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![Page 1: Emerging Technologies for the Treatment of Organic and Aqueous Waste Streams: International and U.S. Department of Energy Case Studies Dennis Kelley, Pacific.](https://reader035.fdocuments.us/reader035/viewer/2022062421/56649cb75503460f9497dba8/html5/thumbnails/1.jpg)
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
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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
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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
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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
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Polymers• N910: styrene block co-polymer– styrene-ethylene/butylenes-styrene
• N960: 100% cross linked, co-polymer of acrylamide
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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
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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”
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U.K. Contacts
• Sellafield• NNL, Workington• AWE, Aldermaston• UKAEA, Harwell• LLWR / NDA• Magnox stations, Berkeley• British Energy• AMEC• NSG Environmental
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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
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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
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I024-A Sample at 24 Hours
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I048-A Sample at 24 Hours
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Oil Solidification at Different Ratios
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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
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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
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U.S. Department of Energy’s Initiatives for Proliferation Prevention in Russia:
Results of Radioactive Liquid Waste Treatment Project, Year 1
Y. Pokhitonov, V. KamachevV.G. Khlopin Radium Institute, Russia
D. KelleyPacific Nuclear Solutions, USA
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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
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Oil SludgeNitric Acid
with Plutonium
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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
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Project Participants
• Russia– 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
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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
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Differential Thermal AnalysisPolymers: N910, N930, N960
Solidified samples with nitric acid and sodium nitrate possess high thermal stability
-8
-6
-4
-2
0
2
fact
um
wei
gh
t ch
ang
e (%
/°C
)
-100
-80
-60
-40
-20
0
20
wei
gh
t ch
ang
e (%
)
0 50 100 150 200 250 300 350 400 Temperature (°C)
910.002 ––––––– 930.001 – – – – 960.001 ––––– ·
Universal V4.4A TA Instruments
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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 second30 days = 77 M Rad+ 73 days = 270 M Rad
• Brittle, size reduction, no degradation / leaching• Conducted for gas generation tests
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Stability and IrradiationCobalt 60, gamma installation, dose rate 3.9·10⁶ grayN960 polymer, HNO₃, 1M, after irradiationN910 polymer, oil + TBP, after irradiation
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Irradiation Tests
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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
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Rate of gas release during irradiation of sample: N910 polymer + 50%-TBP / 50%-oil
-0,02
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
0,18
0,20
0 100 200 300 400 500 600 700 800 900 1000
Dose, Grx103
W, m
l/h
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Characteristic (composition)
of wastesConditions of solidification
Results
Volume of waste used, ml
Amount of # 960 used, g
Amount of # 910 used, g
4232Sludge residue from the bottom of the apparatus (aqueous phase). U-80g., NaNO₃~200g, HNO₃-0,8 M/I
6 8 0,5Successfully
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.
6 8 0,5Successfully
solidified
4237
LL decontaminationg solution with low amounts of organic substances, U-153 g/l, NaNO₃~100-150g, HNO₃
2,5 M/I
12 8 0,5Successfully
solidified
4238
LL decontaminating solution with low amounts of organic substances. U-153 g/l, NaNO₃~100-150g, HNO₃
2,5 M/I
20 4 2Successfully
solidified
4125U-20 g, NaNO₃40g, HNO₃1,2 M/I.
There was a precipitate in the solution.
15 16 0,5Successfully
solidified
4283Uranium re-extracts. U-70g, HNO₃
0,07M/I. 20 4 1Successfully
solidified
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Solidified sample after addition of waterSolution: HNO₃ 1,0M
No volumetric increase
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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
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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
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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
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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
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Markets
• Weapons production sites• Nuclear power plants• Submarine decommissioning• Toxic chemical industrial complexes• Research institutes• Uranium mining• Medical waste• Land & water remediation projects
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Year 2: Work Plan
• Polymer certification– 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
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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
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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
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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
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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
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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
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Solidification of TBP/OK
Test number
Liquid waste
(g)
Polymer (g)
Remarks Stir After 6 weeks
1-1 8g 8g
N910
Waste added to the polymer. Rapid reaction,
about 20 secondsPolymer Not fully consumed
noNo 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
no
Become translucent like glass; elasticity
increase
1-3 24g 8g
N910 + N960
Waste + water added to the polymer. Rapid reaction
Polymer not fully consumed yes
Become translucent like glass; elasticity
increase
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1:1 Ratio after 6 weeks 3:1 Ratio after 6 weeks
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Sodium Cation Exchange Resin Solidification
Test number
Liquid Waste (g)
Polymer (g) Remarks StirAfter 6 weeks
5-1
100g(about 50%
water)
20g N960
Resin particles are embedded in the
polymer massyes
No significant variance
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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
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Irradiation of Vacuum Pump Oil70 Million Rad
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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
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IR Spectra-graph of N910
Red represents after irradiationBlue represents before irradiation
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IR Spectra-graph of N960
Red represents after irradiationBlue represents before irradiation
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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
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TRU Oil Solidification with N990
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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
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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
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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
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Lawrence Livermore Project
• Depleted uranium tailings in oil
• 48 drums – completed
• N910 polymer (90%) + 922 metalbond (10%) formula
• 2 Step Process– Oil + polymer, cure then– Add cement to create a monolith
• Final storage at Nevada Test Site
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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