Nitric Acid

Introduction
Nitric acid, HNO3, also known as aqua fortis, azotic acid or hydrogen nitrate is a chemical of major industrial
importance. Because of its properties as a very strong acid and a powerful oxidizing agent, as well as its ability
to nitrate organics, nitric acid is essential in the production of many chemicals, for example, pharmaceuticals,
synthetic fibers, insecticides, fungicides and explosives (TNT), but is used mostly in the production of
ammonium nitrate for the fertilizer industry. World production today is estimated to 45 million tonnes annually
but consumption declined by about 12% between 1990 and 2002, but is expected to increase marginally through
2008. The declines occurred in the dominant countries, but were partially counteracted by increases in other
regions, particularly Africa. Only Western Europe is expected to record a marginal decline. All other countries
are expected to show some growth. i

The Process
Almost all commercial quantities of nitric acid are manufactured by the oxidation of ammonia with air to form
nitrogen oxides that are absorbed in water to form nitric acid. Some different versions of this process exist.
There are mono-pressure processes which have the same pressure in the oxidation and the absorption. There are
also dual-pressure plants which have a higher pressure in the absorption than the oxidation. The process can be
carried out at medium pressure, 3–6 atmospheres, or at high pressure, 7–12 atmospheres. The high pressure
process has been the most prevalent design. For optimum conversion efficiency, the oxidation should be carried
out at medium pressure and absorption at high pressure, which has led to plant constructors having a dual-
pressure process although this can only be economically justified on high tonnage plants of around 1000 tonne /
day. ii

Ammonia and air are mixed such that there is an excess of oxygen and are passed over a platinum / rhodium
gauze catalyst to produce nitric oxide, water vapour, and much heat. The resulting gases are cooled, thus
generating steam that can be exported or used to power the steam turbine. As the process gases cool, nitric
oxide is further oxidized to form nitrogen dioxide, in equilibrium with nitrogen peroxide, N2O4. The process
gases then enter a column where the equilibrium mix of NO2 and N2O4 is absorbed into water, producing nitric
acid. Nitric oxide, released by formation of the nitric acid, must be oxidized to complete the conversion of
nitrogen oxides to nitric acid. Spent gases from absorption contain residual levels of nitrogen oxides, NOx,
which for environmental reasons have to be removed before discharge to the atmosphere. Especially the
emission of N2O from the process is a big issue that needs further measure.

The overall reaction is:

4 NH3 + 5 O2 Æ 4 NO + 6 H2O (1)

2 NO + O2 Æ 2 NO2 (2)
3 NO2 + H2O Æ 2 HNO3 + NO (3)

The oxidation of ammonia with air to nitric oxide is one of the most efficient catalytic reactions with a reaction
time of approximately 10-4 seconds. The residence time on the catalyst is critical if various side reactions are to
be minimised.

The Catalyst
Platinum and rhodium remains the catalyst of choice in this process despite its high cost. It’s used as multiple
layers of a fine wire mesh or gauze, it typically contains 5–10 wt % of rhodium for increased strength and
improved reaction yield. Using such platinum-based catalysts, the conversion of ammonia to nitric oxide is high
(93–98%). The optimum reaction temperature for conversion efficiency increases with operating pressure. At
typical gauze temperatures of 800–940°C, nitric oxide is thermodynamically unstable and slowly decomposes
into nitrogen and oxygen. Decomposition losses are minimized by avoiding excessive catalyst contact time and
rapidly cooling the gases as they exit the converter. Fortunately, the conversion of ammonia to NO is very rapid
and catalyst contact time is as low as 10–4 s. iii

The catalyst is a woven gauze with either 0.060 mm or 0.076 mm wire diameter and 1024 mesh/cm2. Since the
introduction, knitted catalyst has become the industry standard. Loss of platinum and rhodium from the catalyst
has always been an issue for the producers. The use of catchment gauze, which is a gauze made of palladium or
an palladium alloy used to catch particles and volatile oxides from the catalyst, has spared much precious metal.
This subject is further discussed in section 4.1.

Producers
There are many companies that produce nitric acid. In the USA, some of the biggest are El Dorado Nitrogen,
PCS Nitrogen Fertilizer and Mississippi Chemical. iv In Europe Yara (Hydro) and BASF produce it. Producers
of the gauze catalyst include Johnson Matthey, Heraeus and KA Rasmussen.

Hydrogen Cyanide
Introduction
Hydrogen cyanide (HCN) is a colourless gas or liquid. It’s also known as hydrocyanic acid, prussic acid or
formonitrile. It’s a liquid at room temperature with the characteristic smell of bitter almonds. The boiling point
is low, 25.6°C. Hydrogen cyanide hydrolyzes, initially to formamide, and subsequently to ammonium formate.
Upon prolonged standing, it can polymerize explosively. Because of this, storage and shipping of hydrogen
cyanide is difficult and the producers are often the main users. v

The Process
By far the most common method for the manufacture of hydrogen cyanide is the Andrussow process that has
much similarity with the oxidation of ammonia in the production of nitric acid. In the Andrussow process,
methane, ammonia and air are reacted by passing the mixture over a number of rhodium-platinum gauzes. Due
to the operating temperature of between 1000 and 1100°C the gauze composition is 10% rhodium and 90%
platinum. Higher reactor pressure leads to higher yields, but also higher costs. The actual operating pressure
will be set by total process economics.

2 CH4 + 2 NH3 + 3 O2 Æ 2 HCN + 6 H2O (4)

The reaction (4) is exothermal and generates 962.8 kJ / mole. The oxidation of the hydrogen is not complete so
that the converter off-gas contains hydrogen. The overall reaction is carried out adiabatically. This is
accomplished by the addition of air (O2). The air oxidizes a portion of the methane, making the overall reaction
exothermic, even though the reaction of methane with ammonia to form hydrogen cyanide is endothermic. To
obtain an optimum yield of hydrogen cyanide, a very short contact time (milliseconds) is required and
consequently a high operating temperature is required to reach equilibrium. Typical conversion efficiencies are
of the order of 60-70% of the ammonia. vi

The flow sheet below shows the Andrussow process. Another process without the ammonia recycle also exists,
but is not as frequently used.
Flow sheet of the Andrussow process 13

The converters are similar to the ammonia oxidation converters used in the production of nitric acid although
this process operates at somewhat lower temperatures. The feed gases to the converter are premixed. The
optimum operating mixture of feed gas is above the upper flammability limit and caution must be exercised to
keep the mixture from entering the explosive range.

A typical converter is made up of multiple furnaces, each of which contains 8 to 10 reactors. Each reactor is
made up of 10 to 30 sintered alumina tubes lined with platinum. The furnaces are direct fired with natural gas to
1200–1300°C.13

The reactions taking place in the Andrussow process are more complex than that shown above. Most of the heat
required for hydrogen cyanide formation is supplied by combustion of methane. The endothermic reaction
between methane and ammonia requires 251 kJ/mole hydrogen cyanide formed. Preventing the decomposition
of ammonia and hydrogen cyanide is a critical aspect of successful operation. The equilibrium concentration of
hydrogen cyanide in the converter gases at 1100°C is 0%. Therefore, to prevent hydrogen cyanide
decomposition, the converter gases must be quickly quenched to a temperature below 4000C. This is done in a
steam-generating waste-heat boiler located directly below the catalyst gauze.13

Air pollution from this process is a minimal problem because all waste gases are burned for fuel value or flared.
The products of combustion of the waste gases are primarily water from the hydrogen and some carbon dioxide
from the carbon monoxide. Aqueous discharge is essentially the converter water of reaction, which is
contaminated by traces of hydrogen cyanide and other nitriles and the ammonium sulphate. The most common
treatment for this aqueous stream is alkaline chlorination, which converts cyanide to the essentially non-toxic
cyanate.
The typical composition of the off-gases from the Andrussow process can be seen in the table below.

Composition in the off-gases from the Andrussow process

Substance HCN CO2 CO CH4 H2 NH3 O2 N2 H2O
Vol % 5.9 0.2 4.4 0.5 7.5 1.6 0.1 56.7 23.0

The Andrussow process is by far the dominant hydrogen cyanide manufacturing process in use, even though the
converter off-gas stream is dilute in hydrogen cyanide. This forces the absorbers to be large so that they can
handle the large volumes of gas. Preheating the feed gases is claimed to result in an increased hydrogen cyanide
concentration by supplying part of the required reaction heat without in situ combustion. Advantages of the
Andrussow process are low converter investment, low maintenance costs and high natural gas yields when the
waste gas is used as fuel.

Uses
The various uses for hydrogen cyanide are adiponitrile for nylon (41%), acetone cyanohydrin for acrylic plastics
(28%), sodium cyanide for gold recovery (13%), cyanuric chloride for pesticides and other agricultural products
(9%), chelating agents such as EDTA (4%) and methionine for animal feed (2%). vii

There has been a sizable shift in distribution of uses since the early 1980s. The use of hydrogen cyanide for
manufacturing nylon via the adiponitrile route has expanded substantially and the use for producing sodium
cyanide has also grown. Other uses have shown a more normal growth rate. Modest quantities of hydrogen
cyanide go into a large number of relatively small uses, including manufacture of ferro-cyanides, acrylates,
lactic acid, pharmaceuticals and specialty chemicals.

The Catalyst
The standard catalyst used in this process is a 10% rhodium 90% platinum gauze with a wire diameter of
0.076mm. Until the introduction of knitted catalyst, woven gauze with 1024 mesh/cm2 was traditionally used.
Although woven catalyst is still available, knitted catalyst is increasingly becoming the industry standard. The
catalyst bed consists of a number of layers of gauzes arranged in pack.14

Depending on the reactor type and operating conditions, between 6 and 40 gauzes are installed. During
operation the catalyst wires expand by approximately 25% with the top gauzes becoming completely porous.
The degree of porosity normally decreases with the bottom gauzes still retaining a solid core. However, during
the campaign the gauzes become sintered together making separation extremely difficult. As is the case in
ammonia oxidation the surface of the wire develops a crystallite structure that significantly increases the
available surface area. Due to the modest operating conditions, atmospheric or low pressure, metal loss is low, 3
% per campaign approximately.

The activity of a new gauze pack is relatively low, but this increase with on-stream time. The time to reach full
activation can vary widely, from a couple of hours to several weeks. Once the catalyst reaches its peak activity,
this level is maintained for hundreds of hours. Generally, the gauze pack lasts several thousands of hours before
its activity decreases to the point where it has to be changed. The spent gauze is removed from the reactor and
sent back to the catalyst manufacture for reprocessing.

The drop-off in catalyst activity is marked by physical changes in the gauzes. Dark spots appear, pointing to
carbon deposition on the gauze, especially around its periphery that has a lower temperature than the centre. If
the process continues, carbon deposition can cause the catalyst wire to become very brittle and holes can appear
in the gauze.

Contamination of the gauze surface, particularly with iron, can have a very adverse effect on the efficiency of
the reaction. Iron concentration as low as 35 ppm can prevent the catalyst from attaining its full activity.
Sulphur, silica and aluminium are also contaminants that will significantly reduce catalyst.

No catchment gauzes are needed in the hydrogen cyanide production. Compared to nitric acid production the
loss of platinum and is very small, because of the low pressure in the operating plant. There is a small loss of
platinum but it not economically beneficially to install a, for example, palladium catchment gauze. viii

The worldwide annual use of platinum is estimated to be 3.2 tonnes platinum and 360 kg rhodium. This is
calculated on how much that is taken from the newly mined metals, the amount of recycled catalyst is not in this
number. See Appendix C for calculations.

Producers
Dupont, Rohm and Haas Co, ICI (Imperial Chemical Industries) and Degussa are the major manufactures. In
2004 there were 36 companies operating 44 hydrogen cyanide production facilities with a total production
capacity of over two million metric tons in the United States, Western Europe and Japan. DuPont is the
dominant world producer with about 38% of total capacity, either totally or partially owned. No other producer
has above a 7% world capacity share. Dupont have recently signed a licensing deal with Aker Kvaerner which
gives them the right to market and sell Dupont’s technology for hydrogen cyanide production.

In the US alone in 2004, the top thirteen manufacturers of hydrogen cyanide produced 1 million tonnes to fulfil
its demand in other industries such as metallurgy and electroplating. Cyanide can be produced or extracted from
many everyday items such as burning cigarettes, plastics, wool, and silk, and from portions of certain plants like
the roots of cassava plants and the pits of cherries and apricots.15

The biggest producers in USA, location and capacity in thousand tonnes per year.
Producer Capacity
Aventis, Institute, West Virginia. 7
Cyanco, Winnemucca, Nevada. 22
Cytec Industries, Fortier, Lusianna. 30
Degussa, Theodore, Alabama. 34
Dow, Freeport, Texas. 18
DuPont, Memphis, Tennessee. 100
DuPont, Orange, Texas. 145
DuPont, Victoria, Texas. 180
FMC, Green River, Wyoming. 15
Novartis, St. Gabriel, Lusianna 40
Rohm and Haas, Deer Park, Texas. 90

Heraeus and Johnson Matthey are the biggest producers of the catalyst for this process.

The future
The increasing price of gold the last year has led to a bigger sodium cyanide demand in the mining industry, the
chemical's primary driver. The gold price has recently reached an all time high (560$/oz – 060116), which may
increase the mining of gold and also the demand for sodium cyanide.

Overall demand for HCN continues to grow at about 2.7 percent annually. This is mainly due to the relatively
strong performance of nylon 6/6. Strong exports of adiponitrile and sodium cyanide continue to be key growth
factors for HCN.