Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes

• US 4,097,401 A
• Filed: 10/30/1975
• Issued: 06/27/1978
• Est. Priority Date: 07/30/1975
• Status: Expired due to Term

• Current Assignee: Gesellschaft Fur Kernforschung mbH
• Original Assignee: Gesellschaft FUER Kernforschung
• Inventors: Hild, Werner, Guber, Walter, Daruschy, Paul, Saidl, Jaroslav
• Primary Examiner(s): Padgett, Benjamin R.
• Assistant Examiner(s): Kyle, Deborah L.
• Application Number:
  US05/627,310
• Time in Patent Office: 971 Days
• Field of Search: 65/17, 65/1, 65/33, 252/301.1 W, 106/39.7
• US Class Current: 588/12
• CPC Class Codes: C03C 10/0036 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
• CPC Class Codes: G21F 9/305 Glass or glass like matrix C03B5/005 takes precedence; compositional aspects C03C

Abstract

Highly radioactive liquid wastes are permanently stored in a solidification matrix containing the components of a known borosilicate glass together with nucleation agents selected from the group consisting of oxides of Li, K, Mg, Mo and Cr, fluorides of those metals and of Al, and pure noble metals in the elemental form with particles with sizes smaller than 0.1 μm in diameter, and up to 35% by weight of waste fission and corrosion products or waste fission and corrosion products and gadolinium oxide. The product is produced by denitrating and calcining the radioactive waste solution, melting the calcined waste product together with a borosilicate frit containing nucleation agents at a temperature of between 1,050° and 1,200° C, and maintaining it in its melted state for 3 to 5 hours, subsequently cooling the resulting mixture until to a given temperature and maintaining it at this temperature for a given time period to permit nucleation to occur, then elevating the temperature of the mixture with an constant heating rate until to a given higher temperature, maintaining it at this higher temperature for about 24 hours, and finally cooling it with a constant cooling rate to ambient temperature.

Claims

1. A thermodynamically stable microcrystalline glass ceramic or glass ceramic-like product for permanent disposal and storage of highly radioactive wastes in a manner harmless to the environment or the biocycle, comprising:

(a) a solidifying matrix containing the components of a borosilicate glass including, by weight of the thermodynamically stable product, 35 to 50% SiO₂, 3 to 6% TiO₂, 5 to 10% Al₂ O₃, 3 to 6% B₂ O₃, 0 to 5% Na₂ O;

(b) a plurality of nucleation agents, including, by weight, 3 to 6% MgO, 8 to 10% Li₂ O and 3 to 6% K₂ O; and

(c) 20 to 30% by weight of waste fission and corrosion products;

said thermodynamically stable product is producible by a process with a highest process temperature used of 1200°

C or less.

2. A product as defined in claim 1, which contains at least one further nucleation agent, selected from the group consisting of oxides of Mo and Cr, fluorides of the metals Li, K, Mg, Mo, Cr and Al, and pure noble metals in the form of particles with sizes between 0.01 and 0.1 μ

m in diameter.

3. A product as defined in claim 1, which further contains 0 to 11% Gd₂ O₃, where the sum of the fission and corrosion products and Gd₂ O₃ is not more than 35% by weight.

6. A product as defined in claim 1 in which the glass further includes 3 to 6% CaO.

4. A thermodynamically stable microcrystalline glass ceramic or glass ceramic-like product for permanent disposal and storage of highly radioactive wastes in a manner harmless to the environment or the biocycle, comprising:

(a) a solidifying matrix containing the components of a borosilicate glass including, by weight of the thermodynamically stable product, 35 to 50% SiO₂, 3 to 6% TiO₂, 5 to 10% Al₂ O₃, 3 to 6% B₂ O₃, 0 to 5% Na₂ O;

(b) a mixture of nucleation agents consisting of, by weight, 8 to 10% Li₂ O, 3 to 6% K₂ O, 3 to 6% MgO and 1 to 1.5% noble metal fission products in elemental form with particle sizes between 0.01 and 0.1 μ

m in diameter; and

(c) 20 to 30% by weight of waste fission and corrosion products excluding Ru, Rh, and Pd;

said glass ceramic or glass ceramic-like product is producible with a highest process temperature used of 1200°

C or less.

5. A product as defined in claim 4, which further contains 0 to 11% Gd₂ O₃, where the sum of the fission and corrosion products and Gd₂ O₃ is not more than 35% by weight.

7. A product as defined in claim 4 in which the glass further includes 3 to 6% CaO.