Nitric acid reactor

The key to safety in explosives manufacturing is to use isolated high-velocity nitric acid reactors that have only a veiy small hold up at any one time (that is, only a small amount of dangerous material is held up inside the reactor at any time). Units are widely spaced, so any accident involves only small amounts of explosive and does not propagate through the plant. Fire and electrical spark hazards are rigorously controlled, and manpower reduced to the absolute minimum through automation. 

Naphthali-Sandholm method, 404 dgorithm flowsketch, 411 Nitric acid reactor, 576 Nitrogen fixation, 574,578,588 Nitrotoluene isomers separation, 544 Noncatalytic reactions with solids, 595 Non-Newtonian liquids, 100, 103-109 Bineham. 104.105.107-109 dilatant, 103, 104 laminar flow, 108,109 pressure drop in lines, 106, 109 pseudoplaslic, 103, 104 rheopectic, 104,105 slurries, 71 thixotropic, 104-106 viscoelastic, 105, 106 Notation, 672 NPSH, pumps, 133,146 centrifugal pumps, 146 positive displacement pumps, 134, 135 various pumps, 144 NRTL equation, 475... 

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. 

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. 

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,...

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

Whereas addition of hydrogen to feedwater helps solve the O2 or ECP problem, other complications develop. An increase in shutdown radiation levels and up to a fivefold increase in operating steam plant radiation levels result from the increased volatiUty of the short-Hved radioactive product nitrogen-16, N, (7.1 s half-life) formed from the coolant passing through the core. Without H2 addition, the in the fluid leaving the reactor core is in the form of nitric acid, HNO with H2 addition, the forms ammonia, NH, which is more volatile than HNO, and thus is carried over with the steam going to the turbine. 

An improved solvent extraction process, PUREX, utilizes an organic mixture of tributyl phosphate solvent dissolved in a hydrocarbon diluent, typically dodecane. This was used at Savannah River, Georgia, ca 1955 and Hanford, Washington, ca 1956. Waste volumes were reduced by using recoverable nitric acid as the salting agent. A hybrid REDOX/PUREX process was developed in Idaho Falls, Idaho, ca 1956 to reprocess high bum-up, fuUy enriched (97% u) uranium fuel from naval reactors. Other separations processes have been developed. The desirable features are compared in Table 1. 

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Qua.driva.Ient, Zirconium tetrafluoride is prepared by fluorination of zirconium metal, but this is hampered by the low volatility of the tetrafluoride which coats the surface of the metal. An effective method is the halogen exchange between flowing hydrogen fluoride gas and zirconium tetrachloride at 300°C. Large volumes are produced by the addition of concentrated hydrofluoric acid to a concentrated nitric acid solution of zirconium zirconium tetrafluoride monohydrate [14956-11-3] precipitates (69). The recovered crystals ate dried and treated with hydrogen fluoride gas at 450°C in a fluid-bed reactor. The thermal dissociation of fluorozirconates also yields zirconium tetrafluoride. 

In some processes the reactant bases are too weak to be protonated significantly except in the presence of very strong acids such as fuming sulfuric acid or a mixture of concentrated sulfuric and nitric acids, ie, mixed acid. Nitration of toluene, for example, requires such solutions two Hquid phases are present in the reactor. 

Fig. 1. Schematic of nitric acid from ammonia showing integration of reactor heat recovery, power recovery from tailgas, and air compression (3).

Nitric acid is one of the three major acids of the modem chemical industiy and has been known as a corrosive solvent for metals since alchemical times in the thirteenth centuiy. " " It is now invariably made by the catalytic oxidation of ammonia under conditions which promote the formation of NO rather than the thermodynamically more favoured products N2 or N2O (p. 423). The NO is then further oxidized to NO2 and the gases absorbed in water to yield a concentrated aqueous solution of the acid. The vast scale of production requires the optimization of all the reaction conditions and present-day operations are based on the intricate interaction of fundamental thermodynamics, modem catalyst technology, advanced reactor design, and chemical engineering aspects of process control (see Panel). Production in the USA alone now exceeds 7 million tonnes annually, of which the greater part is used to produce nitrates for fertilizers, explosives and other purposes (see Panel). 

For this reason, operation around atmospheric pressures is typical. Space velocity should he high to avoid the reaction of ammonia with oxygen on the reactor walls, which produces nitrogen and water, and results in lower conversions. The concentration of ammonia must he kept helow the inflammahility limit of the feed gas mixture to avoid explosion. Optimum nitric acid production was found to he obtained at approximately 900°C and atmospheric pressure. 

The resistance of titanium in nitric acid is good at most concentrations and at temperatures up to boiling . Thus tubular heat exchangers are used in ammonium nitrate production for preheating the acid prior to its introduction into the reactor via titanium sparge pipes. In explosives manufacture, concentrated nitric acid is cooled in titanium coils and titanium tanks are... 

Other preparations and isolations. If damp methylenedi(nitroformamide) is allowed to stand for several days, the odor of formic acid is noticed, and MEDINA can be isolated from the residue (Ref 11, p 14). The details of scale-up to 150 lb batches, including exp details and flow sheets, and further scale-up with the aim of prodn of 1000 lbs are given. The report describes a fume-off and fire which occurred during the S3rd run. The cause was attributed to a stuck valve which allowed nitric acid to build up in the reactor (Ref 13, p 57). In Ref 16, p 73 there are cost analysis data for pilot plant and large scale prodn, flow sheet for a proposed coml plant, and material balances. The action of acet anhydr on N,Nf-bis(hydroxy-methyl)MEDlNA regenerates MEDINA (Ref 6) the diNa salt of N. N trinitrotrimethylene-diamine, on warming with me ale, ppts the Na salt of MEDINA... 

Influence of the mode of operation on process performance. The mode of operation of stirred-tank reactors can also significantly affect reactor performance. The history of concentrations will be changed by the time policy of reactant(s) addition to the reaction mixture. In view of our very limited possibility of controlling of temperature in stirred-tank reactors, the temperature-time dependencies for different policies of dosing will also be different. For example, the result of nitration depends upon the method of addition of nitric acid to aromatics, and the choice which phase is dispersed and which is continuous. Consequently, if the reaction is concentration- or temperature-sensitive the result will be dependent on the mode of operation (see Example 5.3.1.5). 

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