Nitric processes

Simplified Grassmann diagram of the nitric process shown in Figure 14.2. 

The DSN (Direct Strong Nitric) process is a general name for processes that concentrate nitric acid from the 50% to 70% range up to the 98% range by adding dinitrogen tetroxide. 

Catalytic gas-phase reactions play an important role in many bulk chemical processes, such as in the production of methanol, ammonia, sulfuric acid, and nitric acid. In most processes, the effective area of the catalyst is critically important. Since these reactions take place at surfaces through processes of adsorption and desorption, any alteration of surface area naturally causes a change in the rate of reaction. Industrial catalysts are usually supported on porous materials, since this results in a much larger active area per unit of reactor volume. 

Nitrations are usually carried out at comparatively low temperatures at higher temperatures there may be loss of material because of the oxidising action of the nitric acid. For substances which do not nitrate readily with a mixture of concentrated nitric and sulphuric acids ( mixed acid ), the intensity of the reaction may be increased inler alia by the use of fuming sulphuric acid (containing up to 60 per cent, of sulphur trioxide) or by fuming nitric acid. Thus nitrobenzene is converted by a mixture of fuming nitric acid and concentrated sulphuric acid into about 90 per cent, of wi-dinitrobenzene and small amounts of the o- and p-isomers the latter are eliminated in the process of recrystallisation ... 

A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

The zeroth-order rates of nitration depend on a process, the heterolysis of nitric acid, which, whatever its details, must generate ions from neutral molecules. Such a process will be accelerated by an increase in the polarity of the medium such as would be produced by an increase in the concentration of nitric acid. In the case of nitration in carbon tetrachloride, where the concentration of nitric acid used was very much smaller than in the other solvents (table 3.1), the zeroth-order rate of nitration depended on the concentrationof nitric acid approximately to the fifth power. It is argued therefore that five molecules of nitric acid are associated with a pre-equilibrium step or are present in the transition state. Since nitric acid is evidently not much associated in carbon tetrachloride a scheme for nitronium ion formation might be as follows ... 

The evidence outlined strongly suggests that nitration via nitrosation accompanies the general mechanism of nitration in these media in the reactions of very reactive compounds.i Proof that phenol, even in solutions prepared from pure nitric acid, underwent nitration by a special mechanism came from examining rates of reaction of phenol and mesi-tylene under zeroth-order conditions. The variation in the initial rates with the concentration of aromatic (fig. 5.2) shows that mesitylene (o-2-0 4 mol 1 ) reacts at the zeroth-order rate, whereas phenol is nitrated considerably faster by a process which is first order in the concentration of aromatic. It is noteworthy that in these solutions the concentration of nitrous acid was below the level of detection (< c. 5 X mol... 

The argument for the S 2 process, when the transition from acetic acid as solvent to nitric acid as solvent is considered, is less direct, for because of the experimental need to use less reactive compounds, zeroth-order nitration has not been observed in nitric acid. It can be estimated, however, that a substance such as nitrobenzene would react about 10 faster in first-order nitration in nitric acid than in a solution of nitric acid (7 mol 1 ) in acetic acid. Such a large increase is understandable in terms of the S z mechanism, but not otherwise. 

Although the term ester used without a modifier is normally taken to mean an ester of a carboxylic acid alcohols can react with inorganic acids m a process similar to the Fis cher esterification The products are esters of inorganic acids For example alkyl nitrates are esters formed by the reaction of alcohols with nitric acid... 

The carboxylic acid produced m the greatest amounts is 1 4 benzenedicarboxylic acid (terephthahc acid) About 5 X 10 Ib/year is produced m the United States as a starting material for the preparation of polyester fibers One important process converts p xylene to terephthahc acid by oxidation with nitric acid... 

A more constrained opportunity for nitrate bioremediation arose at the US-DoE Weldon Spring Site near St. Louis, Missouri. This site had been a uranium and thorium processing faciUty, and treatment of the metal had involved nitric acid. The wastestream, known as raffinate, was discharged to surface inpoundments and neutralized with lime to precipitate the metals. Two pits had nitrate levels that requited treatment before discharge, but heavy rains in 1993 threatened to cause the pits to overflow. Bioremediation by the addition of calcium acetate as a carbon source successfully treated more than 19 million liters of water at a reasonable cost (75). 

The urea produced is normally either prilled or granulated. In some countries there is a market for Hquid urea—ammonium nitrate solutions (32% N). In this case, a partial-recycle stripping process is the best and cheapest system. The unconverted NH coming from the stripped urea solution and the reactor off-gas is neutralized with nitric acid. The ammonium nitrate solution formed and the urea solution from the stripper bottom are mixed, resulting in a 32—35 wt % solution. This system drastically reduces investment costs as evaporation, finishing (priQ or granulation), and wastewater treatment are not required. 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

Fig. 3. Typical nitric acid oxidation process. A, reactor B, optional cleanup reactor C, bleacher D, NO absorber E, concentrating stUl F, crude crystallizer G, centrifuge or filter H, refined crystallizer I, centrifuge or filter , dryer K, purge evaporator L, purge crystallizer M, centrifuge or filter N,...

In order to control the concentration of lower dibasic acid by-products in the system, a portion of the mother liquor stream is diverted to a purge treatment process. Following removal of nitric acid by distillation (Fig. 3, K), copper and vanadium catalyst are recovered by ion-exchange treatment (Fig. 

N). This area of the process has received considerable attention in recent years as companies strive to improve efficiency and reduce waste. Patents have appeared describing addition of SO2 to improve ion-exchange recovery of vanadium (111), improved separation of glutaric and succinic acids by dehydration and distillation of anhydrides (112), formation of imides (113), improved nitric acid removal prior to dibasic acid recovery (114), and other claims (115). 

Other processes explored, but not commercialized, include the direct nitric acid oxidation of cyclohexane to adipic acid (140—143), carbonylation of 1,4-butanediol [110-63-4] (144), and oxidation of cyclohexane with ozone [10028-15-5] (145—148) or hydrogen peroxide [7722-84-1] (149—150). Production of adipic acid as a by-product of biological reactions has been explored in recent years (151—156). 

Sulfur Dioxide Processing, Repriuts of 1972—1974 Chem. Eng. Prog, articles, AIChE, New York (1975). Contaius thirteen papers on flue gas desulfurization, two on SO2 control iu pulp and paper, one on sulfuric acid tail gas, one on SO2 from ore roasting, and two on NO from nitric acid. 

Dry nitrocellulose, which bums rapidly and furiously, may detonate if present in large quantities or if confined. Nitrocellulose is a dangerous material to handle in the dry state because of sensitivity to friction, static electricity, impact, and heat. Nitrocellulose is always shipped wet with water or alcohol. The higher the nitrogen content the more sensitive it tends to be. Even nitrocellulose having 40% water detonates if confined and sufftcientiy activated. AH large-scale processes use nitric—sulfuric acid mixtures for nitration (127—132). 

Pentaerythritol may be nitrated by a batch process at 15.25°C using concentrated nitric acid in a stainless steel vessel equipped with an agitator and cooling coils to keep the reaction temperature at 15—25°C. The PETN is precipitated in a jacketed diluter by adding sufficient water to the solution to reduce the acid concentration to about 30%. The crystals are vacuum filtered and washed with water followed by washes with water containing a small amount of sodium carbonate and then cold water. The water-wet PETN is dissolved in acetone containing a small amount of sodium carbonate at 50°C and reprecipitated with water the yield is about 95%. Impurities include pentaerythritol trinitrate, dipentaerythritol hexanitrate, and tripentaerythritol acetonitrate. Pentaerythritol tetranitrate is shipped wet in water—alcohol in packing similar to that used for primary explosives. 

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