1. Emerging Technologies for the Treatment of Organic and Aqueous Waste Streams: International and U.S. Department of Energy Case Studies Dennis Kelley, Pacific Nuclear Solutions

2. Objectives of Presentation
Examine several case studies that describe polymer solidification technology for use on complex liquid waste streams:
STMI-Areva, France
British Nuclear Group, Sellafield, U.K.
Cernavoda, Romania; Krsko, Slovenia & OPG Canada
Khlopin Radium Institute, St. Petersburg, Russia
China Institute of Atomic Energy, Beijing, China
U.S. DOE Rocky Flats, Colorado
U.S. DOE Mound, Ohio

3. Nochar Polymer Technology
ABsorbent, mechanical process; not an ADsorbent material (surface collector)
Not an encapsulation technology
Minimal volumetric increase: 5% or less
No leaching / no liquid release
Solidification time: 1 hour to 48 hours depending on waste stream composition
Mechanical / chemical reaction; no heat build-up, no heat release
Polymers reduce the risk of fire; suppress vapor

4. Polymer Technology Stability of Solidification: Cobalt 60 gamma
270 million rad on organic / acid waste
90 million rad on organic waste – TBP
75 million rad on aqueous waste – 14.2 pH
Helps to immobilizes heavy metals
Safe / simple process: mixing or no mixing, depends on composition of waste stream
Final product for short, intermediate or final storage / burial
Incineration: less than .02% ash
Combined with grout / cement for monolithic matrix possible

5. Polymers N910: styrene block co-polymer
styrene-ethylene/butylenes-styrene
N960: 100% cross linked, co-polymer of acrylamide

6. France Partner: STMI (Areva Group)
2003, analyzed 20 year old tank waste
4 phase complex organic / aqueous waste stream, with alcohol and solid material
Good characterization made testing easy
Polymer formulas created according to each phase
2 : 1 bonding ratio for each phase
Encapsulation of polymer waste in cement

8. France
Cementation tests – passed ANDRA requirement, but not cost effective
ANDRA does not accept sorbent (organic) materials
Incineration at Centraco
2007 project at AREVA – Marcoule
Complex aqueous waste stream with low pH
2010 project at AREVA SICN Veurey
DU, oils & solvents + low amount of water, classified as “liquid muds”

9. U.K. Contacts Sellafield NNL, Workington AWE, Aldermaston
UKAEA, Harwell
LLWR / NDA
Magnox stations, Berkeley
British Energy
AMEC
NSG Environmental

10. United Kingdom - Sellafield
Oil immobilization program initiated by British Nuclear Group: 2006
Waste oil, non-standard waste stream, treatment and disposal issues on site
Waste Characterization & Clearance group and PNS conducted 3 experimental campaigns
Small scale test program: 90+ oil types

11. Experimental Methodology
Polymers: N910, N935, N960
1.5 : 1 ratio (liquid to polymer by weight)
Light mixing applied if “pooling” occurred on surface, due to quick solidification
Curing period: 24 – 48 hours
Polymers blended, depending on waste composition
Compositions unknown

12. I024-A Sample at 24 Hours

13. I048-A Sample at 24 Hours

14. Oil Solidification at Different Ratios

15. Results of Experiments: British Nuclear Group Analysis
Polymer systems proved effective in immobilization of waste oil into a solid product
No leaching of liquid on compression
Need to test for compatibility of polymers to waste and assess ratios on case by case basis
2 : 1 ratio is optimum for economic and security reasons

16. Cementation Test Program
UK Conditions for Acceptance for LLW disposal call for compressive strength minimum
Consider cement encapsulation of polymer solidification to be suitable for final disposal
Tests demonstrated oil solidification + grout can form a safe, non-compactable matrix suitable for final disposal

17. U.S. Department of Energy’s Initiatives for Proliferation Prevention in Russia: Results of Radioactive Liquid Waste Treatment Project, Year 1
Y. Pokhitonov, V. Kamachev
V.G. Khlopin Radium Institute, Russia
D. Kelley
Pacific Nuclear Solutions, USA

18. Russia since 2002 Partner: Khlopin Radium Institute, St. Petersburg
Over 60 tests conducted on complex liquid waste streams: Gatchyna and RADON – Sosnvoy Bor NPP
Sludge types from decontaminating solutions
Several forms of TBP from extraction facility for spent fuel reprocessing
Spent extractant solutions with heavy metal content

19. Nitric Acid with Plutonium
Oil Sludge
Nitric Acid with Plutonium

20. Purpose of Project
Program sponsored by DOE to engage Russian weapons scientists in peaceful use of existing and newly developed technologies
DOE’s IPP program is a mechanism for U.S. private sector companies to enter Russian market: radwaste treatment
Introduce USA environmental technology to weapons sector and seek joint technologies
Investigate solutions for Russia & USA liquid radwaste problems resulting from Cold War
DOE compensates scientists to participate in program
Long-term, commercialize project, employ scientists

21. Project Participants Russia USA
Russian State Atomic Energy Corporation (ROSATOM)
VG Khlopin Radium Institute (project manager)
Seversk (SCC ), Zheleznogorsk (MCC), Ozersk (MAYAK), Gatchyna
90+ participants, 68 weapons scientists
USA
Department of Energy (GIPP)
Argonne National Lab
Pacific Nuclear Solutions (project manager)
International Science & Technology Center (ISTC)
Project administrator, Moscow

23. Experiments Stability (Differential Thermal Analysis) Irradiation
Gas generation
* Polymer solidification /capacity / evaporation
* Leaching / water contact
* Encapsulation in cement
* Represents test data / results published in paper

24. Differential Thermal Analysis
Polymers: N910, N930, N960
Solidified samples with nitric acid and sodium nitrate possess high thermal stability

25. Irradiation Tests / Results
Extensive irradiation testing conducted, required for ROSATOM certification
All high dose rates
Cobalt 60 gamma irradiator
One example: nitric / organic solution
30 rad per second
30 days = 77 M Rad
+ 73 days = 270 M Rad
Brittle, size reduction, no degradation / leaching
Conducted for gas generation tests

26. Stability and Irradiation
Cobalt 60, gamma installation, dose rate 3.9·10⁶ gray
N960 polymer, HNO₃, 1M, after irradiation
N910 polymer, oil + TBP, after irradiation

27. Irradiation Tests

28. Gas Generation Tests
Preliminary tests, more testing and analysis is required
Tests required to determine fire and explosion safety conditions
Tests carried out under static conditions in sealed glass ampoules
N960 polymer + nitric solution: no changes in the solidification and no gas release
N910 polymer + TBP / oil: variable results
Preliminary judgment: polymers are not gas generators

29. Rate of gas release during irradiation of sample: N910 polymer + 50%-TBP / 50%-oil

30. Characteristic (composition) of wastes Conditions of solidification
Characteristic (composition) of wastes
Conditions of solidification
Results
Volume of waste used, ml
Amount of # 960 used, g
Amount of # 910 used, g
4232
Sludge residue from the bottom of the apparatus (aqueous phase). U-80g., NaNO₃~­200g, HNO₃-0,8 M/I 6 8
0,5
Successfully solidified
4231
Sludge residue from the top of the apparatus (occurrence of organic phase is probable). U-80g., NaNO₃~­200g, HNO₃-0,8 M/I. Very thick black liquid.
4237
LL decontaminationg solution with low amounts of organic substances, U-153 g/l, NaNO₃~­ g, HNO₃­2,5 M/I 12
4238
LL decontaminating solution with low amounts of organic substances. U-153 g/l, NaNO₃~­ g, HNO₃­2,5 M/I 20 4 2
4125
U-20 g, NaNO₃­40g, HNO₃­1,2 M/I. There was a precipitate in the solution. 15 16
4283
Uranium re-extracts. U-70g, HNO₃­0,07 M/I. 1

31. Solidified sample after addition of water Solution: HNO₃ 1,0M
No volumetric increase

32. Polymer Solidification/ Capacity / Evaporation: Conclusions
Polymer technology is irreversible, liquid permanently immobilized in polymer matrix
Advantage: direct application of polymer to waste without conditioning / additives
Little or no volumetric increase in the process
Appreciable volume reduction through evaporation; no measurement of water vapor
Polymers slow evaporation process
Polymers are versatile, solidify aqueous / organic waste of varying acidities, specific activities, suspensions and sludge types & salts

33. Chemical Stability – Leach Test
Various leach tests conducted
samples with cesium and water contact
samples mixed with cement
Aqueous polymer has capacity limits, water contact will cause leaching
Cementation may be required by regulators
Cementation tests not conducted properly; precise bonding ratios are necessary
Results:
Immediate contact with water after solidification caused leaching
Better results when sample had aged 1 month

34. Encapsulation of Polymer Solidification
Cementation tests at AREVA & Sellafield successfully completed, with 90% organic / 10% aqueous streams
When aqueous is above 10%, new technique for encapsulation is required
Encapsulation research underway:
additives to solidification
additives to cement
tests with inorganic materials encouraging

35. Applications Waste in above ground & underground tanks
Small containers / drums / self-contained generator (Yttrium -90)
Direct application to closed vessels to prevent leakage
Emergency spills at NPPs
Decommissioning sites, legacy waste

36. Markets Weapons production sites Nuclear power plants
Submarine decommissioning
Toxic chemical industrial complexes
Research institutes
Uranium mining
Medical waste
Land & water remediation projects

37. Year 2: Work Plan Polymer certification Commence sub-site test work
Required to import & sell polymer in Russia
Licenses required for health / safety, fire / explosion, irradiation / stability
Final certification issued by ROSATOM
Commence sub-site test work
Active solutions
Problematic waste streams
Continuation of experiments

38. Cernavoda, Romania Cernavoda NPP approval – 2005
CNCAN approval – early, 2007
Waste streams to be solidified:
mineral oil with tritium / cesium, 200+ drums completed
machine oil with tritium
scintillation fluid
Interim storage on-site (20+ years), plan to incinerate at Studsvik, Sweden

39. Krsko, Slovenia First Nochar user in Europe, 2002
Oil with tritium / solvents
Waste transported to Studsvik Nuclear, Sweden for incineration
Incineration with excellent results
Safety booms in power plant for emergency spills

40. Ontario Power Generation - Canada
2010 test program
FRF, Fire Resistant fluid for turbine governing system
Paint, latex (used N930)
Glycol (used N935)
Kodak developer (used N960)
Solvents, machine oil

41. China China Institute of Atomic Energy, Beijing Test program 2004-2005
Formal paper published
Waste treatment regulations to be changed
Repository conditions, similar as WIPP-DOE, desert conditions
1st large scale project underway

42. Waste Streams Six simulant waste streams tested:
Tri-butyl phosphate: 30% TBP / 70% kerosene
Acidic (nitric) solution: less than 0 pH
Alkaline solution: more than 14 pH
Ion exchange resin: anion to cation – 2:1
Sodium type-beads, chlorine type-beads & 50% water
Vacuum pump oil
Scintillation fluid

43. Solidification of TBP/OK
Test number
Liquid waste (g)
Polymer (g)
Remarks
Stir
After 6 weeks
1-1 8g
N910
Waste added to the polymer. Rapid reaction, about 20 seconds
Polymer Not fully consumed no
No significant variance
1-2
24g
8g N910
Waste added to the polymer. Rapid reaction. Not fully consumed - small amount of dry polymer at bottom of beaker
Become translucent like glass; elasticity increase
1-3
8g N910 + N960
Waste + water added to the polymer. Rapid reaction
Polymer not fully consumed
yes

44. 1:1 Ratio after 6 weeks
3:1 Ratio after 6 weeks

45. Sodium Cation Exchange Resin Solidification
Test number
Liquid Waste (g)
Polymer (g)
Remarks
Stir
After 6 weeks
5-1
100g
(about 50% water)
20g
N960
Resin particles are embedded in the polymer mass
yes
No significant variance

46. Irradiation Tests
Objectives of irradiation tests of solidified waste streams:
Evaluate degradation of waste form and polymers
Leaching
Durability
Waste sealed in individual ampoules
Cobalt-60, gamma source irradiator
Dose rate: 28 rad per second / 70 million rad
All samples exposed to same dose rate
Loose polymers also irradiated at same dose rate

47. Irradiation of Vacuum Pump Oil 70 Million Rad

48. IR Spectra-graph Tests/Results
Objective: check for degradation of polymers resulting from irradiation
100,000 rad for 100 hours = 10,000,000 rad
Conclusion: Little or no degradation of polymer

49. IR Spectra-graph of N910 Red represents after irradiation
Blue represents before irradiation

50. IR Spectra-graph of N960 Red represents after irradiation
Blue represents before irradiation

51. U.S. Department of Energy – Rocky Flats,Colorado
One of DOE’s first major nuclear weapons sites declared a full closure site
Objective: treat and remove all “orphan” waste streams
Polymers evaluated and approved for solidification of transuranic (TRU) waste with leach tests (EPA # 1311), hydrogen gas tests
Replaced cementation as treatment method
TRU oil with plutonium waste streams solidified:
- methanol with organic contaminants such as cyclohexane
- mixed organic waste consisting of freon, carbon tetrachloride and trichloroethylene
- contaminated used pump oil
TRU acid (cerium nitrate) with plutonium

52. TRU Oil Solidification with N990

53. DOE – Rocky Flats
Create layering process, 10 kgs per layer to avoid mixing
Packaging: 55 gallon steel drums
Final disposal at Waste Isolation Pilot Plant (WIPP), DOE’s ILW repository
All waste moved and stored at WIPP
Estimated DOE cost savings exceeded $10 million

54. U.S. Department of Energy – Mound, Ohio
In 2000, full scale solidification of vacuum pump oil with tritium under EM-50 program
8,000 liters of oil
DOE required bonding ratio: 1 : 1 (liquid:polymer by weight)
N990 formula – to solidify oil and water, includes catalyst for aged, low volatile oil
50,000 curies of oil waste solidified over 3 year period
2,200 curie per liter solidified / shipped to NTS

56. DOE – Mound Extensive leach testing conducted
Extensive bench testing to determine solidification production methodology
Final process - No mixing
Packaging: polyethylene liner / drum overpack
DOE estimated cost savings: $ 1 million +
Final storage / burial at Nevada Test Site (NTS) – DOE’s LLW site

57. Lawrence Livermore Project
Depleted uranium tailings in oil
48 drums – completed
N910 polymer (90%) metalbond (10%) formula
2 Step Process
Oil + polymer, cure then
Add cement to create a monolith
Final storage at Nevada Test Site

58. Conclusions
Accurate characterization of waste stream is critical to ensure good solidification
Conduct bench test on each and every waste stream; eliminate surprises
Packaging: must meet each country’s final disposal requirements; liners, drums, boxes, encapsulation in cement / other matrix, incineration
Mixing: keep process simple / small batches