Toward Understanding the Effect of Low‐Activity Waste Glass Composition on Sulfur Solubility

The concentration of sulfur in Hanford low-activity waste (LAW) glass melter feed will be maintained below the point where the salt accumulates on the melt surface. The allowable concentrations may range from near zero to over 2.05 wt% (of SO3 on a calcined oxide basis) depending on the composition of the melter feed and processing conditions. If the amount of sulfur exceeds the melt tolerance level, a molten salt will accumulate which may upset melter operations and potentially shorten the useful life of the melter. At the Hanford site, relatively conservative limits have traditionally been placed on sulfur loading in melter feed, which in turn significantly increases the amount of LAW glass that will be produced. Crucible-scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. An empirical model was developed to predict the solubility of SO3 in glass based on 253 simulated Hanford LAW glass compositions. This model represents the data well, accounting for over 85% of the variation in data, and was well validated. The model was also found to accurately predict the maximum amount of sulfur in melter feed that did not form a salt layer in 13 scaled melter tests of simulated LAW glasses. The model can be used to help estimate glass volumes and make informed decisions on process options (e.g., scale of supplemental LAW treatment facility, and pretreatment facility performance requirements). The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that increase sulfur solubility most are Li2O > V2O5 > CaO ≈ P2O5 > Na2O ≈ B2O3 > K2O. The components that decrease sulfur solubility most are Cl > Cr2O3 > Al2O3 > ZrO2 ≈ SnO2 > Others (i.e., the sum of minor components) ≈SiO2. The order of component effects is similar to previous literature data, in most cases.

[1]  Greg F. Piepel A Component Slope Linear Model for Mixture Experiments , 2007 .

[2]  Jason L. Loeppky,et al.  Augmenting Scheffé Linear Mixture Models with Squared and/or Crossproduct Terms , 2002 .

[3]  N. Hyatt,et al.  Incorporation and speciation of sulphur in glasses for waste immobilisation , 2009 .

[4]  C. Jantzen,et al.  Dependency of Sulfate Solubility on Melt Composition and Melt Polymerization , 2012 .

[5]  R. Hand,et al.  Sulphate incorporation and glass formation in phosphate systems for nuclear and toxic waste immobilization , 2008 .

[6]  R. W. Goles,et al.  Test Summary Report INEEL Sodium-Bearing Waste Vitrification Demonstration RSM-01-1 , 2001 .

[7]  W. Stolte,et al.  Determination of Sulfur Environments in Borosilicate Waste Glasses Using X-ray Absorption Near-Edge Spectroscopy , 2004 .

[8]  D. Neuville,et al.  Quantitation of sulfate solubility in borosilicate glasses using Raman spectroscopy , 2009 .

[9]  P. Hrma,et al.  Drainage of primary melt in a glass batch , 1991 .

[10]  D. Peeler An Assessment of the Sulfate Solubility Limit for the FRIT 418 - Sludge Batch 2/3 System , 2004 .

[11]  D. Neuville,et al.  Sulfur behavior in silicate glasses and melts: Implications for sulfate incorporation in nuclear waste glasses as a function of alkali cation and V2O5 content , 2007 .

[12]  K. Fox,et al.  Retention of Sulfate in Savannah River Site High‐Level Radioactive Waste Glass , 2010 .

[13]  W. Buchmiller,et al.  Preliminary Investigation of Sulfur Loading in Hanford LAW Glass , 2004 .

[14]  N. Soelberg,et al.  Test Summary Report INEEL Sodium-Bearing Waste Vitrification Demonstration RSM-01-2 , 2002 .

[15]  D. Matson,et al.  Chemical and Structural Elucidation of Minor Components in Simulated Hanford Low-Level Waste Glasses , 1996 .

[16]  M. Plodinec,et al.  Evaluation of glass as a matrix for solidifying Savannah River Plant waste: properties of glasses containing Li/sub 2/O , 1979 .

[17]  I. Pegg,et al.  Raman studies of sulfur in borosilicate waste glasses: sulfate environments , 2001 .

[18]  T. Hanada,et al.  Compositional dependence of solubility of sulphate in silicate glasses , 1998 .

[19]  M. Zitnik,et al.  A Multi-spectroscopic Investigation of Sulphur Speciation in Silicate Glasses and Slags , 2010 .

[20]  John D. Vienna,et al.  Sulfur Partitioning During Vitrification of INEEL Sodium Bearing Waste: Status Report , 2001 .

[21]  John D. Vienna,et al.  The effects of melting reactions on laboratory-scale waste vitrification , 1995 .

[22]  S. Weisenburger,et al.  The Materials Balance-Scientific Fundamentals for the Quality Assurance of Vitrified Waste , 1981 .

[23]  D. Matson,et al.  Phosphate-sulfate interaction in simulated low-level radioactive waste glasses , 1995 .

[24]  A. K. Tyagi,et al.  Role of Sulfate in Structural Modifications of Sodium Barium Borosilicate Glasses Developed for Nuclear Waste Immobilization , 2008 .

[25]  P. Hrma,et al.  Sulfate Retention and Segregation in Simulated Radioactive Waste Borosilicate Glasses , 2000 .

[26]  P. Hrma,et al.  Mechanism of sulfate segregation during glass melting , 2002 .

[27]  M. T. Coolbaugh,et al.  Compositional dependence of redox equilibria in sodium silicate glasses , 1994 .

[28]  T. Lorier Initial Sulfate Solubility Study for Sludge Batch 4 (SB4) , 2005 .

[29]  David K. Peeler,et al.  Glass Formulation Development for INEEL Sodium-Bearing Waste , 1999 .