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Alternative High-Level Waste Treatments at the Idaho National Engineering and Environmental Laboratory (1999) / Chapter Skim
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2 Calcine Characterization, Retrieval, and Dissolution
Pages 15-28

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From page 15...
... Dry calcine contains particles of various sizes, some of the right size to constitute a significant respirable hazard. Therefore, appropriate measures will have to be taken to ensure that releases cannot occur during sampling, installation of equipment for retrieval, and He actual ' In long calciner runs, after approximately a week of operation, the bed particles were used up and not needed as a substrate; that is, the chemical constituents in the radioactive waste "feed" stream were a sufficient input to solidify upon heating to form calcine particles.
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From page 16...
... Regarding the third source mentioned above, the only samples of actual calcine that have been retrieved from bins consist of two core samples collected from the second bin set (Calcined Solids Storage Facility (CSSF)
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From page 17...
... Temperature Stability Zirconia calcine Volatilize residual NO3 Reduce NO3 to 900 ppm in 15 min Volatilize Cs Cs recondenses at Volatilize Ru Volatilize F Alumina calcine Volatilize Ru Volatilize Cs Cs recondenses at Volatilize Sr Volatilize Ce Volatilize B Volatilize NO3 Volatilize Hg Sintering ejects Zirconia calcine Fluoride volatility at 900 °C Not volatilized: Fluidized-bed calciner 500 °C CaMg(CO3~2 dolomite Approximately 75% bed, 25 % fines Approximately 60% bed, 40% fines 200-500 ,um Meter 200-10 ,um (liameter Approximately 1.4 g/cm3 Approximately 2.7 g/cm3 Approximately 0.9 g/cm3 10-80% undisturbed 0.14 W/m-K at 38 °C 0.52 W/m-K at 138 °C 0.34 W/m-K at 600 °C 50-400 W/m3 14~00 W/m3 30°-34° from vertical >700 °C >200 °C 2700 °C Approximately 600 °C Approximately 400-600 °C Approximately 700 °C 450~50 °C 660 °C 2 650-700 °C <600 °C >800 °C >900 °C Approximately 800 °C Approximately 800 °C <600 °C 1200 °C 1200 °C 1200 °C < 600 °C < 600 °C at 1050 °C at 1200 °C at 1380 °C Density increases by 45% at 1200 °C in 24 hr 0% 4% 22% 85% Ce, Pu, U Calcine Characterization, Retrieval and Dissolution 17
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From page 18...
... 0.97 0.21 14.5 3.16 32.6 0.37 0.61 0.81 46.77 Zirconia Type Analytical Results (wt%) 4.51 0.46 22.8 12.2 19.3 1.06 0.56 6.04 33.07 This table reports data on calcine types generated in 1993.
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From page 19...
... TABLE 2-3 Summaly-Calcine Chemical Composition, Weight Percent Calculated from Flowsheets A1 CalcineZR Calcine CSSF #1CSSF #4CSSF #2CSSF #3CSSF #5CSSF #6b A12O388.2113.7035.7116.9115.8061.50 Al2(SO4~32.340.000 000 000 000 00 AlPO40.110.000.000.000.000.00 B2O30.682.351.451.992.260.44 CaCO30.001.321.953.492.140.96 CaF20.0052.7742.6150.9941.164.17 CaO0.004.540.882.296.730.61 Ca3(PO4) 20.000.000.401.610.010.00 CdO0.000.000.000.002.500.40 Cr2O30.000.380.260.450.120.12 Fe2O30.200.530.130.250.570.60 Gd2O30.000.010.000.000.000.00 HgO3.040.050.910.060.190.17 KAlO20.000.800.000.000.000.45 K2SO40.150.000.330.411.782.35 MgCO30.001.111.642.941.900.81 ~O0.000.000.000.010.020.17 MoO30.000.000.000.000.000.02 NaAlO20.001.090.360.570.8722.02 NaC10.000.170.000.060.280.36 NaF0.000.000.000.000.000.64 NaNO33.945.612.062.8310.562.09 Na3(PO4121.330.000.000.000.000.34 Na2SO40.000~000.160.121.960.28 Nb2Os0.000.000.000.000.260.00 NiO0.000.000.000.000.010.05 ~00.000.000.000.000.000.05 SnO20.000.220.160.210.150.01 ZrO20.0015.3310.9914.7910.731.39 To~1100.00100.00100.00100.00100.00100.00 To~1 Volume, flc317,24930,23838,54135,02042,079 To~1 Volume, m34888561,0919921,192 Specific Gravity1.201.601.441.591.541.20 Densi~, g/cm3 Mhss, kg259,754779,2851,226,2111,726,2091,526,7781,426,633 NOTE: Compositions for each CSSF for exisdng calcine were calcula~d as described in Garcia (1997: p.l9~.
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From page 20...
... RETRIEVAL, HANDLING, AND BLENDING OF CALCINE FROM BINS Several successive calcining campaigns produced calcines of different compositions (e.g., alumina- and zirconia-based calcines, each differing in the relative abundance of aluminum, zirconium, and other elemental constituents such as calcium) that were injected into the bin sets.
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From page 21...
... Certainly, as a minunum, Here will be some fines left on He bin surfaces, and Here might be s Indeed, sintered bonding may be speculated based on analogy with the gamma alumina used as catalyst supports in the oil refining industry. These materials are made under conditions similar to Idaho National Engineering and Environmental Laboratory (INEEL)
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From page 22...
... , by retrieving a large volume into one or several bins in which it is mixed to provide a large quantity of feed of a reasonably uniform composition, or by similarly blending a large volume after dissolution. Blending to provide large volumes of uniform feed is commonly used in successful radioactive waste treatment operations.
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From page 23...
... The committee concluded from Table 24 Hat a total UDS content of 1 to 10 percent is a reasonable estimate during fill-scale calcine dissolution operations, with dissolution of Al calcine near 90 percent and dissolution of Zr calcine near 98, assuming ample contact time. Dissolution values of 90 to 99 percent result in a total volume of UDS of 63.5 to 635 Calcine Characterization, Retrieval and Dissolution 23
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From page 24...
... Unfortunately, the testing program has been too restricted to obtain data for a representative variety of the full range of calcine samples present in the bins. Characteristics of IJDS While the dissolution data available to the committee are subject to considerable uncertainty for reasons outlined above, the data do suggest that parametric studies have identified the master variables of acid/calcine ratio, the final nitric acid concentration, contact time, and temperature.
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From page 25...
... (1995) , without readily available information to verify it, is that this form of alumina is absent in actual aged calcine.
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From page 26...
... These surrogates and the few samples of actual aged calcine available for testing are not fully representative of all the calcine contents in all six bins. Additional characterization studies are needed to provide definitive conclusions about the full range of calcine characteristics and bounds on important calcine properties.
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From page 27...
... will be adequate to meet the demanding separation factors required by the proposed flowsheets, particularly in meeting Class A waste levels. The key question, which is one of judgment as well as adequacy of resources devoted to the problem, is whether the required information can be obtained in parallel with design efforts, as suggested in Fluor Daniel, Inc.
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Key Terms

  • aged calcine
  • bin sets
  • kpa max
  • actual calcine
  • sample tubes

  • heel recycle
  • contact time
  • calcine dissolution
  • calcine properties
  • characterization data

  • bin set
  • six bin
  • fluidized bed
  • nitric acid
  • analytical results

  • total volume
  • calcine samples
  • calcine types
  • zirconia calcine
  • calcine particles

  • calcine retrieved
  • percent dissolution
  • environmental laboratory
  • ultimate fate
  • sintered bonding

  • percent range
  • retrieval operations
  • national engineering
  • required information
  • real calcine


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