Safety nitration

The conversion of a diazo ketone to an acid amide may be accomplished by treating a warm solution in dioxan with 10-28 per cent, aqueous ammonia solution containing a small amount of silver nitrate solution, after which the mixture is heated at 60°-70° for some time. Precautions should be taken (by use of a. safety glass shield) when heating mixtures containing ammoniacal silver nitrate. 

Safety has been greatly increased by use of the continuous nitration processes. The quantity of nitroglycerin in process at any one time is greatly reduced, and emulsification of nitroglycerin with water decreases the likelihood of detonation. Process sensors (qv) and automatic controls minimize the likelihood of mnaway reactions. Detonation traps may be used to decrease the likelihood of propagation of an accidental initiation eg, a tank of water into which the nitrated product flows and settles on the bottom. 

The two procedures primarily used for continuous nitration are the semicontinuous method developed by Bofors-Nobel Chematur of Sweden and the continuous method of Hercules Powder Co. in the United States. The latter process, which uses a multiple cascade system for nitration and a continuous wringing operation, increases safety, reduces the personnel involved, provides a substantial reduction in pollutants, and increases the uniformity of the product. The cellulose is automatically and continuously fed into the first of a series of pots at a controlled rate. It falls into the slurry of acid and nitrocellulose and is submerged immediately by a turbine-type agitator. The acid is deflvered to the pots from tanks at a rate controlled by appropriate instmmentation based on the desired acid to cellulose ratio. The slurry flows successively by gravity from the first to the last of the nitration vessels through under- and overflow weirs to ensure adequate retention time during nitration. The overflow from the last pot is fully nitrated cellulose. 

Black Powder. Black powder is mainly used as an igniter for nitrocellulose gun propellant, and to some extent in safety blasting fuse, delay fuses, and in firecrackers. Potassium nitrate black powder (74 wt %, 15.6 wt % carbon, 10.4 wt % sulfur) is used for military appHcations. The slower-burning, less cosdy, and more hygroscopic sodium nitrate black powder (71.0 wt %, 16.5 wt % carbon, 12.5 wt % sulfur) is used industrially. The reaction products of black powder are complex (Table 12) and change with the conditions of initia tion, confinement, and density. The reported thermochemical and performance characteristics vary greatly and depend on the source of material, its physical form, and the method of determination. Typical values are Hsted in Table 13. 

Typically, dry potassium nitrate is pulverized in a ball mill. Sulfur is milled into cellular charcoal to form a uniform mix in a separate ball mill. The nitrate and the sulfur—charcoal mix are screened and then loosely mixed by hand or in a tumbling machine. Magnetic separators may be used to ensure the absence of ferrous metals. The preliminary mix is transferred to an edge-mimer wheel mill with large, heavy cast iron wheels. A clearance between the pan and the wheels is required for safety purposes. The size of this gap also contributes to the density of the black powder granules obtained. Water is added to minimize dusting and improve incorporation of the nitrate into the charcoal. The milling operation requires ca 3 to 6 h. 

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

Sodium Nitrate and Sodium Nitrite. Nitrates and nitrites ate used in meat-curing processes to prevent the growth of bacteria that cause botulism. Nitrates have been shown to form low, but possibly toxic, levels of nitrosamines in certain cured meats. For this reason, the safety of these products has been questioned, and use is limited (80). 

The carcinogenicity of nitrosamines has created widespread concern over the safety of food products that are significant sources of nitrates and nitrites. Nitrosamines are readily formed by reaction of secondary amines with nitrites at acid pH, conditions which may occur in the gastrointestinal tract. 

The precipitated acetyHde must be decomposed with hydrochloric acid after the titration as a safety measure. Concentrated solutions of silver nitrate or silver perchlorate form soluble complexes of silver acetyHde (89). Ammonia and hydrogen sulfide interfere with the silver nitrate method which is less... 

Many redundant safety features were provided at the SRP. These included a moderator dump tank, gadolinium nitrate solution as emergency absorber, continuously mnning diesel generators, and a 95 x 10 -L (25 x 10 -gal) elevated water tank for each reactor, for assurance of cooling. 

The plutonium extracted by the Purex process usually has been in the form of a concentrated nitrate solution or symp, which must be converted to anhydrous PuF [13842-83-6] or PuF, which are charge materials for metal production. The nitrate solution is sufficientiy pure for the processing to be conducted in gloveboxes without P- or y-shielding (130). The Pu is first precipitated as plutonium(IV) peroxide [12412-68-9], plutonium(Ill) oxalate [56609-10-0], plutonium(IV) oxalate [13278-81-4], or plutonium(Ill) fluoride. These precipitates are converted to anhydrous PuF or PuF. The precipitation process used depends on numerous factors, eg, derived purity of product, safety considerations, ease of recovering wastes, and required process equipment. The peroxide precipitation yields the purest product and generally is the preferred route (131). The peroxide precipitate is converted to PuF by HF—O2 gas or to PuF by HF—H2 gas (31,132). 

Safety Considerations. Ammonium nitrate can be considered a safe material if treated and handled properly. Potential hazards include those associated with fire, decomposition accompanied by generation of toxic fumes, and explosion. 

Health and Safety Factors. The strontium ion has a low order of toxicity, and strontium compounds are remarkably free of toxic hazards. Chemically, strontium is similar to calcium, and strontium salts, like calcium salts, are not easily absorbed by the intestinal tract. Strontium carbonate has no commonly recognized hazardous properties. Strontium nitrate is regulated as an oxidizer that promotes rapid burning of combustible materials, and it should not be stored in areas of potential fire hazards. 

Dioitroanthraquiaoae and 1,8-dinitroanthraquinone can also be prepared by nitration of anthraquiaone ia coaceatrated nitric acid (70). The 1,5-isomer can then be easily separated from the reaction mixture by filtration, since 1,8- or other isomers than 1,5-dinitroanthraquinone are completely dissolved in concentrated nitric acid. However, this process is unsuitable for industrial production for safety reasons the mixture of dinitroanthraquiaone and concentrated nitric acid forms a detonation mixture (71). Addition of sulfuric acid makes it possible to work outside the detonation area. 

Nitrous gases originating from the combustion units in nitric acid plants carry small amounts of unreacted ammonia, NH3. The ammonia may react with the nitrous gas to form microscopic particles of ammonium nitrate that adhere to solid surfaces. Within a short time, there is a growing layer of ammonium nitrate salt covering the internal surface of the nitrous gas compressor (Figure 4-27). This layer can obstruct the flow passages because it tends to increase the power consumption, provoke excessive vibrations, and even present a safety hazard since ammonium nitrate explosions can occur. 

MC No 3 Powder. Austrian safety expl (1898) contg Amm nitrate 91.6 and collodion cotton 8.4%... 

L.F. Albright C. Hansen, Eds, Industrial and Laboratory Nitrations , ACS Symposium Series 22, ACS, Washington, DC (1976). Excellent modern review. Ten chapters emphasize various aspects of the chemistry and mechanism of nitrations, including oxidation and ipso-nitration side reactions. Six chapters discuss the chemistry and physical transfer steps between phases. Eight chapters discuss plant operation-improvements, safety features, and new operations. The final chapter is devoted to vapor phase nitrations... 

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