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

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Presentation on theme: "Emerging Technologies for the Treatment of Organic and Aqueous Waste Streams: International and U.S. Department of Energy Case Studies Dennis Kelley, Pacific."— Presentation transcript:

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

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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 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 – 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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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 3.9·10 ⁶ gray N960 polymer, HNO ₃, 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 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., NaNO ₃~­ 200g, HNO ₃ -0,8 M/I 680,5 Successfully solidified 4231 Sludge residue from the top of the apparatus (occurrence of organic phase is probable). U-80g., NaNO ₃~­ 200g, HNO ₃ -0,8 M/I. Very thick black liquid. 680,5 Successfully solidified 4237 LL decontaminationg solution with low amounts of organic substances, U-153 g/l, NaNO ₃~­ 100-150g, HNO ₃­ 2,5 M/I 1280,5 Successfully solidified 4238 LL decontaminating solution with low amounts of organic substances. U-153 g/l, NaNO ₃~­ 100-150g, HNO ₃­ 2,5 M/I 2042 Successfully solidified 4125 U-20 g, NaNO ₃­ 40g, HNO ₃­ 1,2 M/I. There was a precipitate in the solution. 15160,5 Successfully solidified 4283 Uranium re-extracts. U-70g, HNO ₃­ 0,07 M/I. 2041 Successfully solidified

31 Solidified sample after addition of water Solution: HNO ₃ 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 – 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 1 st 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) RemarksStirAfter 6 weeks 1-18g N910 Waste added to the polymer. Rapid reaction, about 20 seconds Polymer Not fully consumed no No significant variance 1-224g 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 1-324g 8g N910 + N960 Waste + water added to the polymer. Rapid reaction Polymer not fully consumed yes Become translucent like glass; elasticity increase

44 1:1 Ratio after 6 weeks3:1 Ratio after 6 weeks

45 Sodium Cation Exchange Resin Solidification Test number Liquid Waste (g) Polymer (g)RemarksStir 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

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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%) + 922 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


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