Process for waste confinement by vitrification in metal cans

• US 10,538,448 B2
• Filed: 07/28/2009
• Issued: 01/21/2020
• Est. Priority Date: 07/28/2008
• Status: Active Grant

• Current Assignee: Commissariat a L'Energie Atomique (AES Corporation)
• Original Assignee: Commissariat a L'Energie Atomique (AES Corporation)
• Inventors: Gruber, Philippe, Pinet, Olivier, Rabiller, Helene, Boen, Roger, Bousquet, Nicolas, Dussossdy, Jean-Luc, Lacombe, Jacques
• Primary Examiner(s): Davis, Sheng H
• Application Number:
  US12/737,617
• Publication Number:
  US 20110144408A1
• Time in Patent Office: 3,829 Days
• Field of Search: None
• CPC Class Codes: B09B 3/29 involving a melting or softening step
• CPC Class Codes: C03B 5/005 of glass-forming waste materials disposal or transformation of solid waste in general B09B; treatment of radioactive waste G21F9/00
• CPC Class Codes: C03B 5/06 in pot furnaces C03B5/02 takes precedence
• CPC Class Codes: Y02P 40/50 Glass production, e.g. reusing waste heat during processing or shaping

Abstract

Process for confinement of waste containing at least one chemical species to be confined, by in-can vitrification in a hot metal can into which waste and a vitrification additive are added, the waste and the vitrification additive are melted to obtain a glass melt which is then cooled, characterised in that at least one oxidising agent is also added into the metal can and in that the concentration of oxidising agent(s) expressed as oxide(s) in the glass melt is between 0.1 and 20% by mass, preferably 4 and 20% by mass, even more preferably 5 and 15% by mass, and even more preferably 10 and 13% by mass of the glass melt mass.

Claims

1. Process for confining a waste containing at least one chemical species to be confined, by vitrification in a heated metal can composed of either an iron-based alloy or a nickel-based alloy, wherein the process consists of adding only the waste, a vitrification additive and at least one oxidizing agent into the iron-based alloy or nickel-based alloy metal can, such that the waste and the vitrification additive melt in reactive contact with said metal can during the vitrification process for producing a glass melt and the glass melt is cooled, characterized in that the vitrification additive is an oxide or mixture of oxides selected from the group consisting of:

SiO₂, B₂O₃, Al₂O₃, Na₂O, Fe₂O₃, CaO, Li₂O, ZnO, ZrO₂, and Nd₂O₃ and wherein the at least one oxidizing agent is selected from the group consisting of multivalent oxidizing species of iron, chromium, vanadium, antimony, titanium, arsenic, cerium, manganese, chromium, ruthenium and mixtures thereof, and wherein the at least one oxidizing agent is provided separately from the vitrification additive, wherein the at least one oxidizing agent is not part of the waste wherein either the at least one oxidizing agent is mixed with the waste before the waste is fed into the metal can, or the at least one oxidizing agent is mixed with the vitrification additive before either the vitrification additive is fed into the metal can, or the oxidizing agent is fed directly into the metal can, separately from the waste and the vitrification additive, and wherein the concentration of said at least one oxidizing agent expressed as an oxide or oxides in the glass melt is in a range of from 0.1 to 20% by mass of the mass of the glass melt for allowing minimal reduction of the glass melt by the metal can to occur while minimizing degassing and foaming from occurring during the vitrification process thereby improving the glass melt properties.

2. Process according to claim 1, wherein said multivalent oxidizing species is selected from the group consisting of Fe³⁺, Ce⁴⁺, Mn⁴⁺, Sb⁵⁺, As⁵⁺, V⁵⁺, Ru⁴⁺, and mixtures thereof.

3. Process according to claim 1, wherein said at least one oxidizing agent is selected from the group consisting of one or more oxides or precursors of oxides.

4. Process according to claim 1, wherein said at least one oxidizing agent is an agent that has a limiting effect on the corrosion of the metal can.

5. Process according to claim 1, wherein the concentration of the oxidizing agent, for an oxidizing agent used alone, is in a range of from 0.1% to 1% by mass when the oxidizing species is chromium (Cr³⁺), expressed as Cr₂O₃;

from 1 to 15% by mass when the oxidizing agent is vanadium (V⁵⁺), expressed as V₂O₃;

from 0.5 to 8% by mass when the oxidizing agent is antimony (Sb⁵⁺), expressed as Sb₂O₅;

from 1 to 15% by mass when the oxidizing agent is titanium (Ti⁴⁺), expressed as TiO₂;

from 0.5% to by mass when the oxidizing agent is arsenic (As⁵⁺), expressed as As₂O₅;

from 0.5 to 10% by mass when the oxidizing agent is cerium (Ce⁴⁺), expressed as CeO₂;

from 0.1 to 2% by mass when the oxidizing agent is manganese (Mn⁴⁺), expressed as MnO₂; and

from 1 to 20% by mass when the oxidizing agent is iron (Fe³⁺), expressed as Fe₂O₃.

6. Process according to claim 5, wherein when the oxidizing agent is iron, the concentration is in a range from 1.0 to 15% by mass.

7. Process according to claim 6, wherein the concentration is in a range from 3.0 to 13% by mass.

8. Process according to claim 7, wherein the concentration is in a range from 4.0 to 13% by mass.

9. Process according to claim 8, wherein the concentration is in a range from 5.0 to 13% by mass.

10. Process according to claim 9, wherein the concentration is in a range from 10 to 13% by mass.

11. Process according to claim 10, wherein the concentration is in a range from 12 to 13% by mass.

12. Process according to claim 11, wherein the concentration is 12.6% by mass.

13. Process according to claim 1, wherein the oxidizing agent is added in the form of a powder.

14. Process according to claim 13, wherein the powder is a mixture of oxide powders.

15. Process according to claim 1, wherein the oxidizing agent is added in the form of a glass.

16. Process according to claim 15, wherein the oxidizing agent is selected from the group consisting of a glass frit, glass beads and glass pieces.

17. Process according to claim 1, wherein the oxidizing agent is fed into the metal can continuously.

18. Process according to claim 1, wherein the oxidizing agent is fed into the metal can discontinuously.

19. Process according to claim 1, wherein the vitrification additive is either in the form of a mixture of oxide powders or a glass.

20. Process according to claim 19, wherein when the vitrification additive is a glass, it is selected from the group consisting of a glass frit, glass beads and glass pieces.

21. Process according to claim 1, wherein the vitrification additive is a borosilicate glass or a silicate glass.

22. Process according to claim 1, wherein the chemical element to be confined is selected from the group of the following chemical elements:

Al, As, B, Ba, Ca, Ce, Cd, Cr, Cs, F, Fe, Gd, Hg, Li, Mg, Mn, Mo, Na, Ni, Nd, P, Pb, S, Sb, Tc, Ti, V, Zn, Zr, actinides, platinoids and mixtures thereof.

23. Process according to claim 22, wherein the chemical element to be confined is a radioactive isotope.

24. Process according to claim 1, wherein the waste is in a solid or liquid form.

25. Process according to claim 24, wherein the nuclear waste is a radioactive liquid effluent.

26. Process according to claim 25, wherein the radioactive liquid effluent is a radioactive solution.

27. Process according to claim 26, wherein the radioactive solution is a medium activity solution.

28. Process according to claim 24, wherein the nuclear waste is a cullet of radioactive liquid effluent.

29. Process according to claim 28, wherein the nuclear waste is a medium activity effluent.

30. Process according to claim 1, wherein the waste is a waste derived from the incineration of radioactive waste or household waste.

31. Process according to claim 1, wherein the glass melt is cooled in the metal can in which it was prepared.

32. Process according to claim 1, wherein the concentration of the oxidizing agent in the glass melt ranges from 4.0 to 20% by mass.

33. Process according to claim 32, wherein the concentration of the oxidizing agent in the glass melt ranges from 5.0 to 15% by mass.

34. Process according to claim 33, wherein the concentration of the oxidizing agent in the glass melt ranges from 10 to 13% by mass.

35. Process according to claim 1, wherein the vitrification additive is a glass frit comprising about 80% of SiO₂, B₂O₃, Al₂O₃ and Na₂O.

36. Process according to claim 1, wherein the vitrification additive comprises from 20 to 80% by mass of SiO₂, from 0 to 40% by mass of B₂O₃, from 0 to 20% by mass of Fe₂O₃, from 0 to 20% by mass of Al₂O₃, from 0 to 20% by mass of CaO, from 0 to 20% by mass of Li₂O, from 0 to 20% by mass of ZnO, and from 0 to 15% by mass of ZrO₂.

37. Process for confining a waste containing at least one chemical species to be confined, by vitrification in a heated metal can composed of either an iron-based alloy or a nickel-based alloy, wherein the waste and a vitrification additive are fed into the iron-based alloy or nickel-based alloy metal can, such that the waste and the vitrification additive melt in reactive contact with said metal can during the vitrification process for producing a glass melt with improved glass melt properties, and the glass melt is cooled, characterized in that the vitrification additive is not part of the waste and includes oxides selected from the group consisting of:

SiO₂, B₂O₃, Al₂O₃, Na₂O, Fe₂O₃, CaO, Li₂O, ZnO, ZrO₂, and Nd₂O₃ and includes additional additives selected from glass precursors consisting of carbonates, nitrates, oxides, borides, nitrates, carbides, sulphates, sulphides, hydroxides and mixtures thereof and wherein at least one oxidizing agent selected from the group consisting of multivalent oxidizing species of iron, chromium, vanadium, antimony, titanium, arsenic, cerium, manganese, chromium, ruthenium and mixtures thereof is further fed into the metal can as an addition, independent and separate from the addition of the waste and said vitrification additive, said oxidizing agent(s) expressed as an oxide or oxides in the glass melt, added in a concentration ranging from 0.1 to 20% by mass of the mass of the glass melt for allowing minimal reduction of the glass melt by the metal can to occur while minimizing degassing and foaming from occurring during the vitrification process.