v/EPA United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-011 Oct. 1982 Project Summary Emerging Technologies for the Control of Hazardous Wastes Barbara H. Edwards, John N. Paullin, and Kathleen Coghlan-Jordan :. Environmental Protection Agency '; C:c--;;.-. DC, .rijorn Street 'cago, iinnois 60604. .-.;> Investigations were conducted of new and emerging technologies for the disposal of hazardous wastes. These methods involve new techno- logies or a recent variation on an established one. In addition, a survey was made of potential users of haz- ardous waste information. The need for a data base for emerging hazardous waste technologies and/or a news- letter was evaluated. Information on the emerging technologies was ac- quired by computerized search, library searching, and personal contacts. The emerging technologies discussed include molten salt combustion, f luidized bed incineration, high energy electron treatment of trace organic compounds in aqueous solution, the catalyzed wet oxidation of toxic chemicals, dehalogenation of com- pounds by treatment with ultraviolet (UV) light and hydrogen, UV/ chlo- rinolysis of organics in aqueous solution, the catalytic hydrogenation- dechlorination of polychlorinated bi- phenyls (PCBs), and ultraviolet/ozone destruction. Theory, specific wastes treated, and economics are discussed. The major technologies investigated in detail were molten salt combustion, fluidized bed incineration, and ultra- violet/ozone destruction. Among the wastes treated by emerg- ing technologies are PCBs, various Dioxins, pesticides and herbicides, chemical warfare agents, explosives and propellents, nitrobenzene, and hydrazine plus its derivatives. This document encompasses a target audience ranging from laymen to natural scientists. The information presented here was derived solely for application to hazardous wastes. Readers requiring more specific in- formation about theory and the eco- nomics of start-up plus operating and maintenance costs for technologies that may by applied to a specific haz- ardous waste not discussed in this re- port are referred to the literature cited in this report and to documents about state-of-the-art situations for a parti- cular technology. This Project Summary was devel- oped by EPA's Industrial Environ- mental Research Laboratory. Cincin- nati, OH. to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction The material for the identification and evaluation of these technologies has been gathered through an intensive literature survey conducted over the course of a year. Although extensive use has been made of manual and computerized data bases, it was also necessary to monitor the recent liter- ature and forthcoming conferences and symposia abstracts access material not yet in the literature. Personal commun- ications were alsp used in the survey. Major hazardous waste generators in the United States were surveyed for their hazardous waste information needs. Fifty-three of the 72 companies surveyed were identified by a Waste Disposal Site Survey Report from the House of Representatives Committee on Interstate and Foreign Commerce ------- (Subcommittee on Oversight and In- vestigations) as the largest domestic generators of hazardous waste. Conclusions Molten salt combustion Molten salt technology has existed for many years, but it has not been used for the disposal of hazardous wastes until recently In the process, hazardous material is combusted at temperatures below its normal ignition point, either beneath or on the surface of a pool of molten salt Individual alkali carbonate salts such as sodium carbonate, or mixtures of these salts, are usually used as the melt, but other salts can be employed based on the characteristics of the waste. Containers for the molten salts are made of ceramics, alumina, stainless steel, or iron. Ideally, during the molten salt process, organic sub- stances are totally oxidized to carbon dioxide and water. Generally, the salt bath is stable, nonvolatile, nontoxic, and may be recycled for further use until the bath is no longer viable. The technology has progressed from bench-scale through the pilot plant stage to the construction of a demonstration-sized coal gasifi- cation unit. Portable units mounted on trucks have been tested. Some of the advantagesof molten salt combustion are as follows: Combustion is nearly complete. Non-polluting off-gases are gen- erally emitted. * Operating temperatures are lower than in normal incineration; thus, they are fuel efficient. The system is amenable to recy- cling generated heat. A wide variety of wastes can be combusted. Bulky wastes can be combusted after recycling. Many wastes can be combusted in compliance with EPA regula- tions. Some of the problems of mol- ten salt combustion are as follows: Particulate emissions from some wastes are high. The technology is not readily adaptable to aqueous wastes. Eventually waste salt and ash must be disposed of or the fluidity of the melt will be destroyed. A hazardous waste with greater than 20% ash cannot be com- busted. Detailed economic information for a demonstration-sized system is not currently available for many wastes (1980). 2 Fluid/zed bed incineration Fluidized bed systems have had many industrial uses since the technology was proposed by C.E. Robinson about a century ago, yet fluidized bed inciner- ation of hazardous wastes is a relatively new technique. A hot fluidized bed is ideal for combustion. Air passage through the bed produces strong agitation of the bed particles, which promotes rapid and relatively uniform mixing of carbonaceous materials The bed mass is large in relation to the injected waste, and bed temperatures, which usually range from 750°-1000°C, are usually uniform Bed materials have included sand, sand mixtures, dolomite, and alumina. Some advantages of fluidized bed incineration are as follows: The combustor design is simple and does not require moving parts after the initial feeding of fuel and waste. Fluidized bed incineration has a high combustion efficiency. Designs are more compact due to high volumetric rates. Comparatively low gas temper- atures and excess air require- ments minimize the formation of nitric oxide. In some cases, the bed itself neutralizes some of the hazardous products of combustion. A vertical induced draft inciner- ator was converted into a fluidized bed. The bed mass provides a large surface area for reaction. Temperatures throughout the bed are relatively uniform Fluidized beds are able to process aqueous waste slurries If the waste contains sufficient calorific value, the use of auxiliary fuel is unnecessary; moreover, the excess heat'may be recycled in some cases. The bed can function as a heat sink; start-up after weekends may require little or no pre-heat time. Disadvantages of fluidized bed com- bustion are as follows: Bed diameters and height are limited by design technology. Ash removal presents a potential problem. Systems requiring low tempera- tures may have carbon build-up in the bed due to increased residence time. Certain organic wastes w cause the bed to agglomerate. Paniculate emissions can be major problem. UV/ozone destruction Ozone treatment is an estabhshe technology for the treatment of som hazardous wastes; the combination c UV light and ozonation recently ha been found to be a more effectiv process for destroying hazardous wast than the use of ozonation alone. Th addition of UV light to the ozonatio process has greatly expanded th number of compounds that can b destroyed. PCBs are among the halo genated compounds destroyed Com pounds with shielded multi-bondei carbon atoms, sulfur compounds, ani phosphorous compounds are les susceptible to UV/ozonation. Dioxms nitrobenzene, and hydrazines hav< been destroyed by UV/ozonation Some advantages of UV/ozonatior are as follows: Aqueous or gaseous waste streams can be treated. Capitol and operating costs are not excessive. Chemical carcinogens and mut agens can be treated. The system is readily adaptable to on-site treatment of the haz- ardous waste. It can be used as a final treatment to supplement partial treatment systems. It can be used as a preliminary treatment for certain hazardous wastes. It can be used to meet effluent discharge standards. Modern systems are usually automated, thereby reducing labor requirements. Some disadvantages of UV/ozonation are as follows: Ozone is a non-selective oxidant; therefore, the waste stream should contain primarily the waste of interest. UV/ozone systems are generally restricted to 1 % or lower levels of hazardous compounds. Frequent- ly, hazardous substances are treated at ppm levels Ozone decreases rapidly with increasing temperature; therefore excess heat must be rapidly removed. ------- Results of hazardous waste information survey. Fifty-three major hazardous waste generators were surveyed for their hazardous waste information needs. Major information needs are new technologies for hazardous waste disposal, state-of-the-art methods for hazardous waste disposal, best technologies available for destruction of specific wastes plus costs, updated federal and state regu- lations for waste generation, transportation, storage, and de- struction of landfills, techniques to identify mixed waste streams, toxicity data on specific hazardous wastes, location of approved hazardous waste disposal sites and tech- nology available at the site; identity of hauling contractors, waste exchange and recycling information. Recommendations The emerging technologies evaluated in this study can be considered as alternatives to landfill disposal of hazardous waste. It is presumed that the emerging technologies will destroy the waste or at least attenuate it to acceptable levels. The advantages and disadvantages of each emerging tech- nology presented must be carefully considered when selecting the technol- ogy most suitable for the control of specific hazardous wastes is selected. The information needs for major hazardous waste generators could best be met by the use of a hazardous waste data base supplemented by newsletters and telephone "hotlines " Hazardous wastes destroyed by emerging technologies A. Molten salt combustion: Miscellaneous PCB's Chloroform Perchloroethylene distillation bottoms Trichloroethane Tributyl Phosphate Nitroethane Monoethanolamine Diphenylamine HCI Rubber tire buffings Para-Arsanilic Acid Contaminated ion exchange resins (Dowex and Powdex) High-Sulfur Waste Refinery Sludge Acrylics Residue Tannery wastes Aluminum Chlorohydrate Pesticides and herbicides Chlordane Weed B Gone DDT powder Malathion Sevm DDT powder with Malathion 2, 4-D Herbicide-Tar Mixed waste Real and simulated pesticide containers plastic, rubber, and a blend of these Feasible pesticides and nitrite herbicides Pesticides Nitrile Herbicides trifluralin 2, 4, 5-T dichlorobinil MCPA dieldrin heptachlor aldrin toluidme B. Fluidized bed incineration: Miscellaneous HCI spent pickling liquor Organotin in spent steel slag blasting abrasive Organic dye slurries red dye slurry (1 -methylaminoan- thraquinone and starch gum) yellow dye slurry (dibenzpyrene- quinone and benzanthrone) Chlorinated hydrocarbons PVC waste from a chemical plant PVC mixed with coal PVC insulation over copper wire Chlorinated hydrocarbon waste with 90% chlorine Munitions (slurry) TNT RDX(cyclotrimethylenetrinitramme) Composition B C. UV/ozonation technology: Miscellaneous PCB's TCDD (2, 3, 7, 8-tetrachlorodi- benzo-p-dioxin) OCDD (octachlorodibenzo-p-dioxin) Chlorodioxins (other dioxins are feasible) Hydrazine Monomethyl hydrazine Dimethyl hydrazine (asymmetrical) Copper process waste stream Nitrobenzene Barbara H. Edwards, John N. Paullin, and Kathleen Coghlan-Jordan are with Ebon Research Systems, Washington, DC 20011 T. L. Baugh is the EPA Project Officer (see below). The complete report, entitled "Emerging Technologies for the Control of Hazardous Wastes," (Order No. PB 82-236 993; Cost: $15.00, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 ĞU.8.GOVERNMENTHtlNTWa OFFICE: 1M2-559-017/0839 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 RETURN POSTAGE GUARANTEED 0000329 Postage and Fees Paid Environmental Protection Agency EPA 335 CHICAGO 6060?TRCET ------- |