svEPA United States Environmental Protection Agency Office of Emergency and Remedial Response Washington, DC 20460 Office of Research and Development Cincinnati, OH 46268 Superfund EPA/540/S-92/010 October 1992 Engineering Bulletin Pyrolysis Treatment Purpose Section 121(b) of the Comprehensive Environmental Re- sponse, Compensation, and Liability Act (CERCLA) mandates the Environmental Protection Agency (EPA) to select remedies that "utilize permanent solutions and alternative treatment technologies or resource recovery technologies to the maxi- mum extent practicable" and to prefer remedial actions in which treatment "permanently and significantly reduces the volume, toxicity, or mobility of hazardous substances, pollut- ants, and contaminants as a principal element." The Engineer- ing Bulletins are a series of documents that summarize the latest information available on selected treatment and site remedia- tion technologies and related issues. They provide summaries of and references for the latest information to help remedial project managers, on-scene coordinators, contractors, and other site cleanup managers understand the type of data and site characteristics needed to evaluate a technology for potential applicability to their Superfund or other hazardous waste site. Those documents that describe individual treatment technolo- gies focus on remedial investigation scoping needs. Addenda will be issued periodically to update the original bulletins. Abstract Pyrolysis is formally defined as chemical decomposition induced in organic materials by heat in the absence of oxygen. In practice, it is not possible to achieve a completely oxygen- free atmosphere; actual pyrolytic systems are operated with less than stoichiometric quantities of oxygen. Because some oxy- gen will be present in any pyrolytic system, nominal oxidation will occur. If volatile or semivolatile materials are present in the waste, thermal desorption will also occur. Pyrolysis is a thermal process that transforms hazardous organic materials into gaseous components and a solid residue (coke) containing fixed carbon and ash. Upon cooling, the gaseous components condense, leaving an oil/tar residue. Py- rolysis typically occurs at operating temperatures above 800°F [1, pp. 165,167] [2, p. 5].* This bulletin does not: address other thermal processes that operate at lower temperatures or those that operate at very high temperatures, such as a plasma arc. Pyrolysis is applicable to a wide range of organic wastes and is generally not used in treating wastes consisting primarily of inorganics and metals. Pyrolysis should be considered an emerging technology. (An emerging technology is a technology for which perfor- mance data have not been evaluated according to methods approved by EPA and adhering to EPA quality assurance/quality control standards, although the basic concepts of the process have been validated [3, pp. 1-2].) Performance data are cur- rently available only from vendors. In addition, existing data are limited in scope and quantity and frequently of a propri- etary nature. This bulletin provides information on the technology appli- cability, the types of residuals resulting from the use of the technology, the latest performance data, site requirements, the status of the technology, and where to go for further informa- tion. Technology Applicability Pyrolysis systems may be applicable to a number of or- ganic materials that "crack" or undergo a chemical decomposi- tion in the presence of heat. Pyrolysis has shown promise in treating organic contaminants in soils and oily sludges. Chemi- cal contaminants for which treatment data exist include poly- chlorinated biphenyls (PCBs), dioxins, polycyclic aromatic hy- drocarbons, and many other organics. Treatment data discussed in this bulletin were taken from treatability studies conducted by three vendors. Pyrolysis is not effective in either destroying or physically separating inorganics from the contaminated medium. Volatile metals may be desorbed as a result of the higher temperatures associated with the process but are similarly not destroyed. The probable effectiveness of pyrolysis on general con- taminant groups for various matrices is shown in Table 1. Examples of constituents within contaminant groups are pro- vided in "Technology Screening Guide for Treatment of CERCLA Soils and Sludges" [4, pp. 10-12]. Table 1 is based on current available information or professional judgment where no infor- mation was available [1, pp. 165,168] [2, pp. 9-14] [5, pp. 10- 15] [6, p. 9]. The proven effectiveness of the technology for a particular site or waste does not ensure that it will be effective at all sites or that the treatment efficiencies achieved will be acceptable at other sites. For the ratings used for this table, demonstrated effectiveness means that, at some scale, treat- ment results indicated that the technology was effective for [reference number, page number] ------- Table 1 Effectiveness of Pyrolysis on General Contaminant Groups for Soil and Sediment/Sludge Contaminant Croups Halogenated volatiles Halogenated semivolatiles Nonhalogenated volatiles Effectiveness Sediment/ Soil Sludge T T T T T • .0 Nonhalogenated semivolatiles O • §, PCBs ° Pesticides (halogenated) Dioxins/Furans Organic cyanides Organic corrosives Volatile metals Nonvolatile metals § Asbestos fe Radioactive materials Inorganic corrosives Inorganic cyanides §» Oxidizers fcj Reducers • Demonstrated Effectiveness: Succ scale completed. • • T V V • T T n n ci n O Cl o n 0 0 a n n o Cl O n n essful treatability test at some V Potential Effectiveness: Expert opinion that technology will work. Q No Expected Effectiveness: Expert opinion that technology will not work. that particular contaminant and medium. The ratings of po- tential effectiveness or no expected effectiveness are both based upon expert judgment. Where potential effectiveness is indi- cated, the technology is believed capable of successfully treat- ing the contaminant group in a particular medium. When the technology is not applicable or will probably not work for a particular combination of contaminant group and medium,, a no-expected-effectiveness rating is given. Limitations The primary technical factors affecting pyrolytic perfor- mance are the temperature, residence time, and heat transfer rate to the material. There are also several practical limitations which should be considered. As the medium is heated and passes through a pyrolytic system, energy is consumed in heating moisture contained in the contaminated medium. A very high moisture content would result in lower throughput. High moisture content, therefore, causes increased treatment costs. For some wastes, dewatering prior to pyrolysis may be desirable. The treated medium will typically contain less than one percent moisture. Dust can easily form in the transfer of the treated medium from the treatment unit, but this problem can be mitigated by water sprays. A very high pH (greater than 11) or very low pH (less than 5) may corrode the system components. The pyrolysis of halogenated organics will yield hydrogen halides; the pyrolysis of sulfur-containing organics will yield various sulfur compounds including hydrogen sulfide (H2S). Because hydrogen halides and hydrogen sulfide are corrosive chemicals, corrosion control measures should be taken for any pyrolytic system which will be processing wastes with high concentrations of halogenated or sulfur-containing organics. Technology Description Pyrolysis is formally defined as chemical decomposition induced in organic materials by heat in the absence of oxygen. Pyrolysis is a thermal process that transforms organic materials into gaseous components and a solid residue (coke) containing fixed carbon and ash. The pyrolysis of organics yields combus- tible gases including carbon monoxide, hydrogen, methane, and other low molecular weight hydrocarbons [7, pp. 252- 253]. Pyrolysis occurs to some degree whenever heat is applied to an organic material. The rate at which pyrolysis occurs increases with temperature. At low temperatures and in the presence of oxygen, the rates are typically negligible. In addi- tion, the final percent weight loss for the treated material is directly proportional to the operating temperature. Similarly, the hydrogen fraction in the treated material is inversely pro- portional to the temperature. The primary cleanup mechanisms in pyrolytic systems are destruction and removal. Destruction occurs when organics are broken down into lower molecular weight compounds. Re- moval occurs when pollutants are desorbed from the contami- nated material and leave the pyrolysis portion of the system without being destroyed. Pyrolysis systems typically generate solid, liquid, and gas- eous products. Solid products include the treated (and dried) medium and the carbon residue (coke) formed from hydrocar- bon decomposition. Various gases are produced during pyroly- sis, and certain low-boiling compounds may volatilize rather than decompose. This is not typically a problem. Gases may be condensed, treated, incinerated in an afterburner, flared, or a combination of the above. Depending on the specific compo- nents, organic condensate may be reusable. Other liquid streams will include process water used throughout the system. A general schematic of a pyrolytic process is shown in Figure 1. As shown in Figure 1, the first step in the treatment process is the excavation of the contaminated soil, sludge, or sediment. Oversized rejects such as large rocks or branches are removed and the material is transferred to the pyrolysis unit. The treat- ment system may include a desorption stage prior to pyrolysis. If so, the desorbed gases flow to the gas treatment system for treatment and/or recovery, and the contaminated matrix (mi- nus any desorbed chemicals) is transferred to the pyrolysis chamber [1, p. 166] [2, pp. 3-6]. Engineering Bulletin: Pyrolysis Treatment ------- The temperature in the pyrolysis chamber is typically be- tween 800 and 2,100° F, and the quantity of the oxygen present is not sufficient for the complete oxidation of al! con- taminants. In pyrolysis, organic materials are transformed into coke and gaseous components. Gas treatment options include: 1) condensation plus gas cleaning and 2) incineration plus gas cleaning. Pyrolysis forms new compounds whose presence could impact the design of the offgas management system. For example, compounds such as hydrogen halides and sulfur- containing compounds may be formed. These must be ac- counted for within the design of the Air Pollution Control (APC) system. There are three pyrolytic systems which will be discussed in this bulletin. These systems are: the HT-V system marketed by TDI Thermal Dynamics (formerly Southdown Thermal Dynam- ics), a process developed by Deutsche Babcock Anlagen AC, and an "anaerobic thermal processor" (ATP) marketed by SoilTech, Inc. The HT-V Thermal Distillation System is a mobile thermal desorption system which may be operated in a pyrolytic mode. The Thermal Distillation System processes waste by applying heat in a nitrogen atmosphere. Gravity and a system of annular augers are used to transfer waste through a series of three electrically heated distillation chambers. The temperature is ambient at the entrance to the distillation chambers and in- creases to full operating temperature (up to 2,100°F) as the waste progresses through the chambers. The continuous intro- duction of a nitrogen sweep gas removes and separates the volatile contaminants [8, p. 3]. The sweep gas must be periodi- cally sent to a flare to reduce the noncondensible combustible portion. TDI is currently conducting bench-scale tests on the Ther- mal Degradation System, which was developed for use in con- junction with the Thermal Distillation System. The full-scale design of the system is currently theoretical, but TDI envisions that Thermal Degradation will follow Thermal Distillation and will be used primarily for pyrolysis. In recent bench-scale tests, the Thermal Degradation System was operated at approxi- mately 2/000°F and a copper catalyst was used to enhance the pyrolysis of halogenated organics [2, pp. 3-6] [5, pp. 3-7]. A German company, Deutsche Babcock Anlagen AG, de- veloped a pyrolytic process which utilizes an indirectly heated rotary kiln. In the first step of the Deutsche Babcock system, pyrolysis occurs at a temperature of 1,100 to 1,200°F. If volatile or semivolatile organics are present, they will be desorbed in this step. In the second step, the gases produced by pyrolysis (as well as other volatilized organics) are combusted in an afterburner at a high temperature (1,800 to 2,400°F). Heat produced during the second step may provide at least a portion of the energy for the first step, which is endothermic. Prior to discharge, effluent gases from the second step are scrubbed to remove various pollutants including hydrogen halides and sul- fur oxides [1, p. 166]. The pyrolysis systems marketed by Deutsche Babcock are not currently available in mobile or transportable configura- tions and are therefore not directly applicable to onsite remediation of Superfund sites. These systems were included in this discussion to provide additional data and to indicate the potential viability of pyrolysis. In addition, full-scale applica- tions and testing of the Deutsche Babcock system have in- cluded the cleanup of contaminated soils [1, pp. 165-168]. Figure 1. Schematic Diagram of Pyrolysis Gas Treatment System Rejects Clean Offgas Condensed Vblatiles •^- Spent Carbon -^- Water E 1 Excavate -*• Material Handling ^ -^ Desorption (optional) ^ Pyrolysis ireaieu Medium ^ ^ Oversized Engineering Bulletin: Pyrolysis Treatment ------- ana* S'h f ' nC (Can°nie Environ™ntal) markets an anaerobic thermal processor (ATP) which may be operated in a pyrolyt,c mode. The ATP is also known as the AOSTRA-Taduk process and is essentially an indirectly-heated rotary kiln A transportable ATP with a nominal processing rate of10 tons per hoy, is available for onsite demonstrations and remediation \y, p. 3j. The ATP unit includes four chambers: preheat, reaction combustion, and cooling. In the preheat chamber, volatile materials are desorbed at temperatures up to 500°F Pyrolvtic conditions and temperatures between 700 and 1 ISoVare ZTrl Hn thC reaCtl'°n Chamber The desorPt;°n and/or pyrolysis of heavier organics will occur in this chamber Coke and noncombustible hydrocarbons produced by pyrolysis are transferred to the combustion chamber and burned [9, pp A-l to A-2J. Additional fuels such as gas or oil must be available for start-up, for control, and to supplement the pyrolysis products when they do not provide adequate fuel. Solids and gases from the combustion chamber proceed into the cooling zone The cooling zone and the preheat zone function as a heat ex- changer in which heat is transferred from the combustion residuals to the feed [10, p. 3]. Process Residuals H Hr 9enerated by Pyolytic systems typically in- elude solid, liquid, and gaseous residuals. Solid products in- clude debris, oversized rejects, dust, ash, and the treated me- dium Dust collected from particulate control devices may be combined with the treated medium or, depending on analyses C°ntamination' recycled throu9h the treatment Depending on the individual system, the flue gases from the pyrolysis unit will generally be treated by wet or dry AP(~ systems before discharge through a stack. In the Deutsche Babcock System, offgases are treated by incineration [1, p. 1 66]. Ash and treated soil/solids from pyrolysis may be contami- nated with heavy metals. APC system solids, such as fly ash may contain high concentrations of volatile metals If these residues fail required leachate toxicity tests, they can be treated by a process such as solidification/stabilization and disposed of onsite or in an approved landfill [1 1, p. 8.97]. If the treated medium and ash pass all required tests, they may be disposed of onsite without further treatment. Depending on the specific pyrolysis system, liquid streams may include condensed organics or water from the APC sys- tem After organics are removed, condensed water may be used as a dust suppressant for the treated medium. Scrubber purge water can be purified and returned to the site wastewa- ter treatment facility (if available), discharged to the sewer or used for rehumidification and cooling of the hot, dusty media. Liquid waste from the APC system may contain excess alkali, high chlorides, volatile metals, organics, metals particu- lates, and inorganic particulates. Treatment may require neu- tralization, chemical precipitation, settling, filtration, or carbon adsorption before discharge. Site Requirements Pyrolytic treatment processes are not expected to have significantly different site requirements than those for thermal desorption or incineration processes. Note that the pyrolytic systems marketed by Deutsche Babcock are not currently available in mobile or transportable configurations. The HT-V system and the ATP are transport- able, and vendors claim that they can be set up in a matter of days. 4«n v/ rec*uirements incl"de electric power (440 or 480 V, 3-phase) and water. The quantity of water required is design- and site-specific. M Treatment of contaminated soils or other waste materials require that a site safety plan be developed to provide for personnel protection and special handling measures. Storage should be provided to hold the process product streams until they have been tested to determine their acceptability for disposal or release. Depending upon the site, a method to store waste that has been prepared for treatment may be necessary. Storage capacity will depend on waste volume Onsite analytical equipment capable of monitoring site- specific organic compounds for performance assessment make the operation more efficient and provide better information for process control. Performance Data Limited performance data are available for pyrolytic sys- tems treating hazardous wastes containing PCBs, dioxins and other organics [1, pp. 165,168] [2, pp. 9-14] [5, pp. 10-15] [6, p. 9]. The quality of this information has not been determined These data are included as a general indication of the perfor- mance of pyrolysis equipment and may not be directly transfer- able to a specific Superfund site. Good site characterization and treatability studies are essential in further refining and screening the pyrolysis technology. The HT-V system's performance on oily sludges contami- nated with dioxins and PCBs was evaluated in bench-scale readability tests conducted by Law Environmental on April 25 V L2' PP> 9"14] [5' PP"1 °-15]' The Sl'm"lated waste used in the dioxm test was contaminated with 2378- tetrachlorodibenzo-p-dioxin (TCDD). A decontamination effi- ciency of over 99.99% was calculated, as no 2,3,7,8-TCDD was detected ,n the treated residue, offgases, or condensate In addition, the test report claims that no significant quantities of new toxic compounds were synthesized by the process [2, pp. 9- A second bench-scale treatability study was conducted on a rruxture of PCB-contaminated soil, PCB-contaminated oil, and Engineering Bulletin: Pyrolysis Treatment ------- water. All process streams were sampled and analyses indi- cated a decontamination efficiency of over 99.99%. PCB levels were below the detection limits in all effluent streams and the test report claims that no significant quantities of new toxic compounds were synthesized by the process [5, pp. 10-15]. Although these results appear promising, complete closures of mass balances are not possible with the information collected during the HT-V treatability tests. The Deutsche Babcock system was tested in an industrial- scale demonstration in May and |une 1988. Prior to this demonstration, the same system was used to treat 35,000 tons of soil. The plant is located in Unna-Bonen, West Germany, at a former coke oven site. The unit had a design rate of 7 tons/ hour with a soil moisture content of 21 percent and 5 percent volatile compounds. The destruction of 17 polycyclic aromat- ics was measured. A system decontamination efficiency of 99.77 percent was achieved. The results are summarized in Table 2 [1, p. 168]. Note that this test was conducted in Table 2 Deutsche Babcock Pyrolytic Rotary Kiln Contaminated Soil Results Date Pollutant Naphthalene 2-methylnaphthalene 1 -methylnaphthalene Dimethylnaphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[e]pyrene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Dibenz[a, h]anthracene Benzo[g, h, ijperylene March 8, Input mg/kg 101.00 40.20 23.40 n.d. n.d. n.d. 156.00 686.00 281.00 n.d. 236.00 155.00 214.00 66.60 112.00 43.70 86.60 16.80 14.00 Indenop, 2, 3-cd]pyrene 33.80 Sum n.d. = not detectable 2266.10 Decontamination efficiency in % 1989 Output mg/kg 1.7 0.5 0.3 n.d. n.d. n.d. 0.1 0.6 0.1 n.d. 0.1 0.2 0.5 0.4 0.1 0.1 0.2 0.1 0.1 0.1 5.2 99.77 January 27, 1989 Input mg/kg 161.60 73.80 42.90 93.20 68.20 42.30 238.00 1055.30 226.00 688.60 398.20 2259.20 1 34,60 111.50 168.50 81.90 138.10 23.20 60.20 69.50 61 34.80 Output mg/kg 0.5 0.1 0.1 0.3 0.1 0.1 0.1 1.4 0.3 1.3 0.6 0.3 0.9 1.1 5.2 0.3 0.4 0.1 0.1 0.1 13.4 99.78 Germany and that the majority of the applications of the Deutsche Babcock system have been in Germany. German requirements regarding incineration were not researched and may differ significantly from US requirements. The Soiltech ATP is being used in conjunction with chemi- cal dehalogenation to remediate the Wide Beach Superfund site. Much of the soil in the small community of Wide Beach, New York is contaminated with PCBs from road oils. PCB levels range from approximately 10 ppm to over 5,000 ppm; the primary cleanup requirement is to reduce PCB concentrations to less than 2 ppm [6, pp. 2-3]. The system used at Wide Beach is similar to the ATP described previously but also includes a reagent mix system. The reagent mix system adds dechlorination chemicals (potas- sium hydroxide and polyethylene glycol) to a stream of oils recycled from the system effluent [6, p. 4] [12, p. 45]. PCB concentrations in the treated soil were below the reporting limit of 70 ppb, which is significantly below the required level. In addition, the process water contained no more than 1 ppb PCBs, stack gas PCB levels were less than 33 percent of the New York State Department of Environmental Conservation (NYDEC) limits, fugitive emissions were within NYDEC limits, and treated soils passed the toxicity characteris- tic leaching procedure (TCLP) [6, pp. 2,9]. At the beginning of the cleanup effort, treated soil was returned to local sites. The treated soil, however, does not have the same consistency as untreated soil, and current plans are to landfill the soil rather than returning it to the original sites [12, p. 45]. Technology Status Pyrolysis has been used to treat various hazardous wastes as documented in the Performance Data section of this bulle- tin. In particular, pyrolysis has been applied to the remediation of the Wide Beach Superfund site (in conjunction with chemi- cal dehalogenation) [6, pp. 1 -2] and to the cleanup of contami- nated soils in Germany [1, pp. 165-168]. EPA Contact Technology-specific questions regarding pyrolysis may be directed to: Mr. Donald Oberacker U.S. Environmental Protection Agency Risk Reduction Engineering Laboratory 26 West Martin Luther King Drive Cincinnati, Ohio 45268 Telephone: (513) 569-7510. Acknolwedgments This bulletin was prepared for the U.S. Environmental Protection Agency, Office of Research and Development (ORD), Risk Reduction Engineering Laboratory (RREL), Cincinnati, Ohio, Engineering Bulletin: Pyrolysis Treatment ------- by Science Applications International Corporation (SAIC) under contract no. 68-C8-0062. Mr. Eugene Harris served as the EPA Technical Project Monitor. Mr. Gary Baker (SAIC) was the Work Assignment Manager, and Ms. Sharon Krietemeyer and Mr. Richard Gardner (SAIC) were co-authors of this bulletin. The authors are especially grateful to Mr. Donald Oberacker and Mr. Paul de Percin of EPA, RREL, who have contributed signifi- cantly by serving as technical consultants during the develop- ment of this document. The following other contractor personnel have contributed their time and comments by participating in the expert review meetings and/or peer reviewing the document- Mr. James Cudahy Dr. Steve Lanier Focus Environmental, Inc. Energy and Environmental Research Corp. REFERENCES i. 2. 3. 4. 5. 6. Schneider, D., and B.D. Beckstrom. Cleanup of Contami- nated Soils by Pyrolysis in an Indirectly Heated Rotary Kiln. Environmental Progress (Volume 9, No. 3), pp 165- 168. August 1990. Test Report of Bench Scale Unit (BSU) Treatability Test for Dioxin Contaminated Oily Sludge. Test Date: April 25, 1991. Prepared by Law Environmental, Inc. for South-' down Thermal Dynamics. June 1991. The Superfund Innovative Technology Evaluation Program: Technology Profiles. U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response and Office of Research and Development, Washington, D.C. EPA/540/5-90/006. November 1990. Technology Screening Guide for Treatment of CERCLA Soils and Sludges. EPA/540/2-88/004, U.S. Environmen- tal Protection Agency, 1988. Test Report of Bench Scale Unit (BSU) Treatability Test for PCB Contaminated Oily Sludge. Test Date: April 25, 1991. Prepared by Law Environmental, Inc. for South- down Thermal Dynamics. June 1991. Vorum, M. PCB-Soil Dechlorination at the Wide Beach Superfund Site: The Commercial Experience of SoilTech Inc. May 1991. 7. Incinerating Hazardous Wastes, H. M. Freeman, Editor. Technomic Publishing Co., Lancaster, PA 1988. 8. Southdown Thermal Dynamics, Marketing Brochures circa 1990. 9. The Taciuk Process Technology: Thermal Remediation of Solid Wastes and Sludges. Technical Information. Submitted by SoilTech, Inc. 10. Ritcey, R. and F. Schwartz. Anaerobic Pyrolysis of Waste Solids and Sludges: The AOSTRA Taciuk Process System. Presented to the Environmental Hazards Conference & Exposition, Environmental Hazards Management Institute, Seattle. May 1990. 11. Standard Handbook of Hazardous Waste Treatment and Disposal. H. M. Freeman, Editor. U.S. Environmental Protection Agency, Hazardous Waste Engineering Research Laboratory. McGraw-Hill Book Company New York, pp. 8.91-8.104. 12. Turning "Dirty" Soil into "Clean" Mush. Soils. September- October 1991. 'U.S. Government Printing Office: 1992— 648-080/60093 ------- ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 Official Business Penalty for Private Use $300 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 EPA/540/S-92/010 ------- |