by its dehydrogenation by means of the adsorbed oxygen.
At an additional stage, the adsorbed nitrogen atoms can give N2 or react with other oxygen atoms
on the surface to produce NO. Selectivity to the desired product does not depend on the dilution
of the adsorbed nitrogen atoms with surface oxygen atoms, in other words, on the O2/NH3 ratio
of the initial gas feed. Increased O2/NH3 ratios lead to higher NO yields.
The catalytic oxidation of ammonia can follow different steps depending on the temperature,
obtaining nitrogenous products with different degrees of oxidation in ascending order: N2, N2O
and NO. The competition between the molecules of NH3 and O2 for adsorption, mentioned
above, varies according to temperature. At low temperatures, the adsorption of nitrogen
predominates, while as the temperature increases the dissociative adsorption of oxygen molecules
increases, resulting in a greater formation of oxidized products.
Following this, in the presence of the catalyst at low temperatures (150-200°C), N2 is the only
nitrogen product. As the temperature rises, the formation of N2O begins, passing through a
maximum (at 400°C) with the increase in temperature. The formation of NO, the desired product
for the formulation of nitric acid, starts at 300°C and its performance increases with temperature.
In addition, the influence of temperature on performance is reflected in the amount of N2O
formed. N2O is formed in a secondary reaction stage between adsorbed NO molecules and
nitrogen atoms on the surface of the catalyst. Low temperatures slow down the desorption rate of
the NO molecules from the catalyst surface and cause more N2O emissions from the catalyst.
Under industrial process conditions, the selectivity towards N2O and N2 is sought to be minimal,
this being 1.5-2.5 and 4-4.5%, respectively.
Apart from the unwanted reactions already mentioned (towards obtaining N2 and N2O), it is also
necessary to highlight the reactions between the ammonia that has not reacted with the nitrogen
monoxide, which decreases the yield towards the desired product, NO. Similarly, the
decomposition of NO and ammonia favored processes at temperatures above 1000 °C and long
contact times should be minimized. As a general rule, high flows and linear velocities of 1m/s are
needed to minimize these unwanted reactions.
Not surprisingly, a small improvement in NO selectivity is really attractive, not only due to the
subsequent lower N2O emission but also to the increased production of nitric acid. An increase in
yield of 1% means an increase of approximately 500,000 euros per year.
Low pressures of 1 to 6.5 bar (in dual pressure plants) and 1 to 13 bar (in plants with a single
pressure level) are operated in order to favor the formation of NO in the reaction (4). With regard
to temperature, work is carried out at elevated temperatures, normally between 810-940°C. Under
these process conditions, a variable yield of between 93 and 98% in NO is obtained.
The most commonly used catalyst is composed of 90% platinum and 10% rhodium. The catalyst
consists of a mesh formed from the interlacing of 60-75 µm metal wires. From 3 to 50 catalyst
metal meshes can be fixed in the reactor (diameter up to 5.5 m), depending on the operating
pressure and design of the reactor.

Oxidation of nitric oxide

The effluent gas from the catalytic oxidation reactor is cooled to about 150-200°C in a heat
exchanger train (Figure 4), and the heat generated is used to produce steam (and later electrical
power in the turbine), heat the air that is fed to the ammonia oxidation and increase the
temperature of the absorber effluent gases.
In the condenser temperatures of 40-50°C are reached and 50% of the nitrogen monoxide is
converted into nitrogen dioxide (which is in equilibrium with its N2O4 dimer) without the
presence of catalysts, according to the following reaction:
2NO(g) + O2(g) → 2NO2(g)
The combustion heat of the reaction is -56 kJ/mol. This homogeneous reaction is highly
dependent on process temperature and pressure. Operating at low temperatures and high
pressures promote the production of NO2 within a minimum reaction time.
In the coldest condenser conditions, the water formed in the ammonia oxidation condenses and
absorbs some of the nitrogen dioxides to form nitric acid. The current at the outlet of the
condenser is fed to the absorption column.
 Absorption of nitrogen dioxide
The current at the outlet of the condenser is pumped to the bottom of the absorption tower while
the deionized water is fed countercurrent. An air stream is also introduced into the column to
oxidize NO that has not been converted to NO2.
The oxidation reaction occurs between the plates in the column while the absorption reaction
(shown below) takes place in the plates.
3NO2(g) + H2O(l) → 2HNO3 (g) + NO(g)
An aqueous solution with 55-65% nitric acid is usually obtained at the bottom of the column. The
acid concentration can vary between 30% and 68% (due to the azeotrope formed with water). The
acid concentration at the exit of the column depends on the temperature, pressure, number of
absorption stages and the concentration of nitric oxide at the entrance of the absorber.
To maximize performance, the temperature is kept low (about 50°C) and the pressure high (9-10
atm). The absorption of nitrogen dioxide into the water to form nitric acid has a yield of 99.9% so
the overall yield from ammonia fluctuates around 95%; about 300kg of ammonia are consumed
per tonne of nitric acid.
High-efficiency perforated plates or bubblers are used in the tower. The spacing between plates
increases progressively from the bottom to the top of the absorber. Many of the trays are
equipped with internal cooling coils to eliminate reaction heat (as the reaction is slightly
exothermic). The absorption section may consist of one or more columns.
The acid solution at the outlet of the absorption section is rich in dissolved nitrogen oxides so that
it passes to a bleaching tower where it comes into contact with a countercurrent airflow. The air
stream and nitrogen oxides that have been stripped are joined to the exhaust gases of the cooling
section and recycled to the absorption section.
The tail gas of the absorber is fed to a drag separator to remove acid mist. After this, the gas is
reheated by taking advantage of the heat released by the oxidation of ammonia to approximately
200°C.
In a final stage, the gas (once the concentration of nitrogen oxides has been reduced) expands in a
turbine, and the energy obtained can be used to drive the compressor.
All these processes to obtain nitric acid involve risks and problems especially in the
environmental field since almost all industrial processes are large-scale and involve toxic
compounds.
This is a schematic of the nitric acid production:

Finally, it should be mentioned that the main problem involved in the use or production of Nitric
Acid are the gases released when it reacts with other substances under certain conditions, when it
undergoes excessive heating processes or when they are emitted in the production process. These
gases are constituted mainly by Nitrogen monoxide (NO) and Dioxide (NO2), which are very
toxic substances by respiratory and cutaneous routes. In European countries, it is stipulated that
the maximum permitted emissions of NOX must be 200 ppm (1996) and that the gases and
vapors generated can only be discharged into the atmosphere when they are free of red or yellow
colorations. All modern Nitric Acid production plants include Nitrogen oxide emission recovery
operations. The recovery is carried out with methods called improved absorption, chemical
purification, catalytic reduction, and adsorption. A detailed description of each of these methods
is given at Ullman´s Encyclopedia of Industrial Chemistry.
The treatment of gases of continuous emission product of the decomposition or generation of
Nitric Acid is developed in towers of absorption with water where the main variables that are
taken into account for the design correspond to the pressure and temperature of operation and the
partial pressures of the oxides of Nitrogen and Oxygen in the gas stream.
REFERENCES
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http://www.epa.gov/oar/aqtrnd97/brochure/no2.html
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(Nitric Oxide, Nitrogen Dioxide, etc.) [online]. April de 2002 [Referenced june 26th
2003]. Available in http://www.atsdr.cdc.gov/tfacts175.html
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Seguridad, Ácido Nítrico. Last Updated: 2003. Bogotá, Colombia.