Waste waters

The technology of nitration processes is unavoidably associated with the problem of waste water disposal. The water, which comes from washing the nitration product, contains acid components from the nitrating mixture, and nitro compounds. 

Both the acids and the nitro compounds in solution, or suspended, or in both states are highly noxious for the flora and fauna of rivers and lakes. 

nitro compounds in a concentration as low as a few milligrams per litre are lethal to fish. Wastes from the manufacture of hexyl (hexanitrodiphenylamine) are particularly toxic, killing fish at a concentration as low as 0.1 mg of hexyl per litre. For this reason, the removal of these compounds from the waste water prior to its discharge is of primary importance. 

As a rule acids are removed from waste water by discharging it into pits filled with limestone, where they are neutralized. 

Simpson and Evans [I 31 reported that nitrophenols such as o- and p-nitrophenols, 2,4-dinitrophenol or such a nitro compound as chloramphenicol could be destroyed by some Pseudomonas species to form nitrous acid salts. 

Refineries generate contaminated process water, oily runoff, and sewage. Water is used by just about every process unit, especially those that require wash water, condensate, stripping water, caustic, or neutralization acids. Contaminated process water may contain suspended solids, dissolved salts, phenols, ammonia, sulfides, and other compounds. As much as possible, waste-water steams are purified and re-used. Present requirements ensure that 

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All the process water streams are collected, the entrained hydrocarbons decanted, and the water is sent to the waste water stripper. 

The upper outlet for water from the condenser should be above the jacket so as to ensure that the condenser is full of water. If the rubber tube, which carries the waste water to the sink, tends to kink, a short copper spiral, made by winding a length of copper wire round a glass tube, may be slipped over the end attached to the condenser. 

Method 1. Place 11 5 g, of clean metallic sodium (compare Section III,7, Note 1), cut into small pieces, into a dry 1 litre round-bottomed fiask fitted with a 25 cm. double surface reflux condenser. Introduce 250 ml. of absolute, but preferably super dry (see Section 11,47, 5) ethyl alcohol all at once. A vigorous reaction ensues if the condenser tends to become flooded with alcohol, cool the flask either by surrounding it with a wet towel or by directing the waste water from the condenser upon... 

Representative Method The best way to appreciate the importance of the theoretical and practical details discussed in the previous section is to carefully examine the procedure for a typical precipitation gravimetric method. Although each method has its own unique considerations, the determination of Mg + in water and waste-water by precipitating MgNH4P04 6H2O and isolating Mg2P20y provides an instructive example of a typical procedure. 

Inorganic Analysis Complexation titrimetry continues to be listed as a standard method for the determination of hardness, Ca +, CN , and Ch in water and waste-water analysis. The evaluation of hardness was described earlier in Method 9.2. The determination of Ca + is complicated by the presence of Mg +, which also reacts with EDTA. To prevent an interference from Mg +, the pH is adjusted to 12-13, precipitating any Mg + as Mg(OH)2. Titrating with EDTA using murexide or Eri-ochrome Blue Black R as a visual indicator gives the concentration of Ca +. 

Federal regulations (40 CFR 261) classify acrylonitrile as a hazardous waste and it is Hsted as Hazardous Waste Number U009. Disposal must be in accordance with federal (40 CFR 262, 263, 264), state, and local regulations only at properly permitted faciUties. It is Hsted as a toxic pollutant (40 CFR 122.21) and introduction into process streams, storm water, or waste water systems is in violation of federal law. Strict guidelines exist for clean-up and notification of leaks and spills. Federal notification regulations require that spills or leaks in excess of 100 lb (45.5 kg) be reported to the National Response Center. Substantial criminal and civil penalties can result from failure to report such discharges into the environment. 

Several methods have been developed to estimate the oxygen demand in waste water treatment systems. Commonly used laboratory methods are biochemical oxygen demand (BOD), chemical oxygen demand (COD), total oxygen demand (TOD), total organic carbon (TOC), and theoretical oxygen demand (ThOD). 

W. G. Stmnk, Treat. DisposalInd. Waste Waters Residues Proc. Nat l Conf. 119 (1977). 

G. Eriedhofen, H. Kerres, J. Rosembaum, and R. Thiel, "Wet Air Oxidation of Waste Water," report to Bundesministerium fur Eorshung und Technologic (BMFT), Dec. 1980. 

When low boiling ingredients such as ethylene glycol are used, a special provision in the form of a partial condenser is needed to return them to the reactor. Otherwise, not only is the balance of the reactants upset and the raw material cost of the resin increased, but also they become part of the pollutant in the waste water and incur additional water treatment costs. Usually, a vertical reflux condenser or a packed column is used as the partial condenser, which is installed between the reactor and the overhead total condenser, as shown in Figure 3. The temperature in the partial condenser is monitored and maintained to effect a fractionation between water, which is to pass through, and the glycol or other materials, which are to be condensed and returned to the reactor. If the fractionation is poor, and water vapor is also condensed and returned, the reaction is retarded and there is a loss of productivity. As the reaction proceeds toward completion, water evolution slows down, and most of the glycol has combined into the resin stmcture. The temperature in the partial condenser may then be raised to faciUtate the removal of water vapor. 

Sodium alumiaate is an effective precipitant for soluble phosphate ia sewage and is especially useful ia wastewater having low alkaliaity (20,21). Sodium alumiaate hydrolyzes ia water to Al(OH)2 and Al" which precipitate soluble phosphate as aluminum phosphate [7784-30-7], AlPO. Sodium alumiaate has also been described as an effective aid for the removal of fluorides from some iadustrial waste waters (22). Combiaations of sodium alumiaate and other chemicals are being used to improve the detackification of paint particles ia water from spray-painting operations (23). 

Water and Waste Water Treatment. PAG products are used in water treatment for removal of suspended soHds (turbidity) and other contaminants such as natural organic matter from surface waters. Microorganisms and colloidal particles of silt and clay are stabilized by surface electrostatic charges preventing the particles from coalescing. Historically, alum (aluminum sulfate hydrate) was used to neutralize these charges by surface adsorption of Al cations formed upon hydrolysis of the alum. Since 1983 PAG has been sold as an alum replacement in the treatment of natural water for U.S. municipal and industrial use. 

After leaving the reactor, the reaction mixture consisting of aniline, water, and excess hydrogen is cooled and condensed prior to the purification steps. First, the excess hydrogen is removed and recycled back to the reactor. The rest of the mixture is sent to the decanter where the water and aniline are separated. The cmde aniline, which contains less than 0.5% of unreacted nitrobenzene and about 5% water, is distilled in the cmde aniline column. The aniline is further dehydrated in the finishing column to yield the purified aniline. Meanwhile, the aqueous layer from the decanter, which contains about 3.5% aniline, is extracted to recover the aniline and clean up the water before it is sent to the waste-water treatment plant. 

Fig. 5. Typical industrial waste-water treatment plant, eg, 25 x 10 L/day, Mobay Corporation plant at New Martinsville, W.V. (66).

Aminophenols have been detected in waste water by investigating uv absorptions at 220, 254, and 275 nm (87). These compounds can also be detected spectrophotometricaHy after derivatization at concentrations of 1 part per 100 million by reaction in acid solution with /V-(1-napbtby1)etby1enediamine [551-09-7] (88) or 4-(dimethylainino)ben2aldehyde [100-10-7] (89), and the Schiff base formed can be stabilized in chloroform by chelation to increase detection limits (90). 

Because the aminophenols are oxidized easily, they tend to remove oxygen from solutions. Hence, if they are released from industrial waste waters into streams and rivers, they will deplete the capacity of these environments to sustain aquatic life. Concern has also been raised that chlorination of drinking water may enhance the toxicity of aminophenols present as pollutants (138) chlorinated aminophenols are known to be more toxic (139). 

Ammonia and ammonium ions in industrial water streams, including waste-water streams, can be determined by either of two methods (ASTM Procedure D1426). In the first, the sample is buffered to a pH of 7.4 and distilled into a solution of boric acid where the ammonia nitrogen is deterrnined colorimetricaHy with Nessler reagents or titrated using standard sulfuric acid. 

P. A. Vesilind, Treatment and Disposal of Waste Water Sludges, Ann Arbor Science PubHshers, Ann Arbor, Mich., 1974. 

Many cities of the world do not levy a separate fee on water distributed, and even in those places where water is in shortest supply, a minimal ration may be free to everyone. The problem of wasted water and unmetered water a dding to the overall water demand is not new. In ancient Rome, fountains were coimected to the pubHc water by privately installed and owned lead pipelines, many of which were unrecorded, illegal, and hence untaxed. Frontius, the water commissioner of Emperor Nerva of Rome in AD 96, developed cmde meters to increase revenue and cut demand. 

Filtration is used in addition to regular coagulation and sedimentation or precipitation softening for removal of soHds from surface water or waste water. This prepares the water for use as potable, boiler, or cooling makeup. Waste water filtration helps users meet more stringent effluent discharge permit requirements. 

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