Nitric Acid emissions

By analogy to the sulfur system, atmospheric nitrate sources can be distinguished into primary, gas phase, aqueous phase, and aerosol phase. Primary nitric acid emissions are considered to be small (U.S. EPA 1996) and can be neglected. 

Control of NO emissions from nitric acid and nitration operations is usually achieved by NO2 reduction to N2 and water using natural gas in a catalytic decomposer (123—126) (see Exhaust control, industrial). NO from nitric acid/nitration operations is also controlled by absorption in water to regenerate nitric acid. Modeling of such absorbers and the complexities of the NO —HNO —H2O system have been discussed (127). Other novel control methods have also been investigated (128—129). Vehicular emission control is treated elsewhere (see Exhaust control, automotive). 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

Highly sensitive iastmmental techniques, such as x-ray fluorescence, atomic absorption spectrometry, and iaductively coupled plasma optical emission spectrometry, have wide appHcation for the analysis of silver ia a multitude of materials. In order to minimize the effects of various matrices ia which silver may exist, samples are treated with perchloric or nitric acid. Direct-aspiration atomic absorption (25) and iaductively coupled plasma (26) have silver detection limits of 10 and 7 l-lg/L, respectively. The use of a graphic furnace ia an atomic absorption spectrograph lowers the silver detection limit to 0.2 l-ig/L. 

Flue gas treatment (FGT) is more effective in reducing NO, emissions than are combustion controls, although at higher cost. FGT is also useful where combustion controls are not applicable. Pollution prevention measures, such as using a high-pressure process in nitric acid plants, is more cost-effective in controlling NO, emissions. FGT technologies have been primarily developed and are most widely used in Japan. The techniques can be classified as selective catalytic reduction, selective noncatalytic reduction, and adsorption. 

Ammonium Nitrate Plants - In ammonium nitrate plants, wet scrubbers can be considered for prill towers and the granulation plant. Particulate emissions of 0.5 kg/t of product for the prill tower and 0.25 kg/t of product for granulation should be the target. Similar loads for ammonia are appropriate. Other effluents that originate in a nitrogenous fertilizer complex include boiler blowdown, water treatment plant backwash, and cooling tower blowdown from the ammonia and nitric acid plants. 

The plant disposes of two waste streams gaseous and aqueous. The gaseous emission results from the ammonia and the artunonium nitrate plants. It is fed to an incinerator prior to atmospheric disposal. In the incinerator, ammonia is converted into NOj,. Ehie to more stringent NO regulations, the conqmsition of ammonia in the feed to the incinerator has to be reduced from 0.57 wt% to 0.07 wt%. The lean streams presented in Table 9.5 may be employed to remove ammonia. The main aqueous waste of the process results from the nitric acid plant. Due to its acidic content of nitric acid, it is neutralized with an aqueous ammonia solution before biotreatment. 

The main use of rhodium is with platinum in catalysts for oxidation of automobile exhaust emissions. In the chemical industry, it is used in catalysts for the manufacture of ethanoic acid, in hydroformylation of alkenes and the synthesis of nitric acid from ammonia. Many applications of iridium rely on... 

The analysis of phosphates and phosphonates is a considerably complex task due to the great variety of possible molecular structures. Phosphorus-containing anionics are nearly always available as mixtures dependent on the kind of synthesis carried out. For analytical separation the total amount of phosphorus in the molecule has to be ascertained. Thus, the organic and inorganic phosphorus is transformed to orthophosphoric acid by oxidation. The fusion of the substance is performed by the addition of 2 ml of concentrated sulfuric acid to — 100 mg of the substance. The black residue is then oxidized by a mixture of nitric acid and perchloric acid. The resulting orthophosphate can be determined at 8000 K by atom emission spectroscopy. The thermally excited phosphorus atoms emit a characteristic line at a wavelength of 178.23 nm. The extensity of the radiation is used for quantitative determination of the phosphorus content. 

In addition to the gaseous emissions from the combustion of fuel, gaseous emissions are also produced by chemical production, for example, SO, from sulfuric acid production, NO from nitric acid production, HC1 from chlorination reactions, and so on. 

A wide range of catalytic materials have been investigated for the selective catalytic reduction of NOx. For stationary emissions, NH3-SCR using vanadium-tungsten oxides supported on titania is the most used method however, when there is a simultaneous emission of NO and NOz (in tail gas from nitric acid plants), copper-based zeolites or analogous systems have been proven to be preferable [31b], In fact, there are two main reactions for NH3-SCR ... 

We may thus conclude after this short overview on DeNO technologies that NH3-SCR using catalysts based on V-W-oxides supported on titania is a well-established technique for stationary sources of power plants and incinerators, while for other relevant sources of NO, such as nitric acid tail gases, where emissions are characterized from a lower temperature and the presence of large amounts of NOz, alternative catalysts based on transition metal containing microporous materials are possible. Also, for the combined DeNO -deSO, alternative catalysts would be necessary, because they should operate in the presence of large amounts of SO,.. Similarly, there is a need to develop new/improved catalysts for the elimination of NO in FCC emissions, again due to the different characteristics of the feed with respect to emissions from power plants. 

There are four main applications of the SCR-NH3 process for the reduction of NO in the emissions (1) power plants, (2) gas turbines, (3) waste incineration and (4) nitric acid plants. Although, often, specific distinction is not made between these cases and the same catalysts are assumed to be applicable in all cases, there are significant differences in terms of composition of the emissions and space velocities. A specific difference between the first three cases (combustion) and the latter (nitric acid plants) regards NO/N02 ratio which is typically close to 20 for combustion processes and close to 1 for the nitric acid plants. Furthermore, no S02 is present in the latter case. 

While vanadia- on titania-based catalysts can be used for both the classes of applications, there are other types of catalysts such as those based on copper [31b], which show good performances in case of mixtures of N0/N02 (nitric acid plants), while performances are worse when applied to emissions from catalytic processes. 

Although often it is considered that a single reaction mechanism occurs in the selective reduction of NO by ammonia, data show that instead different mechanisms are possible and that too depending on the type of catalyst and reaction conditions (feed composition, reaction temperature) - one mechanism may prevail over the others [31b], However, not considering this aspect and making extrapolation regarding the reaction mechanism from one catalyst to another or to different reaction conditions may lead to erroneous conclusions. In addition, it is important to consider all possible opportunities to develop new kinds of catalysts, for example, for the combined removal of NO and N20 from nitric acid plant emissions [25],... 

Other metal oxide catalysts studied for the SCR-NH3 reaction include iron, copper, chromium and manganese oxides supported on various oxides, introduced into zeolite cavities or added to pillared-type clays. Copper catalysts and copper-nickel catalysts, in particular, show some advantages when NO—N02 mixtures are present in the feed and S02 is absent [31b], such as in the case of nitric acid plant tail emissions. The mechanism of NO reduction over copper- and manganese-based catalysts is different from that over vanadia—titania based catalysts. Scheme 1.1 reports the proposed mechanism of SCR-NH3 over Cu-alumina catalysts [31b],... 

Low-temperature activity promotion is an issue in mobile (diesel) applications, but may not be a critical issue in several stationary applications, apart from those where the temperature of the emissions to be treated is below 200°C (for example, when a retrofitting SCR process must be located downstream from secondary exchangers, or in the tail gas of expanders in a nitric acid plant). In the latter cases, a plasmacatalytic process [91] could be interesting. In the other cases, the use of NTP together with the SCR catalyst is not economically viable. However, the synergetic combination of plasma and catalysts has been shown to significantly promote the conversion of hazardous chemicals such as dioxins [92], Although this field has not yet been explored, it may be considered as a new plasmacatalytic SCR process for the combined elimination of NO, CO and dioxins in the emissions from incinerators. 

Berndt et al. [740] have shown that traces of bismuth, cadmium, copper, cobalt, indium, nickel, lead, thallium, and zinc could be separated from samples of seawater, mineral water, and drinking water by complexation with the ammonium salt of pyrrolidine- 1-dithiocarboxylic acid, followed by filtration through a filter covered with a layer of active carbon. Sample volumes could range from 100 ml to 10 litres. The elements were dissolved in nitric acid and then determined by atomic absorption or inductively coupled plasma optical emission spectrometry. 

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