1. Research Coordination Meeting on CRP “Behaviour of Cementitious Materials in Long-Term Storage and Disposal of Radioactive Waste” (Romania, November 24-28, 2008) CEMENTATION OF CERTAN TYPES OF LIQUID RADIOACTIVE WASTE OF RADIOCHEMICAL PLANT L. Sukhanov. P. Poluektov, K. Zakharova, O. Khimtchenko, Yu.Matyunin A.A. Bochvar Research Institute of Inorganic Materials, Moscow Research Coordination Meeting on CRP “Behaviour of Cementitious Materials in Long-Term Storage and Disposal of Radioactive Waste” (Romania, November 24-28, 2008) CEMENTATION OF CERTAN TYPES OF LIQUID RADIOACTIVE WASTE OF RADIOCHEMICAL PLANT L. Sukhanov. P. Poluektov, K. Zakharova, O. Khimtchenko, Yu.Matyunin A.A. Bochvar Research Institute of Inorganic Materials, Moscow

2. Individual project of Leonid Sukhanov (A.A.Bochvar Research Institute) Subject:  Cementation of certain types of liquid ILW generated from SNF reprocessing at radiochemical combine PA Mayak, Urals  Cementation of pulps from storage tanks of the radiochemical combine MCC (Mining and Chemical Combine), Siberia 2

3. MAIN OBJECTIVES AND SCOPE OF INDIVIDUAL PROJECT  Studying processes that occur during production of the cement compounds generated during solidification of some kinds of liquid RW of radiochemical combines - PA Mayak, Urals and MCC, Siberia  Determining of cement compound characteristics (mechanical strength, water resistance, frost resistance, flowability, heat release, loading capacity of waste and others)  Giving recommendations for operation of a commercial facility for production of cement compounds satisfying waste acceptance criteria and national requirements  Assessing behaviour of the produced cement compounds during their storage 3

4. PLANNED INVESTIGATIONS FOR THE FIRST YEAR - - cementation of evaporator concentrates and pulps of PA Mayak Under this work, special emphasis will be given to:  cementation of salt solutions containing hydroxide sludge  production of high-flowable cement compounds  cementation of spent filter materials pulps The researches were carried out using the equipment, instruments, personnel and materials of A. A. Bochvar Research Institute. 4

5. Evaporation, Rectification Ammonia solution Acidic decontamination solution Acidic rafinate from extraction Concentrate from membrane-sorption LLW treatment Evaporation bottom Re-evaporation Condensate Nitric acid Ammonia solution PurificationEvaporator concentrate Cement compound Cementation Long-term storage (disposal) Tritium containing waste Ion-exchange resin pulps Filter perlite pulps Manganese dioxide pulps PA Mayak’s liquid RW planning to send to cementation 5

6. SPECIFIC FEATURES OF PA MAYAK’S LIQUID ILW THAT HAVE EFFECT ON CEMENTATION PROCESS PARAMETERS  A variety of different types of liquid wastes, specifically: - salt alkaline waste (3 types) and acid waste (2 types) - liquid tritium waste - pulps of filter materials and hydroxides (4 types)  Certain components present in LRW can significantly influence the liquid ILW treatment scheme and, specifically, the cementation process and properties of a produced cement compound (iron hydrooxide, ammonia, nitric acid, tritium, etc.)  The cement compound will be stored not in drums or other containers, but in concrete compartments of a storage facility (the volume of each compartment is about 380 m 3 ) 6

7. REQUIREMENTS FOR CEMENT COMPOUNDS AT PA MAYAK REMENTATION COMPLEX The produced cement compound quality must satisfy: The National Standards: –GOST R 51883-2002 “Cementitious Radioactive Waste. General Requirements“ –NP-019-2000 “Reguirements to liquid RW Management” Additional requirements:  sufficient flowability to ensure uniform filling of storage facility compartments  low heat release during the compound solidification in storage facility compartments  maximum loading capacity of a cement compound 7

8. NATIONAL STANDARD REQUIREMENTS FOR CEMENT COMPOUNDS Quality indexPermitted value Specific activity of compound: Beta-activity Alpha-activity <3.7·10 10 Bq/kg (1·10 -3 Ci/g) <3.7·10 7 Bq/kg (1·10 -6 Ci/g) Leaching rate of radionuclides (Cs-137 and Sr-90) <1·10 -3 g/cm 2 ·day Mechanical strength (compressing strength) >50 kg/cm 2 Radiation resistance Mechanical strength should be not less than 50 kg/cm 2 at a radiation dose of 1 mln Gy * Thermal cycle resistance Mechanical strength should be not less than 50 kg/cm 2 after 30 freezing-thawing cycles * Water resistance Mechanical strength should be not less than 50 kg/cm 2 after 90 days of being in water * * but not less than 75% of initial strength 8

9. RESEARCH METHODOLOGY Sample Preparation  The cement paste made through mixing the components by using the laboratory-scale equipment is placed into the device designed for preparation of cement compound samples.  The device represents a dismountable cartridge (cassette) consisting of several cells (molds) to allow making cement cubes 2×2×2 cm in size.  The device is placed in a humid-air atmosphere in an exsiccator with water at the bottom to prevent desiccation (drying).  When held for 28 days, the samples were taken from the cells for further analyses.  Radionuclides used for RW simulation are Sr-90, Cs-137 and tritium. 9

10. RESEARCH METHODOLOGY Matrix Materials  In most experiments a mixture of Portland cement (Grade PC500-D0) and bentonit was used as a matrix material.  The content of bentonit in the matrix material in all the experiments was 10 wt %. Bentonit, which was introduced from a cement compound being in contact with water, acted as a sorbent to reduce leachability of radionuclides, primarily Cs-137.  The Slag Portland cement, a mixture of Portland cement and metallurgical slag, was used in a number of experiments. 10

11. RESEARCH METHODOLOGY  Determination of Ultimate Compressive Strength Ultimate compressive strength is determined by means of a hydraulic press using the standard procedure.  Cement Paste Plasticity Test Plasticity of a cement paste is characterized by degree of its flowability (spreadability) measured by the viscosimeter using the standard procedure.  Frost resistance Frost resistance is determined by the procedure, which included 30 freezing/thawing cycles.  Immersion Tests Water resistance is determined by comparison of the strength of the samples held in water for 90 days to the strength of the reference samples held in the air under room conditions.  Long-Term Leaching Tests of Cement Compounds A degree of radionuclide fixation in a cement compound is determined by the rate of radionuclide leaching and by the activity that passed into a solution from a cement compound. 11

12. Measurement of Cement-Paste Flowability Molds for Preparation of Cement by Suttard’s Viscosimeter Measurement of Cement-Paste Flowability Molds for Preparation of Cement by Suttard’s Viscosimeter EXPERIMENTAL TECHNIQUES AND EQUIPMENT Compound Samples 12

13. Hydraulic Press for Testing of Cement-Compound Sample Strength EXPERIMENTAL TECHNIQUES AND EQUIPMENT 13

14. Apparatus for Determination of Cement Hydration Heat EXPERIMENTAL TECHNIQUES AND EQUIPMENT  -,  -Radiometer UMF-2000 14

15. EXPERIMENTAL TECHNIQUES AND EQUIPMENT Exiccator for Damp Curing of Cement Compound Samples 15

16. RESEARCH SUBJECT The following solutions and pulps simulating different liquid RW of PA Mayak were under consideration: salt solutions with iron hydrate sludge filter-material pulps mixture of hydrated-salt sludge and filter-material pulps 16

17. CEMENTATION OF HYDRATED-SALT SLUDGE Assessment of the effect of a compound composition on flowability of cement-paste and mechanical strength of a solid product 17 Composition of hydrated- salt sludge, g/l Composition of compound, % by mass Waste / Cemen t Water/ Cement Loading capacity of compou nd, % by mass Flowabi- lity of compou nd, mm Mechanical strength of cement compound [  comp ] Fe(OH) 3 Na 2 SO 4 NaNO 3 Sludge Cemen t Time, days [  comp ], kg/cm 2 30 24059.540.51.471.115.0120 28 51 360 35 32 45 30 24057.142.91.331.014.1110 28 51 360 34 40 55 30 24054.545.51.20.913.690 28 330 52 95 15 27054.545.51.20.913.6140 32 63 159 32 49 73 15 2704060.00.670.510.070 28 56 155 169

18. CEMENTATION OF HYDRATED-SALT SLUDGE Assessment of the effect of a compound composition on flowability of cement-paste and mechanical strength of a solid product Findings of the experiments:  The waste/cement ratio is the key factor that influences the flowability of the cement paste and mechanical strength of obtained compound  If waste/cement ratio decreased, the cement-paste flowability drops considerably and the mechanical strength increases.  When the waste/cement ratio was ~1.5 (water/cement ratio equals 1.1), the mechanical strength does not reach required standardized even within a year. With smaller values of waste/cement ratio (water/cement ratio), the samples develop necessary strength, but very slowly  Reduction of the iron hydroxide content in a cement compound, other conditions being equal, results in increase of the cement-paste flowability, but is of little influence on mechanical strength of a compound  Decrease of the water/cement ratio to 0.5 results in notable increase of strength, but in this case the cement paste practically loses flowability. 18

19. CEMENTATION OF HYDRATED-SALT SLUDGE Assessment of the effect of sludge age on cement compound quality Sludge composition: Fe(OH) 3 – 30 g/l, Na 2 SO 4 – 30g/l, NaNO 3 – 240 g/l Waste/cement ratio – 0.67, water/cement ratio – 0.5, Loading capacity of cement compound – 19 wt %. Age of sludge, days Flowability of cement compound, mm Mechanical strength of cement compound Holding time, days [  comp ], kg/cm 2 No holding 157120275 5130250350 1070235288 1640235350 19

20. CEMENTATION OF HYDRATED-SALT SLUDGE Continuation Assessment of the effect of sludge age on quality of a cement compound Findings of the experiments:  With increasing age of the hydrated-salt sludge, the cement- paste flowability drops, and the mechanical strength variation does not show a clearly defined tendency. Furthermore, in all cases the mechanical strength is much higher than the standardized required value.  During preparation of a cement compound, the false setting effect was observed. On further mixing, this effect disappears. The false-setting start time varies depending on composition of solution, its age and the mixing conditions. 20

21. CEMENTATION OF FILTER MATERIAL PULPS Filter material pulps contents: spent ion-exchange resins (IER) spent filter perlite (FP) manganese dioxide sludge. IER is the mixture of cation and anion exchange resins in the ratio of 1:1 by weight 21

22. Assessment of loading capacity of cement compounds Content of components in pulp, wt % Waste /C Water /C Loading capacity of cement compound, wt % Mechanical strength of cement compound IERFPMnO 2 Holding time, days [  comp ], kg/cm 2 13.27.3-0.830.669.4 42 112 129 122 13.27.3-1.130.9010.9 42 112 65 102 13.27.3-1.701.3513.0 28 680 25 40 7.84.30.650.580.504.6 31 540 250 285 6.83.80.600.650.584.4 29 525 240 300 6.83.80.600.780.656.9 29 520 240 235 CEMENTATION OF FILTER MATERIAL PULPS 22

23. CEMENTATION OF FILTER MATERIAL PULPS Assessment of optimal loading capacity of cement compounds Continuation Findings of the experiments:  During cementation of filter-material pulps (water/cement ratio – 0.9), the loading capacity of a cement compound should not exceed 10 wt % of the solid pulp components to prevent significant reduction of mechanical strength of cement compounds.  With smaller cement-compound loading capacity and water/cement ratio, the samples are developing the strength that exceeds the required standardized value even within a month. 23

24. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Assessment of the effect of the superplasticizer and the method of its introduction on cement-paste flowability Sample composition: Fe(OH) 3 -15 g/l Na 2 SO 4 -19 g/l NaNO 3 -18.5 g/l IER -66 g/l FP - 36 g/l Pulp/cement ratio - 1.0 Loading capacity - 7 wt % 24

25. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Continuation Assessment of the effect of the superplasticizer and the method of its introduction on cement-paste flowability Findings of the experiments: Presence of the plasticizer in the pulp and the plasticizer-introduction method have no significant effect on flowability. Method of С-3 Introduction without С-3 Introduction of С-3 into Pulp Introduction of С-3 into Cement Paste рН781012781012781012 Flowability, mm 103 190 180 224 205164220 178 176- 175 200 175 - Mechanical Strength  comp , kg/cm 2 120110- 113 --125-130127113130 25

26. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Assessment of the effect of pulp age and pH on cement-paste flowability and cement-compound strength Pulp composition: Fe(OH) 3 -28.6 g/l Na 2 SO 4 - 24.2 g/l NaNO 3 - 24.6 g/l IER - 66 g/l FP - 36.3 g/l Pulp/cement ratio - 0.85 (equivalent of the water/cement ratio of 0.72) 26

27. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Continuation Assessment of the effect of pulp age and рН on cement-paste flowability and cement-compound strength Pulp рН Pulp Age, days Flow- ability,m Mechanical Strength  comp  in 35 days, kg/cm 2 7175185 7393195 71088125 721133118 731138145 73 167 710105185 721128136 731129128 121116155 27

28. Continuation Assessment of the effect of pulp age and рН on cement-paste flowability and cement-compound strength Findings of the experiments:  The pulps with рН =7: -the mechanical strength does not practically depend on the pulp age when cementing. -the flowability of the cement paste with the pulp aged 10 and less days is somewhat less than that of the cemented pulps aged 21 and 31 days.  With high alkalinity of the pulp (рН =12), increased time of its holding up to one month prior to cementation does not lead to a noticeable change in the cement-paste flowability and the mechanical strength of the cement compound. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS 28

29. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Assessment of the effect of the binder type on characteristics of cement compounds Pulp composition: Fe(OH) 3 -20 g/l Na 2 SO 4 -20 g/l NaNO 3 -260 g/l IER - 66 g/l FP - 36 g/l 29

30. Binder TypeS/BS/B Pulp рН Cement Paste Flowability, mm Mechanical Strength  comp  in 28 days, kg/cm 2 Portland Cement0.90.910165- Portland Cement0.912150225 Slag Portland Cement 0.912145125 Portland Cement1.012158- Slag Portland Cement 1.012140130 Portland Cement1.110195190 Slag Portland Cement 1.110145125 CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Continuation Assessment of the effect of the binder type on characteristics of cement compounds Findings of the experiments: Using both Portland cement and Slag Portland cement as a matrix, flowability and mechanical strength of cement compounds meet the requirements 30

31. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Frost Resistance and Water Resistance of Cement Compounds with ILW of PA Mayak Cement compound composition, wt %Frost Resistance Water Resistance Fe (OH) 3 Na 2 SO 4 NaNO 3 IERFPН2ОН2ОBinder  comp  frost, kg/cm 2  comp  water, kg/cm 2  comp  frost, kg/cm 2  comp  water, kg/cm 2 Portland cement ( Grade 500-DO) 0.340.2518.6--20.660.2250280215220 0.50 9.0--30.060.0220210220250 0.60 10.8--36.551.5120 10580 ---6.03.436.054.6155162120154 ---7.03.942.146.0757210295 0.80 10.82.71.533.450.0154178-- 0.90 11.32.91.634.847.6138152157160 Slag Portland cement 0.80 10.32.61.431.552.6225238170205 0.80 10.82.71.533.450.0196191120158 0.90 11.32.91.634.847.6103132146162 0.80 10.32.61.431.552.6162140168195 *  comp  frost,  comp  water - mechanical compressive strength of the samples tested for frost resistance and water resistance, and mechanical compressive strength of the reference samples 31

32. CEMENTATION OF MIXTURE OF HYDRATED-SALT SLUDGE AND FILTER-MATERIAL PULPS Continuation Frost resistance and water resistance of cement compounds with ILW of PA Mayak Findings of the experiments  The all solidified samples have the required frost resistance and water resistance  The investigations on the frost resistance and water resistance of the cemented ILW of PA Mayak showed that the ability of the samples to withstand multiple freezing/thawing cycles was sharply dropped if the test samples failed to reach not less than 75 % of the final strength value  Therefore, testing of the samples with 28 days holding (as provided for by the National Standard), often leads to negative findings (important for methodology of cement compound testing) 32

33. CEMENTATION OF TRITIUM-CONTAINING LRW Sample Composition, wt % Tritium fraction of (… ×10 -3 %) washed out from the sample within one day after different periods of cement compound hardering 0-1 days1-2 days 2-3 days 3-7 days 7-14 days SPC – 66.5, water – 33.5 2.41.40.80.50.4 PC – 28.5, clinoptilolite – 51.5, water – 20.0 4.72.41.40.50.4 MgO – 43.0, MgSO 4 –14.0, H 2 O – 43.0 5.03.21.81.61.7 Amount of Tritium Transferred to Contact Water from Cement Compounds with Waterproof Coat within One Day 33

34. CEMENTATION OF TRITIUM-CONTAINING LRW Findings of the experiments:  Within the first days of the contact, as revealed by all the experiments, the tritium leaching rate was equal to 1×10 -4 g/cm 2 day. In three days the tritium losses are reducing  The degree of tritium retention in the magnesia-compound- based samples is somewhat less than that when using SPC and PC Continuation Amount of Tritium Transferred to Contact Water from Cement Compounds with Waterproof Coat within One Day 34

35. CONCLUSION AND RECOMMENDATIONS:  A set of the experimental data has been obtained on characterization of the process of cementation of liquid ILW resulting from the reprocessing of PA Mayak’s SNF (hydrated- salt sludge, filter-material pulps and their mixtures0. Using the simulated LRW, it has been shown that the quality of the produced cement compound meets the national standard requirements if the Portland cement and Slug Portland cement are used as the matrix materials.  Next steps in period 2009-2010 to be taken: using the pilot facility, the technological process conditions will be developed and tested for a commercial cementation facility to provide the large-scale production of cement compounds with required quality and flowability to ensure uniform filling of storage facility compartments 35

36. Thank You for Your Attention Leonid Sukhanov Deputy director of SNF and RW Management Centre A.A.Bochvar Research Institute of Inorganic Materials 123060, Russia, Moscow, P.O. Box-369, Rogov Street, 5a Fax: 007-499-730-6427, E-mail: lpsoukh@bochvar.ru 36