Waste stream, oxidation

Oxidizers do not discriminate among compounds and are capable of reacting with any oxidizable compounds in a waste stream. Oxidation is used either to degrade a compound completely or quite often, to degrade a compound partially to a less toxic form or intermediate that can be discharged or if needed, treated further by another process. 

The process is designed from a knowledge of physical concentrations, whereas aqueous effluent treatment systems are designed from a knowledge of BOD and COD. Thus we need to somehow establish the relationship between BOD, COD, and the concentration of waste streams leaving the process. Without measurements, relationships can only be established approximately. The relationship between BOD and COD is not easy to establish, since different materials will oxidize at different rates. To compound the problem, many wastes contain complex mixtures of oxidizable materials, perhaps together with chemicals that inhibit the oxidation reactions. 

Regardless of the techniques used to purify the KA oil, several waste streams are generated during the overall oxidation—separation processes and must be disposed of. The spent oxidation gas stream must be scmbbed to remove residual cyclohexane, but afterwards will stiU contain CO, CO2, and volatile hydrocarbons (especially propane, butane, and pentane). This gas stream is either burned and the energy recovered, or it is catalyticaHy abated. 

The radicals are then involved in oxidations such as formation of ketones (qv) from alcohols. Similar reactions are finding value in treatment of waste streams to reduce total oxidizable carbon and thus its chemical oxygen demand. These reactions normally are conducted in aqueous acid medium at pH 1—4 to minimize the catalytic decomposition of the hydrogen peroxide. More information on metal and metal oxide-catalyzed oxidation reactions (Milas oxidations) is available (4-7) (see also Photochemical technology, photocatalysis). 

Wetox uses a single-reactor vessel that is baffled to simulate multiple stages. The design allows for higher destmction efficiency at lower power input and reduced temperature. Its commercial use has been limited to one faciHty in Canada for treatment of a complex industrial waste stream. Kenox Corp. (North York, Ontario, Canada) has developed a wet oxidation reactor design (28). The system operates at 4.1—4.7 MPa (600 to 680 psi) with air, using a static mixer to achieve good dispersion of Hquid and air bubbles. 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

Air oxidation of dyestuff waste streams has been accompHshed using cobalt phthalocyanine sulfonate catalysts (176). Aluminum has been colored with copper phthalocyanine sulfonate (177,178). Iron phthalocyanine can be used as a drier in wood oil and linseed oil paints (179). 

Chlorine. Chlorine is a weU known disinfectant for water and wastewater treatment, however, it can react with organics to form toxic chlorinated compounds such as the tribalomethanes bromodichloromethane, dibromochloromethane, chloroform [67-66-3] and bromoform [75-25-2]. Chlorine dioxide [10049-04-4] may be used instead since it does not produce the troublesome chlorinated by-products as does chlorine. In addition, by-products formed by chlorine dioxide oxidation tend to be more readHy biodegradable than those of chlorine, however, chlorine dioxide is not suitable for waste streams containing cyanide. 

Waste streams that are treated by wet air oxidation generally are those having dissolved or suspended organic concentrations from 500 to 50,000 mg/L. Below 500 mg/L, oxidation rates are too slow and above 50,000 mg/L, incineration may be more feasible. 

Corrective Action Application At a hazardous waste treatment storage and disposal facility in Washington State, a cyanide-bearing waste required treatment. The influent waste stream contained 15 percent cyanide. Electrolytic oxidation was used to reduce the cyanide concentration to less than 5 percent. Alkaline chlorination was used to further reduce the cyanide concentration to 50 mg/1 (the cleanup objective). The electrolytic process was used as a first stage treatment because the heat of reaction, using alkaline chlorination to treat the concentrated cyanide waste, would be so great that it would melt the reactor tank. 

Several techniques can be used to separate phenol. Solvent extraction using gas oil or lube oil (process MSAs Sj and S2, respectively) is a potential option. Besides the purification of wastewater, the transfer of phenol to gas oil and lube oil is a useful process for the oils. Phenol tends to act as an oxidation inhibitor and serves to improve color stability and reduce sediment formation. The data for the waste streams and the process MSAs are given in Tables 3.4 and 3.5, respectively. 

Recycle of HBr to bromine is highly desirable both from an economic and an environmental standpoint. Catalytic oxidation offers the potential to recycle HBr from contaminated waste streams to bromine. We have demonstrated that the oxidation catalyst is stable against deactivation by a wide range of contaminants found in waste HBr streams. Strategies to deal with the contaminants will depend on the recycle applications in which the catalytic oxidation unit serves. 

This paper discusses in depth advanced technologies for recycled materials from solid waste streams. Chemical depolymerisation, thermal depolymerisation, pyrolytic liquefaction, pyrolytic gasification, partial oxidation, and feedstock compatibility are all explained. The economic feasibility of the methods are considered. 

Thermal oxidation is another alternative for destroying cyanide. Thermal destruction of cyanide can be accomplished through either high-temperature hydrolysis or combustion. At temperatures between 140°C and 200°C and a pH of 8, cyanide hydrolyzes quite rapidly to produce formate and ammonia.23 Pressures up to 100 bar are required, but the process can effectively treat waste streams over a wide concentration range and is applicable to both rinsewater and concentrated solutions22 ... 

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