PERP Program November 1998

Nitric Acid (97/98S12)

Nitric acid is one of the three or four most important inorganic acids in the world. 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 for the production of fertilizers, plastics, pharmaceuticals, dyes, synthetic fibers, insecticides, fungicides, and military and aerospace materials. It is also employed in metallurgy and construction. Weak acid (60-70 weight percent) is suitable for use in the production of fertilizers, but stronger acid (up to 99 weight percent acid) is required for many organic reactions of industrial importance. In concentrations over 86 percent, it is referred to as fuming. The same basic route, the Ostwald process, manufactures almost all nitric acid (HNO3) in the concentration range of 50 to 70 percent acid. Three steps common to most processes are:

Oxidation of ammonia to nitric oxide over a platinum/rhodium catalyst

4NH3 + 5O2
G:\98Q2\4374\RP\4374-1.CDX

4NO + 6H2O

(1)

Oxidation of nitric oxide to nitrogen dioxide with excess oxygen

2NO + O2
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2NO2

N 2 O4

(2)

Absorption of nitrogen dioxide in water to produce dilute nitric acid

3NO2 + H2O
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2HNO3 + NO

(3)

There are three main considerations, which are of prime importance when considering the overall design of a nitric acid plant:

Environmental control Efficiency in the utilization of raw materials Energy economy Water extraction processes Processes that give rise to the superazeotrope by the further absorption of nitric oxides

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Processes that make use of the reaction of dinitrogen tetraoxide with oxygen and
water/dilute acid mixed in stoichiometric proportions Processes may be classified according to pressures at which the oxidation and absorption reactions are carried out. Although operation of the plant at a single pressure throughout is favored on the grounds of reliability and economy, a dual pressure system with combustion at a medium pressure and absorption at a high pressure is preferred in certain situations. A higher oxidation pressure (up to 14 bar(a) or 203 psia) would afford a lower capital cost, but would result in lower conversion efficiencies and higher catalyst losses. High pressure absorption processes (12-14 bar(a) 174-203 psia) are able to contain emissions to below 200 vppm of nitrogen oxides. Dual pressure plants are designed to achieve economic energy use while fully satisfying local environmental constraints, but their complexity is normally justified only in large installations (700 or more metric tons per day). In the United States almost all modern plants are high pressure throughout to minimize capital investment, whereas in Europe they are mainly dual pressure designs designed to optimize ammonia conversion efficiency and catalyst use. This is because the emphasis in Europe has been on energy and ammonia efficiency. In the United States the lower energy costs, lower ammonia conversion, and higher nitrogen oxide losses have been more acceptable since they are offset by capital cost savings. The medium mono pressure, high mono pressure, and medium/high dual pressure processes have more recently dominated new orders for nitric acid plants.