Process and composition for the immobilization of high alkaline radioactive and hazardous wastes in silicate-based glasses

• US 8,575,415 B2
• Filed: 02/13/2012
• Issued: 11/05/2013
• Est. Priority Date: 03/20/2006
• Status: Expired due to Fees

• Current Assignee: Geomatrix Solutions, Inc.
• Original Assignee: Geomatrix Solutions, Inc.
• Inventors: Chekhmir, Anatoly, Gribetz, Arthur
• Primary Examiner(s): GREGORIO, GUINEVER S
• Application Number:
  US13/371,986
• Publication Number:
  US 20120217455A1
• Time in Patent Office: 631 Days
• Field of Search: None
• US Class Current: 588/11
• CPC Class Codes: B09B 3/29 involving a melting or softening step
• CPC Class Codes: C03C 1/002 Use of waste materials, e.g. slags
• CPC Class Codes: C03C 3/064 containing boron
• CPC Class Codes: C03C 3/091 containing aluminium
• CPC Class Codes: G21F 9/16 by fixation in stable solid media G21F9/305 takes precedence
• CPC Class Codes: G21F 9/305 Glass or glass like matrix C03B5/005 takes precedence; compositional aspects C03C

Abstract

The present invention provides processes to immobilize high alkaline radioactive and/or hazardous waste in a silicate-based glass, the waste containing one or more of radionuclides, hazardous elements, hazardous compounds, and/or other compounds. The invention also provides silicate-based glass compositions for use in immobilizing radioactive and/or hazardous waste.

Claims

1. A process for immobilizing high alkaline wastes in glass which achieves a high concentration of waste constituents (waste loading) comprising:

combining a waste stream having one or more of radionuclides, hazardous elements, and hazardous components with glass-forming components in proportion to achieve a mixture capable of forming a high alkaline silicate-based glass consisting essentially of about 1.6 to about 2.2 parts in weight percent of a combination of monovalent cation oxides (R₂O) and divalent cation oxides (RO), about 1 part in weight percent trivalent cation oxides (R₂O₃), and about 2 to about 3 parts in weight percent of a combination of tetravalent cation oxides (RO₂) and pentavalent cation oxides (R₂O₅), wherein Na₂O is present in an amount greater than 23 weight percent, Al₂O₃ is present in an amount greater than about 13 weight percent and less than about 20 weight percent, Si02 is present in an amount greater than about 30 weight percent and less than about 48 weight percent, and B₂O₃ and other flux components are present in a total amount greater than about 9 weight percent and less than about 15 weight percent;

melting the mixture to form a melted glass with integrated waste; and

solidifying the melted glass with integrated waste by cooling to form said high alkaline silicate-based glass.

2. The process of claim 1, wherein said melting step is performed at temperatures up to about 1150 degrees Celsius.

3. The silicate-based glass produced by the process of claim 1, wherein the ratio between the cation oxide components of the glass formed, approximates the ratio between the main components of natural high alkaline ultrabasic rock.

4. The silicate-based glass produced by the process of claim 1, wherein the cation oxide components of said silicate-based glass consisting essentially of:

about 1.6 to about 2.2 parts in weight percent of a combination of monovalent cation oxides (R₂O) and divalent cation oxides (RO);

about 1 part in weight percent of trivalent cation oxides (R₂O₃);

about 2 to about 3 parts in weight percent of a combination of tetravalent cation oxides (RO₂) and pentavalent cation oxides (R₂O₅); and

wherein Na₂O is present in an amount greater than 23 weight percent, Al₂O₃ is present in an amount greater than about 13 weight percent and less than about 20 weight percent, SiO₂ is present in an amount greater than about 30 weight percent and less than about 48 weight percent, and B₂O₃ and other flux components are present in a total amount greater than about 9 weight percent and less than about 15 weight percent.

5. The silicate-based glass produced by the process of claim 1, wherein the cation oxide components of the silicate-based glass consist essentially of:

about 1.6 to about 2.2 parts in weight percent of a combination of monovalent cation oxides (R₂O), including alkaline oxides, and divalent cation oxides (RO), including alkaline earth oxides;

about 1 part in weight percent of trivalent cation oxides (R₂O₃), including aluminum and ferric oxide;

about 2 to about 3 parts in weight percent of a combination of tetravalent cation oxides (RO₂), including silicon, zirconium and titanium, and pentavalent cation oxides (R₂O₅), including and phosphorus oxide; and

wherein Na₂O is present in an amount greater than 23 weight percent, Al₂O₃ is present in an amount greater than about 13 weight percent and less than about 20 weight percent, SiO₂ is present in an amount greater than about 30 weight percent and less than about 48 weight percent, and B₂O₃ and other flux components are present in a total amount greater than about 9 weight percent and less than about 15 weight percent.

6. The silicate-based glass produced by the process of claim 1, wherein the silicate-based glass has a viscosity of 20 to 100 poise at a temperature of about 1150 degrees Celsius.

7. The silicate-based glass produced by the process of claim 1, wherein the silicate-based glass has specific electrical conductivity ranging between about 0.1 Ω

<sup>−

1</sup> cm<sup>−

1</sup> to about 0.7 Ω

<sup>−

1</sup> cm<sup>−

1</sup> at a temperature of about 1150 degrees Celsius, that is acceptable for processing in vitrification melters.

8. The silicate-based glass produced by the process of claim 1, wherein the silicate-based glass meets the Vapor Hydration Test (VHT) requirements of less than about 50 grams per square meter per day, thus meeting current U.S. waste form acceptance criteria.

9. The silicate-based glass produced by the process of claim 1, wherein the silicate-based glass meets the Product Consistency Test (PCT) requirements of less than about 2 grams per square meter, as defined in the American Society for Testing and Materials (ASTM) C 1285, thus meeting current U.S. waste form acceptance criteria.

10. The silicate-based glass produced by the process of claim 1, wherein the U.S. Environmental Protection Agency'"'"'s (EPA) Toxicity Characteristic Leach Test Procedure (TCLP) (SW-846 Method 13 11) is performed and the silicate-based glass meets the U.S. EPA Universal Treatment Standard (UTS) for all of the analytes listed, thus meeting current U.S. waste form acceptance criteria.

11. The process of claim 1, wherein the divalent cation oxides (RO) are selected from the group consisting of alkaline oxides and alkaline earth oxides.

12. The process of claim 1, wherein the trivalent cation oxides (R₂O₃) are selected from the group consisting of alumina and ferric oxide.

13. The process of claim 1, wherein the pentavalent cation oxides (R₂O₅) are selected from the group consisting of silica, zirconia, titania, and phosphoric oxide.

14. A process for immobilizing high alkaline wastes in glass which achieves a high concentration of waste constituents (waste loading) comprising:

combining a waste stream having one or more of radionuclides, hazardous elements, and hazardous components with glass-forming components in proportion to achieve a mixture capable of forming a high alkaline silicate-based glass consisting in weight percent essentially of about 1.6 to about 2.2 parts of a combination of monovalent cation oxides (R₂O) and divalent cation oxides (RO), about 1 part trivalent cation oxides (R₂O₃), and about 2 to about 3 parts of a combination of tetravalent cation oxides (RO₂) and pentavalent cation oxides (R₂O₅), wherein Na₂O is present in an amount greater than 23 weight percent, Al₂O₃ is present in an amount greater than about 13 weight percent and less than about 20 weight percent, SiO₂ is present in an amount greater than about 30 weight percent and less than about 48 weight percent, and B₂O₃ and other flux components are present in a total amount greater than about 9 weight percent and less than about 15 weight percent;

melting the mixture to form a melted glass with integrated waste;

solidifying the melted glass with integrated waste by cooling to form said high alkaline silicate-based glass;

insuring that the melted glass with integrated waste meets the Vapor Hydration Test (VHT) requirements of less than about 50 grams per square meter per day;

insuring that the melted glass with integrated waste meets the Product Consistency Test (PCT) requirements of less than about 2 grams per square meter, as defined in the American Society for Testing and Materials (ASTM) C 1285; and

wherein the U.S. Environmental Protection Agency'"'"'s (EPA) Toxicity Characteristic Leach Test Procedure (TCLP) (SW-846 Method

     1311) is performed and the silicate-based glass meets the U.S. EPA Universal Treatment Standard (UTS) for all of the analytes listed, thus meeting current U.S. waste form acceptance criteria.

15. A process for immobilizing high alkaline wastes in glass which achieves a high concentration of waste constituents (waste loading) comprising:

combining a waste stream having one or more of radionuclides, hazardous elements, and hazardous components with glass-forming components in proportion to achieve a mixture capable of forming a high alkaline silicate-based glass consisting in weight percent essentially of about 1.6 to about 2.2 parts of a combination of monovalent cation oxides (R₂O) and divalent cation oxides (RO), about 1 part trivalent cation oxides (R₂O₃), and about 2 to about 3 parts of a combination of tetravalent cation oxides (RO₂) and pentavalent cation oxides (R₂O₅), wherein Na₂O is present in an amount greater than 24 weight percent, Al₂O₃ is present in an amount greater than about 13 weight percent and less than about 20 weight percent, SiO₂ is present in an amount greater than about 30 weight percent and less than about 48 weight percent, and B₂O₃ and other flux components are present in a total amount greater than about 9 weight percent and less than about 15 weight percent;

melting the mixture to form a melted glass with integrated waste; and

solidifying the melted glass with integrated waste by cooling to form said high alkaline silicate-based glass.

16. The process of claim 15, wherein Na₂O is present in an amount greater than 25 weight percent.

17. The process of claim 15, wherein Na₂O is present in an amount greater than 26 weight percent.

18. The process of claim 15, wherein Na₂O is present in an amount greater than 27 weight percent.

19. The process of claim 15, wherein Na₂O is present in an amount greater than 28 weight percent.

20. The process of claim 15, wherein Al₂O₃ is present in an amount greater than about 15 weight percent and less than about 20 weight percent.