EPA/540/2-89/015 SUPERFUNDTREATABILITY CLEARINGHOUSE Document Reference: GA Technologies, Inc. "PCB Destruction Facility Circulating Bed Combustor.' Technical report prepared for U.S. EPA. 24 pp. December 1985. EPA LIBRARY NUMBER: Super-fund Treatability Clearinghouse -EUXM ------- SUPERFUND TREATABILITY CLEARINGHOUSE ABSTRACT Treatment Process: Thermal Treatment - Circulating Bed Combustion (CBC) Media: Soil/generic Document Reference: GA Technologies, Inc. "PCB Destruction Facility Circulating Bed Combustor." Technical report prepared for U.S. EPA. 24 pp. December 1985. Document Type: Contractor/Vendor Treatability Study Contact: Hiroshi Dodohara Ogden Environmental Services, Inc. P.O. Box 85178 San Diego, CA 92138-5178 619-455-2383 Site Name: Gulf Oil Corp., Berkley Heights, NJ (Non-NPL) Location of Test: Berkley Heights, NJ BACKGROUND: This treatability study reports on an evaluation of a pilot-scale, transportable, circulating bed combustor (CBC) for the incineration of PCB contaminated soils. This May 1985 test was for a demonstration to support a permit application for operation in California. OPERATIONAL INFORMATION; The CBC demonstration utilized a spiked soil (10,000 ppm PCB concentration) at a feed rate of 400 pounds per hour and a CBC operating temperature of 1800°F. No information was provided on the soil. Three four-hour runs were completed; however, because problems occurred in the sampling of particulates in the initial test, a fourth abbreviated run of two hours was conducted solely for collecting a particulates sample. Three supplementary runs were conducted to evaluate low combustion temperatures (1625°F) and to incinerate PCB-contaminated soil. Feed soil, fly ash, and bed ash were sampled and analyzed. Stack emissions samples were collected for particulates, semi-volatile organics, and volatile organics. PERFORMANCE; Destruction Removal Efficiencies (DREs) ranged from 99.9999% to 99.995% for PCB except for 1 run which resulted in a 99.82% efficiency. No significant PCB stack emissions were indicated. Particulate stack emissions during one test did not meet the standard for stationary air point sources. High particulate emissions were attributed to a high process air supply inadvertently applied to the air bag filtration unit. Another significant test value was the residual dioxin and furan in the treated soil. High values of 1.33 ppb for dioxins and furans were indicated in the fly ash. Several operational problems were reported. The damp, irregularly shaped soil feed material used during the trials clogged the transfer ducts in the unit. Agglomeration of the soil also occurred in the combustor bed, affecting mixing efficiency with direct reduction in the combustion efficiency. 3/89-9 Document Number: EUXM NOTE: Quality assurance of data may not be appropriate for all uses. ------- Other problems occurred with the stack sampling method. During one stack sampling sequence, fly ash was inadvertently dispersed throughout the operating bay, resulting in the evacuation of the entire office/pilot plant building. Siloxanes were present in the stack gas stream and interfered in the laboratory procedures to analyze the stack gas samples. However, the siloxanes may have been from silicone sealant which was used to install an in-line oxygen monitor, or from silicone rubber sealants in the sampling trains or similar sources. The demonstration trial runs and the supple- mentary tests indicated that the formation of agglomerates affected the combustion efficiency of the CBC unit, and increased the emission of products of incomplete combustion (PICs). CONTAMINANTS: Analytical data is provided in the treatability study report. The breakdown of the contaminants by treatability group is: Treatability Group CAS Number Contaminants WOl-Halogenated Aromatic TOT-TCB Total Trichlorobenzenes Compounds W02-Dioxins/Furans/PCBs 11096-82-5 PCB 1260 12672-29-6 PCB-1248 3/89-9 Document Number: EUXM NOTE: Quality assurance of data may not be appropriate for all uses. ------- EVALUATION REPORT GA TECHNOLOGIES, INC. PCB DESTRUCTION FACILITY CIRCULATING BED COMBUSTOR DEMONSTRATION TRIALS FOR NATIONWIDE PERMIT by Hiroshi A. Dodohara 20 DECEMBER 1985 ------- - 1 - GA TECHNOLOGIES INC. DEMONSTRATION TEST RESULTS SUMMARY Background; GA Technologies, Incorporated submitted an application to obtain a PCB disposal operating permit for the Circulating Bed Combustor (CBC), an incinerator using fuidized bed technology. The CBC was demonstrated for approval May 20 through May 29, 1985. As a non-liquid PCB incinerator, the CBC was demonstrated with spiked soil>of 10,000 ppm PCB concentration at a feed rate of0*00 pounds per houFT The combustion temperature was 1800° F^t/Three four-hour runs were completed, however, because problems occurred in the sampling of particulates in the initial test, a fourth abbreviated run of two hours was conducted solely for collecting a particulates sample. Split samples of feed soil, fly ash, and bed ash were taken and analyzed. Stack emissions samples were collected using the Modified Method 5 (MM5) for particulates and for semi- volatile org-anics and th'e Volatile Organics Sampling Train (VOST) for volatile organics. Quality assurance check samples were also submitted to Analytical Technologies Incorporated during the laboratory audit. In addition to the four demonstration tests, three supplementary runs were conducted to evaluate low combustion temperatures and to incinerate PCB-contaminated site soil. Test Results; Performance standards for non-liquid PCB incinerators exclude the criteria for combustion temperatures, residence time and excewss oxygen. All other PCB incinerator standards are applicable. The quality assurance audit of the laboratory indicated adequate performance. Test results are summarized in Table A. One test run resulted in low combustion efficiency (99.82% vs. 99.9% standard). The low combustion efficency however, did not affect the destruction and removal efficiency (ORE). All DREs were above the six 9s criteria for ------- - 11 - PCBs incinerators. No significant PCBs stack emissions were indicated. Particulates stack emission during one test did not meet the standards for stationary air point sources of 0.08 grains/dry standard cubic feet (gr/dscf). Test run 4 resulted in a particulates emission of 0.095 gr/dscf. The high particulates emission was attributed to a high process air supply inadvertently applied to the air bag filtration unit. The other test value of significance is the residual dioxin and furan in the treated soil. High values of 1.33 ppb for dioxins and furans were indicated in the fly ash. The Center for Disease Control indicated a safe value in soil to be 1 ppb for 2,3,7,fl TCDD. Two items remain incomplete. One is the PCBs analysis from solvent extracts of the particulate filter media. The second item is the calibration of the chloride in-line monitoring instrument using a two-feet section tubing and also using a 25 feet tubing section. Values for the two tests will be compared to determine whether or not significant differences exists between the two method. t The comparison will be made in order to resolve the departures from standard chloride sampling techniaues. CONCLUSION Evaluation of test results for both the demonstration trial runs and the supplementary tests indicate that the formation of aaglomerates has some effect on the combustion efficiency of the CBC unit. DREs were not affected significantly although Combustion Efficiency standard of 99.9% was not met in one of the demonstration test and in al of the supplementary runs. Indications are that agglomerate formation also increases the emissions of products of inclomplete combustion (PICs). In one of the supplementary runs, significant concentrations of phthlates were noted in the stack emissions. ------- - Ill - RECOMMENDATIONS Approval for the GA Technologies, Inc. CBC unit to operate does not impose unreasonable risk to health and environment when operated as intended. Therefore, strict operating restrictions must be imposed to assure proper operation of the CBC. The following provisions in addition to the non-liquid PCB incinerator performance standards should be included as conditions of approval to ensure proper operation of the CBC: 1. Operating temperature: 1750 - 1850 °F. 2. Process air supply to Bag House: as recommended by manufacturer. 3. Frequent inspection of the Bag House air supply. 4. Shutdown of the CBC when the Combustion Efficiency falls below the 99.9% standard, when the Combustion Efficiency cannot be brought up to standard after a speciied period of * time, say one hour. 5. Pneumatic transfer system for soil feed should be modified. ------- 1 e A GA TECHNOLOGIES DEMONSTRATIU FEST RESULTS (TESTS 1 THRU 4) TEST PARAMETER TEST TEMPERATURE °F COMBUSTION EFFICIENCY, % DESTRUCTION REMOVAL EFF. % RANGE 1,795-1,815°F 99.82 - 99.97 99.9999 0.000045 - 0.00023 <0.0092 - <0.029 <0.0027 - <0.015 Dioxin, ug/tn Furans, ug/fa Trichloro- ., benzene, ug/m 0.28 - 0.29 Particulates, gr/dscf Carbon Monoxide, ppm Hydrogen Chloride, ppm) Nitrogen Oxides, Ib/MBtu Volatile Org an ics Semi-Volatile Organics Ash Residues 0.0024 - 0.0950 22 - 105 57 - 266 0.035 - 0.156 No significant anissions STANDARD (Reg) 2,191°F for PCB incinerator 99.9 MIN. (§761.70) COMMENTS standard not applicable for non-liquid incinerator 99.82 C.E. caused by formation of agglomerates in combustion bed low combustion efficency did not affect ORE 99.9999 MIN. (§761.70) 0.001 gm outAg PCB introduced (§761.70) No current emissions standards Not detected at detection limits No current onissions standards Not detected at detection limits 0.08 gr/dscf 0.095 gr/dscf result attributed to high process air pressure 200,000 ferroally production (§60.263) 500 petroleum refinery (§103) min. of 1% HC1 entering system highest emission rate was if over 4 Ib/hr HC1 discharged 0.7 Ib/hr 0.2 Ib/M Btu, steam generation most stringent Benzene S. vinyl chloride controlled at NESHAP Siloxanes, phthalates No current standards significant emissions PCDD3, PCDFs No current standards <0.25 - <1.33 All V.O. emissions compared well OSHA PELs, all under limits Phthalates above OSHA PEL limit, no PEL for siloxanes Not detected at detection limits, 1 ppb dioxin considered safe by CDC < I ------- - v - TABLE OF CONTENTS CONTENTS PAGE MO. SUMMARY Background i Test Results i CONCLUS ION i i RECOMMENDATIONS Hi BACKGROUND 1 Demonstration Trials 2 OPERATIONAL PROBLEMS 5 Combustion Bed Agglomerate 5 Negative Stack Pressure Sampling 5 Modified Method 5 Sampling 5 Siloxane Interference in Stack Emission Analysis 5 Pneumatic Transfer Sys-tem 6 TEST RESULTS 6 Combustion Temperature, Residence Time, and Excess Oxygen 7 Combustion Efficiencies 7 DREs 7 Carbon Monoxide, CO 9 Hydrogen Chlor ide, HC1 9 Nitrogen Oxides, NOX 9 Particulates 12 PCB Emissions 13 Dioxins and Furans 13 PICs 14 Ash Res idues 15 PERFORMANCE STANDARDS FIR NON-LIDQUID PCB INCINERATORS 24 ------- - VI - LIST OF FIGURES FIGURES • PAGE NO. FIG. 1. GA TECH CIRCULATING BED COMBUSTOR 3 FIG. 2. GA CBC TRANSPORTABLE CONCEPT 3 FIG. 3. GA CBC FLOW DIAGRAM 4 ------- - VI 1 - LIST OF TABLES TABLES PAGE NO. TABLE A GA TECH DEMONSTRATION TEST RESULTS iv TABLE 1 COMB. EFF.,-DRE, AND STACK EMISSIONS.... 8 TABLE 2 POLLUTANTS IN STACK EMISSIONS 8 TABLE 3 VOLATILE ORGANICS. VOST RESULTS 11 TABLE 4 SEMI-VOLATILE ORGANICS: MM5 RESULTS 12 TABLE 5 GA TECH PCB DEMONSTRATION TEST RESULTS.. 17 TABLE 6 GA TECH DEMONSTRATION TEST RESULTS 18 TABLE 7 GA TECH PCB STUDY TEST RESULTS 19 TABLE 8 GA TECH PCB STUDY TEST RESULTS 20 TABLE 9 DREs ADJUSTED FOR PCB LOSS IN SAMPLING TRAIN 21 TABLE 10 POLLUTANTS EMISSIONS VS. STANDARDS OR CRITERIA, RUNS 1 THRU 3 22 TABLE 11 POLLUTANTS STANDARDS OR CRITERIA, RUNS 5 THRU 7 23 ------- GA TECHNOLOGIES, INC. DEMONSTRATION TRIALS FOR NATIONWIDE PERMIT EVALUATION REPORT BACKGROUND The demonstration trials were conducted to obtain an EPA nationwide permit to operate the PCB destruction facility, a transportable 16" diameter unit located in La Jolla, California. The data generated will be used to design a 36" transportable commercial facility to treat PCB-contaminated soil at a site in Berkeley Heights, New Jersey owned by Gulf Oil Corporation, a subs id ivis ion of Chevron Corporation. Gulf Oil has been working with the New Jersey Department of Environmental Protection (DEP) to quantify the extent of contamination and to determine the best method to clean the site. Some portions of the Berkely Heights site were found to contain as much as 6000 * ppm PCBs. The New Jersey DEP has recently imposed extensive study requirements in the form of a 50 feet by 50 feet sampling grid to gather subsoil data. Consequently Chevron has shifted emphasis to initiate the commercial use of the CBC from the New Jersey location to a PCB-contaminated site in Alaska. GA Technologies demonstrated the Circulating Bed Combustor (CBC) shown in Figures 1 and 2 for disposal of PCB-contaminated soil spiked to 10,000 ppm PCB concentration. The CBC uses high turbulence, low temperatures and recircul ating solids to destroy PCBs. GA claims high turbulence ensures good contact between the waste and both incoming air and recirculating hot solids which rapidly heats the waste to combustion temperature while in the presence of excess air. Combustion takes place along the entire height of the combustion chamber. Solids are separated from ------- - 2 - off-gases by an integral cyclone and returned to the combustor through a nonmenchanical seal. Temperatures are uniform, within _+50°F, throughout the loop. The'entire unit operates slightly below atmospheric pressure to preclude fugitive emissions. As an alternate to a wet scrubbing sytem, limestone is fed into the combustor primarily to neutralize and to reduce HC1 and other acidic gases in the stack gases. A flow diagram illustrates the process in Figure 3. Demonstration Trials; The demonstration trials were conducted during the period from May 24 through May 29, 1985. Three runs each of four-hour duration were reguired to fulfill conditions of the demonstration permit. However, four test runs were completed, the fourth run being of two-hour duration solely to collect a particulates sample to satisfy all sampling reguirements for Test 1. The particulates sampling filter paper became dislodged during Test 1 nullifying the sample and necessitating a fourth make-up test run. * Three additional test runs were completed after the demonstration trials. One test (Test 5) was conducted at a lower combustion temperature with the spiked soil and the other two tests (Tests 6 & 7) were conducted feeding site soil from Berkeley Heights. Although these last three tests were not part of the PCB disposal demonstration, data from these tests are included to provide additional information. The demonstration tests were auditted by Team Leader Jared Flood and Chemical Engineer Hiroshi Dodohara of the PCB Disposal Section of Chemical Regulation Branch, Office of Toxic Substances. Gary Kelso and Fred Bergman of Midwest Research Institute coordinated the sampling of solids streams and the sampling of stack emissions, respectively. The laboratory audit was performed by John Smith of Design Development Branch, Office of Toxic Substances. ------- FLUE GAS TO STACK INDUCED DRAFT FAN FLUE-GAS COOLER COOLING WATER BAGHOUSE FILTER FIGURE 1. GA TECHNOLOGIES CIRCULATING BED COMBUSTOR CYCLONE COMBUSTION CHAMBER FINE ASH REMOVAL I SOLIDS-RETURN LEG SOLID- FEED PORTS AIR INLET COARSE ASH REMOVAL / FIGURE 2. GA CIRCULATING BED CUMBUSTOR TRANSPORTABLE CONCEPT ------- STACK STAC ASH REMOVAL AND COOLING SYSTEM BED ASH OUTPUT GRAB SAMPLE BAG HOUSE FINES THIEF SAMPLE FIGURE 3 CIRCULATIONG 8ED COMBUSTOR FLOW DIAGRAM ------- OPERATIONAL PROBLEMS Combustion Bed Agglomerates; Agglomeration of soil in the combustor bed affected mixing efficiency with direct reduction in the combustion efficiency (CE). Cause of the agglomeration was attributed to power failure from electrical circuit breakers which resulted in flame-out (extinguishment of burner flame). The process upset caused by the flame-out ultimately resulted in hot spots along the combustor system which contributed to the formation of agglomerates. Negative Stack Pressure Sampling; The stack sampling contractor had no experience in the sampling of stacks under small vacuum pressures. Most stacks are under positive pressures or at atmospheric pressures. In one sampling seguence as the sampling instrument was being replaced, a pressure pulse directed back to the baghouse filters caused fly ash to disperse throughout the operating bay resulting -in the evacuation of the entire office/pilot plant building. Wipe test analysis were performed after clean-up and prior to resumption of operations. Modified Method 5 Sampling; The sampling contractor had no prior experience in the Modified Method 5 (MM5) sampling technigue. They received much guidance from the EPA consultant (Fred Bergman of MRI) during the course of operation. Their inexperience caused much delay in start-up of the demonstration tests. The MM5 sampling train is eguipped with an imp ing er to collect chloride emissions. The impinger normally contains caustic solution to absorb the chlorides. For the purpose of this demonstration, mercuric chloride was substituted for the caustic solution. Siloxane Interference in Stack Emission Analysis; Use of silcone sealant to install an in-line oxygen monitor at a more ------- - 6 - advanatageous location apparently caused siloxanes to enter the stack gas stream and ultimately interfered in the laboratory procedures and analysis of the stack gas samples. However, the silicone sealant was not confirmed to be the source of the siloxanes. Silicone rubber sealants in the sampling trains or other similar sources may have been the problem. Pneumatic Transfer System; The soil pneumatic feed transfer system was designed for handling high density, uniform radionuclear particles with right angle bends throughout the unit. The damp, irregularly shaped soil fed during the trials were not ideal for the pneumatic transfer system. Periodic clogging of the transfer ducts caused difficulties during the processing; however, the disposal operations were not affected. Field CBC units to be constructed in the future will likely not incorporate pneumatic feed systems. TEST RESULTS Test results were submitted to EPA on September 4, 1985. Quality assurance (QA) results for the laboratory were not available until December 2, 1985. The QA audit indicated adequate performance by Advanced Technologies, Incorporated of National City, California. These results demonstrated that the GA Technologies CBC incinerator is capable of destroying non- liguid PCB as required by 40 CFR 761.70(b)(l) and (2). Results from triplicate tests indicated less than one part per million (ppm) PCBs in both the bottom ash and the fly ash. Stack gas samples revealed less than the emission standard of 0.001 gram of PCB emitted per kilogram of PCB introduced into non-liquid PCB incinerators. Tables 1 through 4 summarize results of the seven tests runs including DREs, combustion efficiencies, and stack emissions. Tables 5 through 8 tabulates available results from all test ------- - 7 - runs. A discussion of per formance parameters by item follows. Combustion Temperature, Residence Time, and Fxcess Oxvnen: PCB incinerator performance standards pursuant to 40 CFP 761.70(a)(l) for combustion temperatures, residence time, and excess oxyqen do not apply to non-liauid PCB incinerator. Combustion Efficiencies; PCB rules require a combustion efficiency of 99.9% for non-liauid PCB incinerators. Tests 1, 2 and 3 meet this standard. However, Tests 4 through 7 fell short of the 99.9% requirement. Test Nos. Combustion 1234 Efficiency 99.94 99.95 99.97 99.82 99.67 99.80 99.85 According to GA Technology representatives the lower combustion efficiencies obtained in Tests 4 through 7 resulted from the formation of agglomerates in the combustor bed. The agg lone rates reduced the mixing efficiency of the combustor bed resulting in higher carbon monoxide levels than usual and lower combustion efficiencies. Agglomerates were formed initially during Test 3 when power failures resulted from a faulty circuit breaker. Temperature excursions as high as 1900°F and above occured which potentially causing the agglomerate formation. On completion of Test 3 the CBC was shutdown for the long Veterans Day weekend. The following short work week imposed some time constraints, because four tests were scheduled during the folowing four days. With a tight schedule to complete, the CBC was not cleaned out properly and the formation of agglomerates seemingly worsened thoughout Tests 4 through 7 with accompanying low combustion efficincies. _DREs_: Except for Test 7, DREs for all tests were within the PCB incinerator criteria of 99.9999% (six 9s). Tests 6 and 7 initially indicated DREs of 99.999% and 99.995 respectively. ------- - 8 - PCS DESTRUCTION TEST 'RESULTS TABLE 1 COMBUSTION EFFICIENCY, DESTRUCTION AND REMOVAL EFFICIENCY (DRE), AND STACK EMISSIONS TEST NO. 1 2 3 4 5 6 7 TEST NO. 1 2 3 4 5 6 7 TEST TEMPERATURE, °F 1,805 1,805 1,795 1,815 1,625 1,795 1,805 ug/m 0.087 0.49 0.40 (b) 0.038 0.031 0.31 COMB. EFF. % 99.94 99.95 99.97 99.82(a) 99.67(a) 99.80(a) ( 99.85 ( POLLUTANTS DIOXIN 3 ug/m (d) < 0.0092 < 0.029 (b) < 0.0049 < 0.0093 < 0.0019 DRE % > 99.9999 > 99.9999 > 99.9999 (b) > 99.9999 CO HC1 PE*n PPn 35 57 28 202 22 255 105 266 119 266 99.999 124 55 > 99.9999) (c) 99.995(a) 72 29 > 99.9995) (c) NO ppft 25.7 24.8 76.1 22.3 22.9 55.4 18.1 TABLE 2 IN STACK EMISSIONS FURANS., ug/hi (d) < 0.0027 < 0.015 (b) < 0.0032 < 0.0029 < 0.0016 TCB 3 PARTICULATES ug/m gr/dscf < 0.28 < 0.28 < 0.29 (b) l,500(f) 3,890 l,160(f) See Test 4 0.0425 0.0024 0.0950(e 0.0171 0.0219 0.0053 (a) Did no meet PCB incinerator standard of 99.9 % (b) Data not requested, test for particulates only (c) Based on calculated W . derived from chloride mass balance (d) Data not obtained, interference from silicones in analysis (e) Did not meet particulates standard for RCRA and CAA incinerators uof 0.08 gr/dscf ^ i !f) 3 is roughly equivalent m 24.8 , can convert by multiplying by —r—— ------- - 9 - However, when back-calculated for ORE usina mass balance for chlorides, the DREs were 99.9999% and 99.9995%. DRRs for Test Nps. 4 5 99.9999 99.9999 99.9999 * 99.9999 [99.9999] [99.9995] * Test was conducted for particulates samolinq only, ORE was not required. [ # 1 Calculated by use of chloride mass balance. The apparent low DREs for Tests 6 and 7 were caused by cross- contamination of PCBs from spiked soil having the high PCB level of 10,000 ppm. Feed material for Tests 6 and 7 were site soil from Berkely Heights with low PCB levels of 20 ppm and 47 ppm respectively. Residual soil high in PCB in the feed system from previous tests cross-fed into CBC with soil of low PCB levels in Tests 6 and 7. The higher DP.Fs of 99.9999% and 99.9995% were calculated by summing UD inorganic and organic chlorides in the feedstock and in discharges, and then compensating for the additional chlorides introduced into the CBC combustor by the residual soil from previous runs. Carbon Monoxide, CO; Although standards for carbon monoxide emissions do not exist for incinerators, limits are promuloated for ferroalloy production facilities (40 CFR 60.263) of 20% or by volume or 200,000 ppm of carbon monoxide and for petroleum refineries (40 CFR 103) of 0.05% by volume or 500 ppm carbon monoxide. The highest concentration of carbon monoxide discharged during the CBC demonstration was 124 ppm CO in Test fi. Test No. 1 2 3 4 5 6 7 CO, ppm 35 28 22 105 119 124 72 ------- - 10 - Hydrogen Chloride, HCjj Performance standard for RCRA (40 CFR 340) and CAA (40 CFR 61) incinerators is the larqer value of hydroqen chloride discharqed at rates of four (4) pounds per hour or at rates of one per cent of the chorides entering the pollution control eauipment. The hiqhest HC1 emission rate was for Test 4 with a stack rate of 550 dscf/min of qas containinq 266 ppm HC1. This rate is equivalent to an emission rate of about 0.7 Ib/hr of hydrogen chloride, well below the standard for discharges of HC1. Test No. 12345 HC1 , ppm 57 202 225 266 266 55 29 Nitrogen Oxide, NOy; No nitronen dioxide emission standards exists for incinerators; however, standards do exist for steam and electric utility steam qenerating units.The hiqhest NOX emission was 0.156 Ib NC> /MBtu (based on a molecular of 38 x» grams/qram molecular weiqht, as an averaqe of predominant species N02 and NO), as seen below: TEST NO. 1 2 3 4 5 6 7 NOV, ppm 25.7 24.8 76.1 2?.3 22.9 55.4 1R.1 X NO , In/MBtu 0.037 0.036 0.156 0.035 0.036 0.086 0.028 X The most strinqent standards are those for gaseous fuel at 86 nanograms N0v/Joule or 0.2 pounds NO /million Btu of heat X ** input. These standards are based on quantity of nitroqen dioxidp per power rating or heat input rating and are presented at 40CFR 60.40 and 40a as: §60.40 Steam Generating Units of 73 Megawatts or 250 million Btu/hour input or more N0y Emission Standard FUEL TYPE nq/Joule 1 b/M Btu Gaseous fuel with or without 86 0.20 wood residue ------- - 11 - PTCs(a) TABLE 3 VOLATILE ORGANICS:(C*UT6T RESULTS(b) ORGWICS Benzene Bromonrethane 2-butanone Chloroethane Chorofom Chlorcrethane Ethylbenzene Tetrahydrof uran Toluene Total Xylenes 1,1,1 Trichloroethane Trichlorothene Vinyl Chloride Alkanes Alkenes Alkyl furans Aldehydes Sil.anes ORGAN TCS CPM:EOTRATIONS, uo/m 3 (c) TEST 1 >293.68 - - 27.65 >262.8 > 17.14 - - 7.20 0.96 - 0.43 - 0.43 20.04 12.55 0.49 224.37 TEST 2 TEST 3 >389.8 - - 30.10 1,506. 31.74>1 - - 3.58 - 0.42 - 5.17 - 9.53 3.36 - 217.9 >214.6 9.02 - 4.47 >719.9 ,221. 35.62 2.13 1.86 - 11.2 0.39 - 90.96 57.78 3.23 29.66 232.57 TEST 5 38.72 - - - 0.43 4.92 - 2.20 5.02 1.82 - 0.26 - 0.21 6.42 - 0.24 192.4 TEST 6 49.84 - - - >82.54 29.14 0.43 - 6.87 7.31 6.31 - - 1.77 12.22 - 0.23 129.9 TEST 7 39.3 - 6.48 - 2.93 2.28 1.31 0.71 7.53 8.18 - 0.82 - - 8.40 - 0.49 667.9 (a) PICs = Products of Incomplete Combustion (b) Volatile Oroanic Sanplinq Train (c) Each result is an averaqe of 6 sample analyses taken during the test. ------- - 12 - PTCs(a) . TABLE 4 SEMI- VOLATILE OPGWTCS: MM5 RESULTS(b) ORGAN ICS mNPENTRATIONS, ug/m3 ORGAN ICS TEST 1 TEST 2 TEST 3 TEST 5 TEST 6 TEST ~> Acyclic Hydrocarbons - 9,165 23,571 24,645 Aldehvde/ketone 30.24 1.87 38,257 1,887 Carbon acids/bases 58.25 79.57 11,065 - 14,246 11,618 1,2,4-Tr ichlorobenzene - - 1,536 3,885 1,162 Chlorinated hydrocarbon 19.21 - Phenol - 19.21 52.71 - 6,994 2,817 Phthalates 63.8 24.70 - - 56,986 10,738 Siloxanes 99.86 85.06 56,200 2,156 36,264 4,577 (a) PICs = Products of Incomplete Combustion (b) EPA Modified Method 5, a sanoling train for particulates with an addition of an XAD resin cartridge for semi-volatile organic sampling cont'd NDX Emission Standard FUEL TYPE ' no/Joule Ib/M Btu Liauid fossil fuel with or 130 0.30 without wood residue Solid fossil fuel with or 300 0.70 without wood residue §60.40a Electric Utility Steam Generating Units of 73 Megawatts or 250 Btu/hour input or nr>re NZ> Emission Standard FUEL TYPE ng/Joule Ib/M Btu Gaseous fuel (Coal derived) 210 0.50 All others 86 0.20 Liquid fuel (Coal derived) 210 0.50 Shale oil 210 0.50 All others 130 0.30 Solid Fuel 210 0.50 ------- - 13 - Particulates: Emission standards for RCRA and CAA incinerators (40 CFR 264.340 and 40 CFR 60) limit the discharge of particulates to 0.08 or/dscf. Test 4 discharged particulates above the standards (0.095 qr/dscf). This condition was attributed to process air pressure to the haqhouse filter above that recommended by the manufacturer. The high rressure apparently stretched the filter media allowing higher than normal particulates to pass through the media. Test No. Particulates, * 0.0425 0.0024 0.0950 0.0171 0.0219 0.0053 gr/dscf * See Test 4 results PCB Emissions; For non-liguid PCB incinerators, the emission standard is 0.001 g PCB/kg PCB introduced into the incinerator. All tests except for Test 7, complied with this critical standard. PCB stack emissions for the CA CBC unit were: PCB Emissions TEST NO. grans PCBs out/kg PCRs Introduced 1 0.000045 2 0.00019 3 0.00023 4 sanple not reguired 5 0.000017 6 0.00022* 7 0.0046* * Calculated fran chloride mass balance Tn the laboratory analysis of PCBs, rinseate fron the cleaning of the MM5 probe v**s not analyzed for PCBs. Likewise, the particulates collection samples were not extracted for residual PCBs. Fred Bergman of MRI indicates that up to 80 percent of the total guantity of PCBs may reside in the nrobe and in the particulates and particulates filter media. Assuming two values, 50% and 8H%, of the total PCBs to be remaining in the probe and particulates ------- - 14 - system, the D3Es were recalculated. Table 9 indicates that at the 50% level, all but Run 7 met the six 9s criteria (using the chloride mass balance" results). At the 80% level, all tests treating spiked soil (10,000 ppm PCBs) met the six 9s criteria. One run with the site soil feed passed the six 9s criteria and the second failed (usinq the chloride mass balance results). '*, Dioxins and Flirans; No dioxins or furans were detected at the detectable levels indicated, the hiqhest detectable concentrations of dioxins and furans in the stack emission was 0.029 ua/nr (see Table 2). Althouqh emission standards do not exist for dioxins and furans, a ERE of six 9s for the destruction of PCBs Arochlor 1260 meets with conditions for incinerators burninq desiqnated dioxin-containinq waste under PCRA rule 40 CFR 264.343. The incinerator must meet the six 9s DRE for the principal POHCs, in this case Arochlor 1260, which are more difficult to burn than tetra- , penta-, and hexachorodibenzodioxins and furans. The measure of cumbustion difficulty is the heat of combustion, the lower heat of combustion indicating a hiqher degree of combustion difficulty. A comparison is presented below. Dioxins Tetra Ttenta Hex a Heat of Combustion Kcal/qm 3.46 3.10 2.81 » Furans Tetra tenta Hexa Heat of Combustion Kcal/qm 3.65 3.40 3.07 Arochlor 1260 (Composition) Benta (12%] Hexa (38%) Hepta (41%) Octa (8%) Heat of Combustion Kcal/qm 3.65 3.25 2.98 2.72 Althouqh the PCR-spiked soil is not one of the RCRA desionated dioxin- containinq waste, the capability to meet the performance standards has certainly been demonstrated. The concentrations of dioxin and furan residues in the fly ash and the bed ash did not exceed 1.33 ppb (hiqhest detectable levels) for Tests 1, 2 and 3 (see Tables 6 and 8). Dioxin and furan concentrations were no hiqher than 3.8 ppb for Tests 5, 6, and 7, (hiqhest dectable levels) indicatinq that the lower Combustion Efficiency in these tests had a noticeable effect on ash content for these orqanics. Soil contaminants lower than 1 pnb dioxins** is considered by the Center for Disease Control to be environmentally safe. ** Conversation with D. Keehner, Chief, Req. Sect. CRB/EED/OTS 12-12-85. ------- - 15 -' PICs; Products of incomplete combustion (PICs) are listed in Tables 3 and 4 as \folatile and Semi-volatile organics. Dioxins and furans were previously discussed. Tables 10 and 11 tabulates the high emission values for the volatile and semi-volatile organics detected in the stack emissions samples. All but two of the orqanics are currently not renulated under the Clean Air Act. Benzene and vinyl chloride are controlled via the National Emissions Standard for Hazardous Air Pollutanta (NESHAP). Renzene is regulated under the Equipment Leak provisions of NESFAP which controls fugitive emissions. Equipment is reguired to operate at a 500 ppm above background level. Leaks are defined as detections of 10,000 ppm or greater of vapors at the equipment, and are required to be repaired within five days. Vinyl chloride has an emission standard of 10 ppm under NESH?U?. With the need for a benchmark to compare the emission levels of stack gases and vapors, the OStft. standards for worker exposure level to each organic chemical was used. The standards listed in Tables 10 and 11 represent time- weiqhted averages (TWA) of permissible exposure level (PEL) to the organic vapors for a worker during an eight-hour work shift. Comparison of the Volatile Organics emissions to PEL values reveal that they are generally well below the C6HA standards. The Semi-\folatile Organic emissions for Tests 1, 2, and 3 are again generally below the PEL levels; however, emissions for Tests 5, 6, and 7 indicate a tendency for higher levels of Semi-UDlatile Organics. Carbon acids and bases with an emission value of 14.25 mg/nr is greater than •3 -5 the PEL value of 12 mq/m . Pht-.halates emissions were 57 mq/irr and compares poorly with a PEL of 5 mg/nv3. Low combustion efficiencies attained during Tests 5, 6, and 7 may have resulted in higher values of Semi-^latile Organics. k. Ash Residues; The ashes fron the CBC incinerator were predominantly treated soil. Bed ash is discharged from the CBC combustion chamber and fly ash results from treatment of the flue gas by the bagnouse filters. In all cases, the PCB levels were below the concentration necessary for designating the treated soil as non-regulated for PCBs (2ppm or 2,000 ppb per congener). Dioxins and furans were not detected at those detectable limits designated. ------- - 16 - Ash residues containing dioxins and furans in the range from 0.27 to 1.28 ppb fron a RCRA incinerator were proposed for delisting as a hazardous waste (FR 50 23721-23728, Jine 5, 1985). Test No. 1 2 3 4 5 6 7 Bed Ash PCBs, ppb 3.49 33.27 185.9 * 5.3 71.75 314.8 Dioxins, ppb <0.37 <1.22 <1.23 * <3.8 <1.83 <1.89 Furans, ppb <0.25 <0.85 <1.33 * <1.88 <1.21 <1.50 Fly Ash PCBs, ppb 66.45 9.90 32.12 * 26.81 106.0 55.2 nioxins, ppb <0.58 <0.25 <1.33 * <1.24 <0.84 <3.1 Furans," ppb <0.72 <0.54 <0.84 * <1.12 <0.58 <2.8 ------- - 17 - TABLE 5 • GA TECHNOLOGIES, INC. PCB DEMONSTRATIQN TEST RESULTS TEST 1 Soil Feed Rate, Ib/hr 327.5 Total Soil Feed, Ib 1,310 PCB Feed Concentration, ppn\ 11,000 (MRI results, GC/ECD) (9,600) (MRI results, GC/ttS) (8,500) PCB Feed Rate, Ib/hr (W. ) 3.65 in CO, ppm 35 C02, % 6.2 NO , ppm 25.7 X Combustion Eff. % 99.94 Superficial Velocity, ft/sec 18. Residence Time, sec 1.18 Destruction Temp. °F 1,805 Excess 02, % 7.9 Stack HC1, ppn , 57 Stack Gas Flow Rate, dscf/friin 504 TEST 2 411.5 1,646 12,000 (9,500 & 7,900) (9,140 & 7,950) 4.94 28 6.0 24.8 99.95 7 18.7 1.18 1,805 6.8 202 509 PCB Output Rate, Ib/hr (W ) 1.65E-7 9.45E-7 DRE, % > 99.9999 > 99.9999 Participates Concentrations Dry, gr/dscf see Test 4 Wet, gr/acf see Test 4 N/H = not required, Test 4 only for CO Destruction Renoval Efficiency (DRE) 0.0425 0.0227 particulates X 100 W. - W . _ in out 1QQ X 100 in TEST 3 323.8 1,295 9,800 (8,900) (8,050) 3.17 22 7.5 76.1 99.97 18.1 1.22 1,795 6.8 255 486 7.22E-7 > 99.9999 0.0024 0.0013 TEST 4 428.0 856 10,000 - 4.28 105 5.9 22.3 99.82 17.6 1.25 1,815 6.2 266 550 N/R N/R 0.0950 0.0551 ------- - 18 - TABLE 6 GA TECHNOLOGIES, INC. DEMONSTRATION TEST RESULTS PCBs CONCENTRATIONS 1,800 12,000 33.27 9.90 > 1,800 9,800 185.9 32.12 > 1,800 10,000 N/R N/fc DIOXIN CONCENTRATIONS FEED BED ASH FLY ASH ppb ppb ppb < 1.55 < 0.37 < 0.58 < 1.82 < 1.22 < 0.25 < 12.8 < 1.23 < 1.33 N/R * (c) FURAN CONCENTRATIONS ' < 33.8 < 0.25 < 0.72 < 2.62 < 0.25 0.0092 < 12.8 < 1.23 < 1.33 N/R TRICHLOROBENZEN CONCENTRATIONS 1,800 < 0.33 < 0.33 1,500 < 0.33 < 0.33 2,100 < 0.33 < 0.33 ORE STACK GAS % CONC.(ug/in ) 99.9999 0.087 99.9999 0.49 99.9999 0.40 N/R N/R STACK GAS CONC.(ug/fo3) - 0.0092 0.029 - 0.029 < 0.28 < 0.28 < 0.28 (a) = MRI results for bed ash and fly ash are all < 2 ppm by GC/MS method (b) = PCB 1260 (c) = conservative estimate since no standards were available for hex a-, hepta-, or octabenzofuran ------- - 19 - TABLE 7 GA TECHNOLOGIES, INC. FOB STUDY TEST RESULTS PCB Feed Rate, Ib/hr (W. ) in _ TEST 5 Soil Feed Rate, Ib/hr Total Soil Feed, Ib PCB Feed Concentration, ppm 12,000 PCB Fee CO, ppm C02, ppm NO , ppm Combustion Eff. % Superficial Velocity, ft/sec Residence Time, sec Destruction Tenp. °F Excess 0_, % Stack HC1, ppm Stack Gas Flow Rate, dscf/min (a) TEST 6 (a) TEST 7 (a) PCB Output Rate, Ib/hr (W Qut ORE, % Particulates Concentrations Dry, gr/dscf Wet, gr/acf 398.0 1,592 12,000 4.78 119 3.6 22.9 99.67 : 16.6 1.32 1,625 9.7 266 n 540 0 8.02E-8 > 99.9999 0.0171 0.0100 330.3 1,321 1 20 0.0066 124 6.1 55.4 99.80 19.3 1.14 1,795 1 8.6 55 540 6.01E-8 > 99.999 (> 99. 9999) (b) 0.0219 0.0122 285.2 ,711 47 0.00131 72 4.9 18.1 99.85 18.6 1.18 ,805 8.1 29 543 6.45E-7 > 99.996 (> 99. 9995) (b) 0.0053 0.0031 (a) (b) Tests 5 and 6 were 4-hour duration; Test 7 was 6-hour duration Based on calculated W. derived from chloride mass balance in ------- - 20 - TABLE 8 GA TECHNOLOGIES, INC. PCS STUDY TEST RESULTS PCBs CONCENTRATIONS TEST NO. 5 6 7 TEMP FEED(b) BED ASH °F ppm ppb 1,625 12, 1,800 1,800 000 5.3 20(c) 71.75 47(e) 314.8 FLY ASH PPb 26.81 > 106.0 > (> 55.2 > (> ORE STACK GAS % CONC.(ug/m ) 99.9999 0.038 99.999 ... 0.031 I fi t 99.9999Ta; 99.995 ,H. 0.31 99.9995T DIOXIN CONCENTRATIONS TEST NO. 5 6 7 FEED PPb < 7.42 < 1.97 < 2.13 BED ASH ppb < 3.8 < 1.83 < 1.89 FLY ASH PPb < 1.24 < 0.84 < 3.1 STACK GAS CONC.(ug/n3) < 0.0049 < 0.0093 < 0.0019 FURAN CONCENTRATIONS 5 6 7 < 390 ( a) < 1.27 < 1.53 < 1.88 (a) < 1.21 (a) < 1.50 TRICHLOROBENZ ENE 5 6 7 (a) = (b) = (c) = (d) = (e) = 1,300 < 0.17 < 0.17 MRI results PCB 1260 PCB 1248 Values based Mixture of 6 < 0.33 < 0.33 < 0.33 for bed ash and < 1.12 < 0.58 < 2.8 CONCENTRATIONS < 0.33 < 0.33 < 0.33 0.0032 0.0029 0.0016 1,540 3,890 1,160 fly ash are all < 2 ppm by GC/MS met! on chloride mass balance ppm 1248 and 41 ppm PCB 1260 ------- - 21 - TABLE 9 ORES ADJUSTED FOR PCB LOSS IN SAMPLING TRAIN Win TEST 1 2 3 4 5 6 7 Ib/hr 3. 4. 3. 4. 4. 0. [0 0. [0 60 94 17 28 78 0066 .28] 0131 .14] 1 9 7 8 6 6 Wbut Ib/hr .65X10~7 .45X10"7 . 22X10~7 PCBs .02X10"8 .oixio"8 .45X10"7 DREs 99. 99. 99. samples 99. 99. [99. 99. [99. WITH % LOSS 0% 9999954 9999809 9999772 99 99 99 IN SAMPLING TRAIN 50% .9999908 .9999617 .9999545 99 99 99 80% .9999771 .9999044 .9998861 not required 9999983 9990894 9999785] 9950763 9995393] 99 99 [99 99 [99 .9999966 .998178 .9999571] .9901527 .9990786] 99 99 [99 99 [99 .9999916 .9954468 .999893] .9753817 .9976964 Win = PCBs fed into CBC with contaminated soil Wout = PCBs stack emissions [##] = PCB feed rates and DREs based on chloride mass balance noc- Win - Vfout/[l - wt. fraction PCB loss] inn ORE X 100 ------- - 22 - TABLE 10 POLLUTANT EMISSIONS VS. STANDARDS OR CRITERIA RUNS 1 THRU 3 VOLATILE ORGANICS ORGANICS Benzene Brononethane 2-Butanone Chloro ethane Chloroform Chloromethane 1,1 Dichloroethene Ethylbenzene Tetrahyd rofur an Toluene Total Xylenes 1,1,1 Trichloroethane Trichlorothene Vinyl Chloride Alkanes Alkenes Alkyl furans Aldehydes Silanes SEMI-VOLATILE ORGAN ICS Acyclic Hydrocarbons Aid ehyd eA etone Carbon acids/bases 1,2,4-Tr ichlorobenzene Chlorinated hydrocarbon Phenol Phthalates Siloxanes (a) HIGH EMISSION ., CONCENTRATION mg/m" 0.761 0.033 0.122 5.500 4.135 0.0031 0.132 0.0066 0.014 0.027 0.0023 0.0064 0.246 0,656 0.027 0.083 0.660 38.26 11.07 0.019 1.854 0.064 56.21 PEL mg/fri 32 20 590 2600 240 200 (d) 435 590 740 435 1900 (e) 1,800 2,200 590 2.6 (f) (h) 3.6 (i) 2,350 290 12 40 10 19 (j) (k) (1) (o) (m) (c) (n) .(a) NESHAP(b) _ - STANDARD ug/m Equipment Leaks (fugitive emissions); 10,000 ppm defines leaks for pump and valves, must be repaired 500 ppm above background limit fort compressors and closed vent systan 10 ppm (26 mg/ta ) PEL = Permissible Exposure Limit, 8-hr time-weighted average, CSHA Standards, 29 CFR 1910.1000. (b) NESHAP = National Emission Standards for Hazardous Pollutants (c) Skin exposure; (d) Ceiling nunber PELs for: (e) xylene; (f) propane, hexar.e; (g) butadiene; (h) tetrahyrdrofuran; ( i) methyl- and iscbutylamine; (j) octane; (k) diisobutyl ketone; (1) methy- and isopropylamine; (1) hexachloroethane; (n) dimethyl- and dibutylphthalate (o) Threshold Limit Value (TLV) established 1975, An. Conference of Gov't. Industrial Hygienists (ACGIH) ------- - 23 - VOLATILE ORGAN ICS ORGANICS Benzene Bronanethar.e 2-Butanone Chloroethare Choroform Chloronet h are Ethylbenzene Tet r ahyd rof ur an Toluene Total Xylenes 1,1,1 Trichloroethane Trichlorothene Vinyl Chloride Alkanes Alkenes Alkyl furans Aldehydes Silanes SEMI-VOLATILE ORGANICS Acyclic Hydrocarbons Aid ehyd eA et on e Carbon acids/bases 1,2,4-Trichlorcbenzene Chlorinated hydrocarbon Phenol Phthalates Siloxar.es (a) TABLE 11 HIGH EMISSION POLLUTANT STANDARDS OR CRITERIA RUNS 5 THRU 7 CONCENTRATION mg/fa 0.093 0.039 4.69 0.080 0.0079 0.006 0.019 0.033 0.027 0.0019 0.071 0.027 t 0.023 3.380 24.65 3.58 14.25 3.89 0.019 7.00 57.00 36.27 3 ,(a) NESHAP (b) PEL mg/m 32 2Q(c)(d) 590 2600 240(d) 200 435 590 740 435(e> 1900 2.6 l,800(f) 2,200 STANDARD ug/fa Equipment Leaks (Fugitive anissions); 10,000 ppn\ defines leaks for punp: and valves, must be repaired; 500 ppm abovi background limit for compressors and closed vent systems 590 (h) 3.6 (i) 2,350 290 12 40 10 19 (j) (k) (1) (o) (m) (c) (n) 10 ppm (26 mg/m ) PEL = Permissible Exposure Limit, 8-hr time-weighted average, OSHA Standards, 29 CFR1910.1000. (b) NESHAP = National Emission Standards for Hazardous Pollutants, 40 CFR 61 (c) Skin exposure; (d) Ceiling number PELs for: (e) xylene; (f) propane, hexane; (g) butadiene; (h) tetrahyrdrofuran; ( i) methyl- and iscbutylanine; (j) octane; (k) diisobutyl ketone; (1) methy- and isopropylanine; (1) hexachloroethane; (n) dimethyl- and dibutylphthalate (o) Threshold Limit Value (TLV) established 1975, Am. Conference of Gov't Industrial Hygienists (ACGIH) ------- - 24 - PERFORMANCE STANDARDS FOR NON-LIQUID PCB INCINERATORS 1. 40 CFR 761.70(b)(l) Mass air emissions from the incinerator shall be no greater than 0.001 g PCBAg of the PCB introduced into the incinerator. 2. 40 CFR 761.70(b)(2) Incinerator shall comply with the following performance standards: - Incinerator performance standards for temperature and residence time do not apply to non-liquid PCB incinerators - Combustion efficiency of 99.9% - Rate and quantity of PCBs fed to the incinerator shall be measured and recorded every 15 minutes - Incineration temperature measured and recorded continuously - Stack monitoring shall be conducted when: - Incinerator is first used for PCB disposal - Incinerator is first used after modification which may alter stack emissions t - Monitor as a minimum the following: o2 co C02 NOX HC1 Total Organic Chlorides PCBs Total Particulates - Continuous monitoring of CO and 02 and periodic monitoring of CO2 - Shutdown of PCB feed when: - CO, O2, and C02 monitoring system fails - PCB feed monitoring systen fails - Use of water scrubber or alternate to control HC1 ------- |