Design Problem This defines the problem i.e.

what the process facility is expected to do, the process to be used, chemistry involved etc. It also gives the properties and specifications of products and preferred conditions for production (in some cases). The design problem is given by the client, and it is of utmost importance that this document is very clear explicit (any ambiguity in the document results to designs that serve the wrong purpose). A sample design problem is given below. It is proposed to construct a plant that will deliver 280 tonnes per day of 60% (wt) nitric acid. This capacity is based on 8000 hours of operation per year, i.e. 330 days. It is envisaged that this nitric acid production facility will be accommodated within a larger chemical complex to be located in the Bolony region of Western Bolonia. Other plants on this site include an ammonia plant and an ammonium nitrate plant. Approximately 70% of the product acid will be consumed in situ for the production of crystalline ammonium nitrate. The remaining acid will be available to exploit the neighbouring South-East Gologong export market. 1.0 Background Information Nitric acid is a strong acid and a powerful oxidizing agent with enormous possibilities for applications in the chemical processing industry. It has commercial uses as a nitrating agent, oxidizing agent, solvent, activating agent, catalyst and hydrolyzing agent. In relation to world production, approximately 65% of all nitric acid produced is used for the production of ammonium nitrate (specifically for fertilizer manufacture). Nitric acid is now produced commercially using the stepwise, catalytic oxidation of ammonia with air, to obtain nitrogen monoxide and nitrogen dioxide. These nitrogen oxides are subsequently absorbed in water to yield between 50% and 68% strength nitric acid by weight. For applications requiring higher strengths, several methods of concentrating the acid are used. The traditional methods are by: (a) extractive distillation with dehydrating agents such as sulphuric acid or magnesium nitrate; (b) reaction with additional nitrogen oxides. The latter technique has the greatest application in industry. The chemistry of ammonia oxidation is remarkably simple with only six main reactions that need to be considered. There are also seven side reactions appropriate to this process, but for most design purposes they have little bearing on the results. 1.1 Properties and Uses Nitric acid is a colourless liquid at room temperature and atmospheric pressure. It is soluble in water in all proportions and there is a release of heat of solution upon dilution. This solubility has tended to shape the process methods for commercial nitric acid manufacture. It is a strong acid that almost completely ionizes when in dilute solution. It is also a powerful oxidizing agent with the ability to passivate some metals such as iron and aluminium. A compilation of many of the physical and chemical properties of nitric acid is presented in Table A.1 of Appendix A. Arguably the most important physical property of nitric acid is its azeotropic point, this influences the techniques associated with strong acid production. The constant-boiling mixture occurs at 121.9C, for a concentration of 68.4 % (wt) acid at atmospheric pressure. Nitric acid has enormously diverse applications in the chemical industry. It has commercial uses as a nitrating agent, oxidizing agent, solvent, activating agent, catalyst and hydrolyzing agent. The

most important use is undoubtedly in the production of ammonium nitrate for the fertilizer and explosives industries, which accounts for approximately 65% of the world production of nitric acid. Nitric acid has a number of other industrial applications. It is used for pickling stainless steels, steel refining, and in the manufacture of dyes, plastics and synthetic fibres. Most of the methods used for the recovery of uranium, such as ion exchange and solvent extraction, use nitric acid. An important point is that for most uses concerned with chemical production, the acid must be concentrated above its azeotropic point to greater than 95% (wt). Conversely, the commercial manufacture of ammonium nitrate uses nitric acid below its azeotropic point in the range 50-65% (wt). If the stronger chemical grade is to be produced, additional process equipment appropriate to super-azeotropic distillation is required. There is a potential health hazard when handling, and operating with, nitric acid. Nitric acid is a corrosive liquid that penetrates and destroys the skin and internal tissues. Contact can cause severe burns. The acid is a potential hazard, the various nitrogen oxides present as product intermediates in the process are also toxic. An assessment of the health risk must be fundamental to the design of any process. 1.2 Various processes for producing Nitric Acid Prior to the start of the 20 century, Nitric acid was prepared commercially by reacting sulphuric acid with either potassium nitrate (saltpetre) or with sodium nitrate (Chile saltpetre or nitre). Up to four tonnes of the two ingredients were placed into large retorts and heated over a furnace. The volatile product vaporised and was collected for distillation. An acid of between 93-95% (wt) was produced. In 1903 the electric-arc furnace superseded this primitive original technique. In the arc process, nitric acid was produced directly from nitrogen and oxygen by passing air through an electric-arc furnace. Although the process benefitted from an inexhaustible supply of free feed material (air), the power consumption for the arc furnace soon became cost prohibitive. Researchers returned to the oxidation of ammonia in air, (recorded as early as 1798) in an effort to improve production economics. In 1901 Wilhelm Ostwald had first achieved the catalytic oxidation of ammonia over a platinum catalyst. The gaseous nitrogen oxides produced could be easily cooled and dissolved in water to produce a solution of nitric acid. This achievement began the search for an economic process route. By 1908 the first commercial facility for production of nitric acid, using this new catalytic oxidation process, was commissioned near Bochum in Germany. The Haber-Bosch ammonia synthesis process came into operation in 1913, leading to the continued development and assured future of the ammonia oxidation process for the production of nitric acid. During World War 1, the intense demand for explosives and synthetic dyestuffs created an expansion of the nitric acid industry. Many new plants were constructed, all of which employed the ammonia oxidation process. This increased demand served as the impetus for several breakthroughs in process technology. These included: (a) The development of chrome-steel alloys for tower construction, replacing the heavy stoneware and acid-proof bricks. This enabled process pressures above atmospheric levels to be used. (b) The improved design of feed preheaters enabled higher process temperatures to be attained. Higher temperatures improved the yields and capacities, and also reduced equipment requirements. (c) Early developments in automatic process control improved process performance and reduced labour requirements. All of these factors helped to improve the process efficiency. The increasing availability of ammonia reduced processing costs still further. In the late 1920s the development of stainless steels enabled manufacturers to use
th

higher operating pressures. The increase in yield and lower capital requirements easily justified the use of high pressure operation despite increased ammonia consumption. The introduction of higher pressure processes resulted in a divergence of operating technique within the industry. The United States producers opted for a highpressure system, using a constant high pressure throughout the process. The European manufacturers opted for a split-pressure system. This latter system entails operating the ammonia oxidation section at atmospheric pressure, while the absorption unit is operated at higher pressures (capitalising on improved absorption rates). Recent developments in the ammonia oxidation process have included efforts to reduce catalyst losses in the process. Platinum recovery filters have been installed at various stages in the process. Gold/palladium gauze filter pads have been added on the exit side of the catalyst bed, inside the reactor/converter units. These filters have reportedly ensured a platinum recovery of 80% (Ref. PT4). Another trend has been for the use of additional filters in the downstream units. These filters are of alumino-silicate construction. Perhaps the greatest progress in nitric acid production technology has been in the manufacture of strong nitric acid ( >90% by weight). Advances in the areas of super-azeotropic distillation and in high pressure absorption are most significant. Research work is continually being performed in an effort to reduce nitrogen oxide emissions from nitric acid plants. The Humphreys and Glasgow/Bolme nitric acid process is just one example of a new philosophy being applied to the absorption systems of weak nitric acid plants (50-68% by weight). Nitrogen oxide emissions have been reduced from 2000-5000 ppm to less than 1000 ppm. For the production of stronger nitric acid, tail gases are now being treated by selective or non-selective catalytic combustion systems. These innovative units have reduced the nitrogen oxide emissions to below 400 ppm. Notably, all commercial nitric acid production methods used today focus on the oxidation of ammonia. It is therefore appropriate to investigate the chemistry of this process, in the knowledge that it is directly applicable to any of the production processes available. The chemistry of the oxidation of ammonia is surprisingly simple. It begins with a single pure compound, plus air and water, and ends with another pure compound in aqueous solution, with essentially no by-products. The process may be described by just six major reactions as shown in Table 1. With reference to Table 1, Reaction 1 is the overall reaction for the process. This net result is achieved from three separate, and distinct, chemical steps. The first is the oxidation of ammonia to nitrogen monoxide (Reaction 2). The second is the further oxidation of nitrogen monoxide to nitrogen dioxide (Reaction 3), then nitrogen dioxide to nitrogen tetroxide (Reaction 4). The third and final stage involves the absorption of these nitrogen-based oxides into water to form the nitric acid product (Reactions 5 and 6). In most commercial processes, each of these three stages are conducted in separate process units. The first step in the process is the heterogeneous, highly exothermic, gas-phase catalytic reaction of ammonia with oxygen (Reaction 2). The primary oxidation of ammonia to nitric acid (over a catalyst gauze of 9:l platinum/rhodium alloy) proceeds rapidly at process temperatures between 900-970C. The second step in the process involves two reactions (Reactions 3 and 4). These are the oxidations of nitrogen monoxide to the dioxide and tetroxide forms. The equilibrium mixture is loosely referred to as nitrogen peroxide. Both reactions are homogenous, moderately exothermic, gas-phase catalytic reactions.

TABLE 1. Chemical reactions for the oxidation of ammonia Main reactions 1. NH3(g) + 2O2(g) = HNO3(aq) + H2O(l) 2. 4NH3(g) + 5O2 (g) = 4NO(g) + 6H2O(l) 3. 2NO(g) + O2(g) = 2NO2 (g) 4. 2NO2(g) = N2O(g) 5. 3N2O(g) + 2H2O(l) = 4HNO3(aq) + 2NO(g) 6. 3NO2(g) + H2O(I) = 2HNO3(aq) + NO(g) Heat of reaction H (kJ/mole) - 436.918 - 226.523 - 57.108 -28.617 - 15.747 - 58.672

All reactions shown are highly exothermic. The known side reactions and their heats of reaction are presented The third step in the process involves cooling the reaction gases below their dew point, so that a liquid phase of weak nitric acid is formed. This step effectively promotes the state of oxidation and dimerization (Reactions 3 and 4), and removes water from the gas phase. This in turn increases the partial pressure of the nitrogen peroxide component. Finally, nitric acid is formed by the reaction of dissolved nitrogen peroxide with water (Reactions 5 and 6). The formation of two moles of acid is accompanied by the formation of one mole of nitrogen monoxide gas. This nitrogen monoxide must be recycled within the process.