Catalyst nitric acid manufacture

Nitric acid, manufacture, 45, 232 Nitric oxide as catalyst, 227 reaction with oxygen, 26 solubility, 20 Nitrobenzene, 344 Nitrogen... 

EnviNOx Two related processes for removing N20 and NOx from the tailgases from nitric acid manufacture by the Ostwald process. Both variants use two beds of two zeolite catalysts modified with iron. The first variant is for gases hotter than 425°C and involves injecting ammonia between the beds. The second variant, for gases cooler than 425°C, injects ammonia before the first bed and a volatile hydrocarbon between the beds. Developed by Uhde in association with Agrolinz Melamine International. The first variant was installed in Linz, Austria, in 2003. The second variant was installed in Egypt in 2007. The catalysts are supplied by Sud-Chemie. 

Not all catalysts need the extended smface provided by a porous structure, however. Some are sufficiently active so that the effort required to create a porous catalyst would be wasted. For such situations one type of catalyst is the monolithic catalyst. Monolithic catalysts are normally encountered in processes where pressure drop and heat removal are major considerations. Typical examples include the platinum gauze reactor used in the ammonia oxidation portion of nitric acid manufacture and catalytic converters used to oxidize pollutants in automobile exhaust. They can be porous (honeycomb) or non-porous (wire gauze). A photograph of a automotive catalytic converter is shown in Figure CD 11-2. Platinum is a primary catalytic material in the monolith. 

A platinum/rhodium alloy is employed as catalyst for the reaction at a ratio of 9 1 as in nitric acid manufacture. Platinum alone is not stable at reaction conditions. When it is alloyed with rhodium, the catalyst life can range from 4000 to as much as 10,000 hours. The catalyst bed usually is made of layers of 40 mesh gauze made of alloy wire 0.003 inch in diameter. The spent catalyst is mostly recoverable. 

The anunoxidation process operates at a higher temperature than that required for the production of acrolein. This is probably a consequence of the different reactivity of ammonia towards the catalyst, and the difference in reactivities between oxide and imido groups. A similar range of operating temperatures was used during early experiments on the catalytic oxidation of ammonia to produce nitric oxide for nitric acid manufacture. In this work, however, nitrous oxide was the initial product. ... 

Although many variations of the cyclohexane oxidation step have been developed or evaluated, technology for conversion of the intermediate ketone—alcohol mixture to adipic acid is fundamentally the same as originally developed by Du Pont in the early 1940s (98,99). This step is accomplished by oxidation with 40—60% nitric acid in the presence of copper and vanadium catalysts. The reaction proceeds at high rate, and is quite exothermic. Yield of adipic acid is 92—96%, the major by-products being the shorter chain dicarboxytic acids, glutaric and succinic acids,and CO2. Nitric acid is reduced to a combination of NO2, NO, N2O, and N2. Since essentially all commercial adipic acid production arises from nitric acid oxidation, the trace impurities patterns ate similar in the products of most manufacturers. 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Feedstocks. A separate breakdown between fuels and feedstocks (qv) for the chemical industry (2) shows that the quantity of hydrocarbons (qv) used direcdy for feedstock is about as great as that used for fuel (see Fuels, synthetic Gasoline and other motor fuels). Much of this feedstock is oxidized accompanied by the release of heat, and in many processes, by-product energy from feedstock oxidation dominates purchased fuel and electricity. A classic example is the manufacture of nitric acid (qv) [7697-37-2] HNO. Ammonia (qv) [7664-41-7] burned in air on a catalyst at a pressure... 

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... 

Manufacture Ammonia is burned over a catalyst to a mixture of nitrogen oxides which when reacted with water produces nitric acid. NH3 -b O2 NO2 -b H2O ammonia air nitrogen dioxide NO2 -b H2O HNO3... 

Bakke et al. (1982) have shown how montmorillonite catalyses chlorination and nitration of toluene nitration leads to 56 % para and 41 % ortho derivative compared to approximately 40 % para and 60 % ortho derivatives in the absence of the catalyst. Montmorillonite clays have an acidity comparable to nitric acid / sulphuric acid mixtures and the use of iron-exchanged material (Clayfen) gives a remarkable improvement in the para, ortho ratio in the nitration of phenols. The nitration of estrones, which is relevant in making various estrogenic drugs, can be improved in a remarkable way by using molecular engineered layer structures (MELS), while a reduction in the cost by a factor of six has been indicated. With a Clayfen type catalyst, it seems possible to manipulate the para, ortho ratio drastically for a variety of substrates and this should be useful in the manufacture of fine chemicals. In principle, such catalysts may approach biomimetic chemistry our ability to predict selectivity is very limited. 

At least rune manufacturing technologies are available for the production of caprolactam and, in most, hydroxylamine (hyam) is one of the important raw materials. In particular, in the HPO process the hydroxylamine is made by using a precious metal powdered catalyst to selectively hydrogenate nitric acid. Evonik... 

Ammonia is one of the world s most important chemicals, in terms of the quantity manufactured. Some ammonia is processed into nitric acid and various polymers. Roughly 80% of ammonia is used to make fertilizers, such as ammonium nitrate. In the Haher process for manufacturing ammonia, nitrogen and hydrogen combine in the presence of a catalyst. 

Uses Manufacture of acrylonitrile, hydrazine hydrate, hydrogen cyanide, nitric acid, sodium carbonate, urethane, explosives, synthetic fibers, fertilizers refrigerant condensation catalyst dyeing neutralizing agent synthetic fibers latex preservative fuel cells, rocket fuel nitrocellulose nitroparaffins ethylenediamine, melamine sulfite cooking liquors developing diazo films yeast nutrient. 

Nitric acid (HNO ) is an important commercial chemical and was manufactured commercially to produce fertilizers and explosives as well as plastics and many other products. In 1902 a German chemist, WiUrehn Ostwald (1853—1932), developed a process wherein at high temperatures he used platinum catalysts to convert ammonia into nitric acid. When nitric acid is reacted with glycerol, the result is nitroglycerine—an unstable explosive unless dissolved in inert material, such as clay. It can then be stabihzed as dynamite. 

A small amount of adipic acid, 2%, is made by hydrogenation of phenol with a palladium or nickel catalyst (150°C, 50 psi) to the mixed oil, then nitric acid oxidation to adipic acid. If palladium is used, more cyclohexanone is formed. Although the phenol route for making adipic acid is not economically advantageous because phenol is more expensive than benzene, the phenol conversion to greater cyclohexanone percentages can be used successfully for caprolactam manufacture (see next section), where cyclohexanone is necessary. 

Currently, nitric acid is manufactured exclusively by catalytic oxidation of ammonia. Platinum or platinum-rhodium is an effective catalyst of this oxidation (Ostwald process). Three basic steps in such ammonia oxidation process are (1) oxidation of ammonia to form nitric oxide ... 

Platinum also is used extensively as a catalyst in hydrogenation, dehydrogenation, oxidation, isomerization, carbonylation, and hydrocracking. Also, it is used in organic synthesis and petroleum refining. Like palladium, platinum also exhibits remarkable abdity to absorb hydrogen. An important application of platinum is in the catalytic oxidation of ammonia in Ostwald s process in the manufacture of nitric acid. Platinum is installed in the catalytic converters in automobile engines for pollution control. 

Nitric acid is now manufactured by combusting ammonia in air in the presence of a (platinum or other noble metal) catalyst, and the nitrogen oxides thus formed are oxidized further and absorbed in water to form nitric acid. 

The first reaction is run over platinum-rhodium catalysts at around 900°C (1,652°F). In the second and third stages, a mixture of nitric oxide and air circulates through condensers, where it is partially oxidized. The nitrogen dioxide is absorbed in a tower, and nitric acid sinks to the bottom. Nitric acid is mainly used to make ammonium nitrate, most of it for fertilizer although it also goes into the production of explosives. Nitration is used to manufacture explosives such as nitroglycerine and trinitrotoluene (TNT) as well as many important chemical intermediates used in the pharmaceutical and dyestuff industries. 

This reaction is very rapid and has been difficult to study mechanistically. The direct oxidation of ammonia, NH3, to nitric oxide, NO, over platinum catalyst is one of the major steps in the manufacture of nitric acid, HN03. 

Normally, nitration of deactivated compounds (and therefore polynitration of toluene) is carried out using aggressive nitric acid - oleum mixtures. Dinitration of toluene with mixed acids produces a 4 1 ratio of 2,4- and 2,6-dinitrotoluenes, from which the former is isolated for manufacture of toluenediisocyanate (TDI) and toluenediamine, both of which are used in the manufacture of polyurethanes. Zirconium and hafnium derivatives catalyse nitration of o-nitrotoluene, but ratios of 2,4- 2,6-dinitrotoluene are modest (66 34).12 Dinitration of toluene using Claycop (copper nitrate on K10 clay), acetic anhydride and nitric acid in the presence of carbon tetrachloride produced dinitrotoluenes in a yield of 85% with a ratio of 2,4- 2,6-dinitrotoluene of 9 1.13 This method, however, requires a large excess of nitric acid, the use of an unacceptable solvent and long reaction times. The direct nitration of toluene to 2,4-dinitrotoluene using nitric acid over a zeolite P catalyst, with azeotropic removal of water, is reported to give a 2,4 2,6 ratio of 14, but full results are yet to be published.14... 

Escherichia coli (see Draths and Frost, 1994). Hydroquinone is a very practical intermediate in the manufacture of polymeric materials—almost 2 billion kg of adipic acid are produced from it and used annually in the manufacture of nylon 66. Most commercial syntheses of adipic acid utilize benzene as the starting material, derived from the benzene/toluene/xylene (BTX) fraction of petroleum refining. Benzene is hydrogenated over a metal catalyst to form cyclohexane, which is then oxidized over another catalyst that produces both cyclohexanone and cyclohexanol. See Figure 12.6. These molecules are catalytically oxidized in the presence of nitric acid to form adipic acid. 

The Manufacture of Nitric Acid from Ammonia. Much nitric acid is made by the oxidation of ammonia. This oxidation occurs in several steps. Ammonia mixed with air burns on the surface of a platinum catalyst to form nitric oxide ... 

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