PCB Destruction Technologies

1. PCB Destruction Technologies Winston Lue USEPA/OLEM/ORCR/PIID/PB December 7, 2016

3. PCB 101 • clu-in.org/conf/tio/rcraexpert/slides/RCRA-Expert-Brownbag-Series-PCBs.pptx • RCRA Expert Brownbag Series:PCBs 101. Amy Hensley. USEPA Office of Resource Conservation & Recovery. February 3, 2016

4. PCBs are everywhere! • They can be found in: • RCRA corrective action sites • Superfund sites • PCBs cleanup sites • DOD facilities • Buildings built or renovated 1950-1978

5. PCBs

6. Why are PCBs so difficult to destroy? • Chemical tailored to do what it was created to do: to be a flame retardant, dielectric fluid in electrical equipment. • Two benzene rings with chlorine atoms • Aromatic and resonance create stability • High Boiling Point, Melting Points, low vapor pressure • Bond energy of C-Cl difficult to break. • PCBs exists in MODEF (mineral oil dielectric fluid) in electrical equipment. • Incineration standards 2000-2200 F, and 1-3 secs residence time,

7. Thermodynamic data • Need a lot of energy to break C-Cl bonds in PCB molecule, stabilized by resonance of the benzene rings. • The higher the energy used to destroy PCBs, the more effective is the destruction • Need high temperature, pressure, powerful reagent to destroy PCBs.

8. 40 CFR 761.60(e) • Any person who is required to incinerate any PCBs and PCB items under this subpart and who can demonstrate that an alternative method of destroying PCBs and PCB items exists and that this alternative method can achieve a level of performance equivalent to an incinerator approved under § 761.70 or a high efficiency boiler operating in compliance with § 761.71, must submit a written request to the Regional Administrator or the Director, Office of Resource Conservation and Recovery, for a waiver from the incineration requirements of § 761.70 or § 761.71. • Alternative technology equivalent to the performance of a TSCA incinerator • Treatment standard six ‘9s’ DRE and < 2 ppm

9. PCB Approval Authorities • ORCR mobile units, transportable technologies, and non-unique fixed site facilities • EPA Regional (RA) unique fixed site facilities • Cannot be delegated to the States

10. Technical Review of the Operating Approval and Demonstration Test Plan • Use guidance document • Will the process work? • Will it meet the criteria of six 9s DREs? • Will it pose an unreasonable risk?

11. Technical Review of the Operating Approval and Demonstration Test Plan • Is it ex-situ or in-situ? • Was this process ever demonstrated and witnessed by another EPA office? • What type of chemical reagents were used in the process? • What type of Personal Protective Equipment (PPE) or engineering controls are needed?

12. Universe of Cleanup Media that You Might See at RCRA and Superfund Sites • PCB spills from Electrical Equipment and Industrial Processes • PCB contaminated soils • PCB sediments • PCB porous building materials • Oils, oily materials and debris • Other materials

13. Typical Treatment Dig and Haul Send to PCB or PCB/RCRA landfill Send to a RCRA or PCB incinerator (depending on concentration of PCBs) Other option bring another technology on site whether in-situ or ex-situ (60(e) technology). Most of the operating approvals granted by USEPA treat PCBs in oil matrix. Since some PCB contamination are not found in oils as main matrix, PCBs must either end up in an oil matrix or organic solvent to be destroyed.

14. Chemical Technologies to Dispose of PCBs • Chemical Dechlorination-works well with oils • Reduction-liquids and non liquids • Oxidation-liquids and non liquids • New emerging technologies

15. The Universe of Disposal and Decontamination Technology • Chemical • Physical • Thermal and alternative thermal • Biological • Landfills Some of these technologies are not permitted by 60(e)

16. Chemical Dechorination • Chlorine atoms from the PCB molecule are removed by a strong alkali, e.g. sodium emulsion, APEG, KPEG process • Usually operated under nitrogen • Very reactive process • Potential for sodium fires • Potential for hydrogen fires • xNa + R-Clx  xNaCl+ R-H R=biphenyl • Na+H2O NaOH +H2

17. Companies with mobile chemical dechlorination units • Mobile units • EPS – Environmental Protection Services, Wheeling, WVA • FTI – Florida Transformer Inc, Defuniak Springs, FL Fixed sites: Clean Harbor (PPM), LLC, Tucker, GA Transformer Disposer Specialists, Inc., Tonkawa, OK Clean Harbor (PPM), LLC, Coffeyville, KS

18. Alternative Technology – 60(e)Chemical DechlorinationEnvironmental Protection Services, Inc. • EPS, Inc., Wheeling, WV • One of the first companies to be granted national approval • Technology was originally Sunohio PCBX treatment • Operated PCBX as a transformer servicing unit • Bought out by ENSR ca. 1995 • Technology purchased by EPS ca. 2001

21. Solvated Electron Technology (SET) Commodore Advanced Sciences had a 60(e) approval and had demonstrated to HQ for soils, oils, and debris with PCBs. Approval expired in 2005. After several attempts, Commodore was not able to demonstrate destruction to PCBs to less than 2 ppm for three runs during several demonstrations.

22. SETTM Technology Reduction is essentially adding a reducing agent or source of electrons from a mixture to the PCB feed. Na + NH3-- NaNH2 + H2 + e-

23. SETTM Process Diagram

24. Catalytic Hydrogenation • H2 + R-Clx xHCl+ R-H R=biphenyl • 3-5 atmospheres • 300-400 C • Metallic catalyst • Safety Kleen-fixed facility, East Chicago, IN • Hydrodec North America-fixed facility, Canton, OH

25. Hydrodec North America

26. Hydrodec North America Inc.

27. Oxidation (Limited Success) Involve adding an oxidizing agent to the PCB feed to destroy it. Examples: Ozone Hydrogen peroxide (Low concentration) Potassium permanganate Potassium persulfate Fenton Reagent (Iron catalyst and Hydrogen peroxide) Difficulty destroying to <2 ppm

28. Thermal Technologies to Dispose of PCBs Thermal and Alternative thermal Incinerators 761.70 (and variations) High efficency boilers. 761.71 Scrap metal recovery and smelters, 761.72(a) Thermal desorbers with afterburners 761.60(e) Vitrification 761.60(e)

29. Incineration

30. PCB Incinerators Nationwide

31. Mobile Incinerators

32. Mobile Incinerators • EPA HQ had several mobile incinerators permitted in the mid 80s-90s. • Ogden bubbling bed • Shirco infrared • ENSR rotary kiln • Most were pilot scale and were never renewed. ENSR rotary kiln only commercial incinerator and was at BROS superfund site in New Jersey • Interest in mobile incinerators was lost from the sites as public opposition and environmental justice

33. Thermal Desorbers • High Temperature Thermal Desorption • With chillers (condensers) • With afterburners which is in fact an incinerator.

34. Flow Diagram for High Temperature Thermal Desorption

35. In-Situ Vitrification

36. In-Situ Vitrification

39. Technologies that were not permitted

40. Reasons 60(e) Technology was not approved Technology applications which were never approved • Talk is cheap • Incomplete application • No demonstration • Failed demonstration • Insufficient financial assurance • Human error (or stupidity) • After meeting with the company, did not hear from them • Company did not like terms and conditions of the approval • Safety issues e.g. Battelle/ U.S. Navy Based Catalyzed Decomposition Ecosafe Environmental Management System – Oxidation

41. Technologies that did not work • Mechanochemical Destruction • EPA Mobile Incinerator

42. Mechanochemical Destruction (MCD)

43. White Alice System

44. Granite Mountain Radio Relay Station (GMRRS) Picture taken from road going up to top of mountain.

45. Air Transport into Granite Mountain We are looking into potentially having regular flights into and out of Granite Mtn. Maybe daily. The flight takes about 1:15 minutes out of Nome. Weather could delay flights.

46. Garage Building at top of mountain MCD equipment will be setup in here.

47. Mechanical component:MCD treatment utilizes the high energy collisions of a ball mill to fracture soil constituents and produce reactive species on mineral surfaces (e.g. quartz sand). Chemical component:The radicals generated react with PCBs and many other organic molecules (pesticides, dioxins) yielding amorphous carbon and inorganic salts. MCD Principles Collisions create reactive sites on quartz. Reactive sites react with organic compounds.

48. Treatability (with U.S. Navy) Study Conclusions • MCD Process destroyed PCBs from over 100 mg/kg to less than 1 mg/kg in less than 15 minutes • Destruction appears to completely transform PCBs to amorphous carbon and chloride however, some congener shift may occur as well • Organochlorine Pesticides (DDT, Dieldrin) are destroyed in the same process • Preliminary result indicate MCD process is an effective remedial technology for treatment of recalcitrant organic compounds including PCBs and Organochlorine Pesticides.

49. Field Demonstration-Comedy of Errors. • 4500 ppm ended up with 45 ppm • Approval required < 1 ppm per AK DEC • Material handling problems, 88 C noted at drier • No technical personnel present who could trouble shoot problem to EDL • Temperature of soil before going into the milling reactor was 88 C. • Screw conveyor feed system clogged. Chewed up the metal balls. • Had to get metal balls flown in, wrong size balls first time • Finally got right size metal balls (2 days wasted). • Competive reaction of hydroxyl radicals and PCBs for active silica sites. • Had to ship PCBs contaminated soils to landfills in lower 48 states.

50. EPA Mobile Incinerator • Experience from Hiroshi Dodahara • The EPA Mobile Incinerator operated in Missouri • Demonstrated using kitty litter spiked with PCBs • Feeder bay had entrance/exit aisle stacked three levels high with drums on both sides • In preparation for the demonstration, pallets of kitty litter were placed in the aisle, effectively blocking egress from the feeder bay.