Sulfur safety

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. 

Health and Safety Factors. Sulfur hexafluoride is a nonflammable, relatively unreactive gas that has been described as physiologically inert (54). The current OSHA standard maximum allowable concentration for human exposure in air is 6000 mg/m (1000 ppm) TWA (55). The Underwriters Laboratories classification is Toxicity Group VI. It should be noted, however, that breakdown products of SF, produced by electrical decomposition of the gas, are toxic. If SF is exposed to electrical arcing, provision should be made to absorb the toxic components by passing the gas over activated alumina, soda-lime, or molecular sieves (qv) (56). 

The physical properties of the principal constituents of natural gas are Hsted in Table 5. These gases are odorless, but for safety reasons, natural gas is odorized before distribution to provide a distinct odor to warn users of possible gas leaks in equipment. Sulfur-containing compounds such as organic mercaptans, aUphatic sulfides, and cycHc sulfur compounds are effective odorants at low concentrations and are added to natural gas at levels ranging from 4 to 24mg/m. ... 

Copper and Copper-Containing Alloys. Either sulfuric or hydrochloric acid may be used effectively to remove the oxide film on copper (qv) or copper-containing alloys. Mixtures of chromic and sulfuric acids not only remove oxides, but also brighten the metal surface. However, health and safety issues related to chromium(VT) make chromic acid less than desirable. 

Safety provisions have proven highly effective. The nuclear power industry in the Western world, ie, outside of the former Soviet Union, has made a significant contribution of electricity generation, while surpassing the safety record of any other principal industry. In addition, the environmental record has been outstanding. Nuclear power plants produce no combustion products such as sulfuric and nitrous oxides or carbon dioxide (qv), which are... 

The National Safety Council, National Fire Protection Association, and other similar organizations pubHsh technical information that describes general safety practices for use during the testing, handling, storage, and transport of sulfur (21,36—40). Each of these pubHcations include a Hst of references for additional health and safety information. 

Handling and Storage of Solid Sulfur, Data Sheet 612, National Safety Council, 1991. 

Properties and Essential Information for Safe Handling and Use of Sulfur, Chemical Safety Data Sheet SD-74, Manufacturing Chemists Association (CMA), 1959. 

Health and Safety Factors. Sulfur monochloride is highly toxic and irritating by inhalation, and is corrosive to skin and eyes (156). The OSHA permissible exposure limit is 1 ppm (6 mg/m ). Pulmonary edema may result from inhalation. Because its vapor cannot be tolerated even at low concentrations, its presence serves as a warning factor. Sulfur monochloride is not highly flammable, having flash poiats of 118°C (closed-cup) and 130°C (open-cup) and an auto-ignition temperature of 234°C. 

Shipment and Storage. Sulfur dichloride, if kept dry, is noncorrosive at ambient temperatures, thus carbon steel and Hon can be used Hi the constmction of tanks, piping, and dmms. However, when water or humidity is present, materials resistant to hydrochloric acid must be used, eg, glass-lined pipe. Teflon, titanium, HasteUoy C, or possibly a chemically resistant, glass-reiaforced polyester. Threaded pipe joHits should be assembled with Teflon tape. Hoses should be constmcted with a Teflon inner lining with the outer tube constmcted of Neoprene or braided 316 stainless steel protected by an adequate thickness of Teflon. Sulfur dichloride should be stored away from heat and away from dHect rays of the sum. Toluene and sulfur dichloride react exothermically when catalyzed by Hon or ferric chloride. Safety precautions should be foUowed when such a mixture is present (165). 

Health nd Safety Factors. Thionyl chloride is a reactive acid chloride which can cause severe bums to the skin and eyes and acute respiratory tract injury upon vapor inhalation. The hydrolysis products, ie, hydrogen chloride and sulfur dioxide, are beheved to be the primary irritants. Depending on the extent of inhalation exposure, symptoms can range from coughing to pulmonary edema (182). The LC q (rat, inhalation) is 500 ppm (1 h), the DOT label is Corrosive, Poison, and the OSHA PEL is 1 ppm (183). The safety aspects of lithium batteries (qv) containing thionyl chloride have been reviewed (184,185). 

Health, Safety, and Environmental Factors. Sulfur dioxide has only a moderate acute toxicity (183). The lowest pubHshed human lethal concentration is 1000 ppm for 10 months. The lowest pubHshed human toxic concentration by inhalation is 3 ppm for 5 days or 12 ppm for 1 hour. The lowest pubHshed human lethal concentration is 3000 ppm for 5 months. In solution (as sulfurous acid), the lowest pubHshed toxic dose is 500 flg/kg causing gastrointestinal disturbances. Considerable data is available by other modes of exposure and to other species NIOSH standards are a time-weighted average of 2 ppm and a short-term exposure limit of 5 ppm (183). 

Health and Safety Factors. Sodium metabisulfite is nonflammable, but when strongly heated it releases sulfur dioxide. The oral acute toxicity is slight and the LD q (rat, oral) is 2 g/kg. Sodium bisulfite appears to be weakly mutagenic to some bacteria, ia rodent embryos, and ia a human lymphocyte test. There is iaadequate evidence for carciaogenicity (183,343). 

The reduction ia tetraethyl lead for gasoline production is expected to iacrease the demand for petroleum alkylate both ia the U.S. and abroad. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used. However, concerns over the safety or potential regulation of hydrofluoric acid seem likely to convince more refiners to use the sulfuric acid process for future alkylate capacity. 

Those engaged in handling sulfuric acid should obtain detailed information on safe handling practices. Material Safety Data Sheets (MSDS) are available from U.S. and European manufacturers. 

Steel tank cats, often lined to minimize iron contamination, are usually employed for high concentrations of sulfuric acid. Bottom outlets or valves are not allowed, nor are internal steam coils. Tank contents must be unloaded via standpipe. Using air pressure to unload is not recommended for safety reasons, but if air pressure is used, gauge pressures should be held at <0.21 MPa (30 psi). 

The earliest method for manufacturiag carbon disulfide involved synthesis from the elements by reaction of sulfur and carbon as hardwood charcoal in externally heated retorts. Safety concerns, short Hves of the retorts, and low production capacities led to the development of an electric furnace process, also based on reaction of sulfur and charcoal. The commercial use of hydrocarbons as the source of carbon was developed in the 1950s, and it was still the predominate process worldwide in 1991. That route, using methane and sulfur as the feedstock, provides high capacity in an economical, continuous unit. Retort and electric furnace processes are stiU used in locations where methane is unavailable or where small plants are economically viable, for example in certain parts of Africa, China, India, Russia, Eastern Europe, South America, and the Middle East. Other technologies for synthesis of carbon disulfide have been advocated, but none has reached commercial significance. 

Safety. Chlorosulfuric acid is a strong acid and the principal ha2ard is severe chemical bums when the acid comes into contact with body tissue. The vapor is also ha2ardous and extremely irritating to the skin, eyes, nose, and respiratory tract. Exposure limits for chlorosulfuric acid have not been estabhshed by OSHA or ACGIH. However, chlorosulfuric acid fumes react readily with moisture in the air to form hydrochloric and sulfuric acid mists, which do have estabhshed limits. The OSHA 8-h TWA limits and ACGIH TLV—TWA limits are sulfuric acid = 1 mg/m hydrochloric acid = 5 ppm or 7 mg/m (ceiling limit). 

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. 

Properties and Applieations. Aryloxyphosphazene elastomers using phenoxy and J-ethylphenoxy substituents have found interest in a number of appHcations involving fire safety. This elastomer has a limiting oxygen index of 28 and contains essentially no halogens. It may be cured using either peroxide or sulfur. Peroxide cures do not require the allyhc cute monomer. Gum physical properties are as follows (17) ... 

Neoprene Type TW was shown to have low oral toxicity in rats. The LD q was found to be in excess of 20,000 mg/kg. Human patch tests with Types GN, W, WRT, and WHV showed no skin reactions (169). The FDA status of Du Pont Neoprene polymers is described (172). Although polychloroprene itself has not been shown to have potential health problems, it should be understood that many mbber chemicals that may be used with CR can be dangerous if not handled properly. This is particularly tme of ethylenethiourea curatives and, perhaps, secondary amine precursors often contained in sulfur modified polychloroprene types. Material safety data sheets should be consulted for specific information on products to be handled. 

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