# Patent

## Title
Mitigation of secondary phase formation during waste vitrification

## Abstract

A method for vitrification of waste to reduce the formation of persistent secondary phases comprising separating at least one glass frit constituent from an initial glass frit to form a modified glass frit. The waste, modified glass frit, and the at least one glass frit constituent are mixed together with the modified glass frit and the at least one glass frit constituent being added as separate components. The resulting mixture is vitrified.

## Background
CROSS REFERENCE TO RELATED PATENT APPLICATIONS
This is a continuation of U.S. patent application Ser. No. 12/677,490, titled “Mitigation of Secondary Phase Formation During Waste Vitrification,” filed on 10 Mar. 2010, issued as U.S. Pat. No. 8,530,718, which is a continuation of International Patent Application No. PCT/US2008/076381, filed on 15 Sep. 2008, which claims the benefit of Japanese Patent Application Serial No. 2007-244041, filed 20 Sep. 2007, all of which are incorporated by reference herein in their entirety.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to improvements in the process for vitrifying waste materials, and more particularly, to improvements especially for the vitrification of radioactive waste materials by changing the chemical form and physical characteristics of additives that are added to the waste material to obtain a suitable vitrified product, such that the reactions between the additives and the waste materials suppress the formation of undesirable secondary phases.
2. Description of Related Art
Large quantities of radioactive nuclear waste materials that are produced as byproducts from activities such as weapons programs, nuclear fuel recycling, medical isotope production, are stored in various countries around the world. Vitrification of these waste materials to produce a durable glass product is the preferred approach for treating and disposing of these waste materials because of the high durability of the glass waste form as compared to other waste forms such as grout. Vitrification of radioactive high level waste (HLW) to produce a borosilicate glass product is the internationally accepted waste treatment method. Vitrification of the waste materials is done in melters such as Joule Heated Ceramic Melters (JHCM), Induction Melters (IM), Cold Crucible Melters (CCM), and the like.
In waste vitrification, the waste materials are mixed with appropriate amounts of raw materials, known as “additives”, and melted at a high temperature (typically 1150° C. for JHCMs, typically somewhat lower for IMs, and typically somewhat higher for CCMs) in order to produce glass products that meet pre-specified product quality requirements. The product quality requirements mostly relate to the chemical durability of the glass product as measured by standard test procedures.
Many waste materials are stored in tanks in slurry or solution form. The additives have been used either in the form of pre-melted chemicals (frit) with a specified composition, or raw materials in the form of minerals or chemicals. The additive minerals or chemicals are commonly referred to as glass forming chemicals (GFCs). In either case, the waste materials with the additives are designed to melt and form a glass product with a predetermined oxide composition. The waste materials mixed with the appropriate amounts of frit or GFCs are referred to as melter feeds. These materials may be mixed either outside or inside the melter.
In many situations, the melter feed is introduced from the top of the melter to the melt pool surface so that a layer of feed material covers the hot glass melt underneath. This layer is commonly referred to as the cold-cap. The cold-cap extends from partially melted melter feed in contact with the melt pool to unreacted melter feed at the top. In other situations such as batch-style induction melters, the melt zone progresses from the hot wall on the outside into the bulk. Consequently, in this case also there is a boundary zone between predominantly melted material and predominantly unmelted feed material. This zone is also referred to as a cold cap. Reactions in the cold-cap, and controlling these reactions, are the key approach to mitigating undesirable secondary phase formation.
Due to the complexity of the waste materials, and the number of different constituents, persistent secondary phases are often formed during the melting process. The extent of formation of these secondary phases depend on various factors such as concentrations of troublesome constituents, the types of additives, waste processing rates, processing temperatures, etc. One of the common waste constituents that show a tendency to form secondary phases during nuclear waste vitrification is molybdenum. Formation of secondary molybdate phases is undesirable because they lead to both processing and product quality issues. Molybdate phases are easily leachable, leading to unacceptable product quality. In addition, these secondary phases tend to selectively incorporate high concentrations of other components such as cesium leading to additional product quality issues. Alkali molybdate phases can accumulate on the melt surface causing excessive corrosion of melter components that are in contact with this phase. Alkaline earth molybdates tend to sink to the bottom of the melter and accumulate. The accumulation of molybdate secondary phases at the melter bottom can cause problems with glass discharge, especially for melters that use a bottom discharge.
The molybdate phase formation is a result of the high molybdenum concentration in the HLW feed to the vitrification facility in combination with complex reaction kinetics in the cold-cap. The molybdenum secondary phase formation initially occurs near the interface between the molten glass pool and the cold-cap. Our studies showed that kinetically controlled cold-cap conversion processes are responsible for the generation of molten molybdate salt, rather than solubility limits of molybdates in the underlying glass melt.
When the melter feed is prepared by mixing glass frit with the HLW material in slurry form, or when HLW is fed continuously and glass frit is fed periodically in small batches to the center of the cold-cap, the molybdate secondary phase tends to form before the underlying glass melt reaches saturation with respect to molybdate. If the feed chemistry can be altered to suppress the molybdate secondary phase formation until its concentration reaches close to the solubility limit, the amount of waste incorporated into unit amount of glass produced (waste loading) can be increased leading to substantial cost savings in HLW treatment and disposal.
Sulfur is another component in waste streams that at high concentrations causes the formation of secondary sulfate layers during the melting process. The sulfate concentration in the glass that causes secondary phase formation can be as low as 0.5 wt % in certain glass compositions. In this case also, the secondary sulfate layer is formed well before the underlying glass melt reaches sulfate solubility limit. Again, improvements to the feed chemistry by judicious choice of additives to delay the formation of sulfate secondary phases until the sulfate concentration reaches close to the solubility limit, has enormous economical advantage. The same principles should be effective for mitigating other troublesome salt-forming species such as chlorine, fluorine, chromium (chromate), and phosphorous.
Accordingly, it is an object of the present invention to provide improved efficiency for vitrification of waste material, especially for radioactive waste materials.
It is a further object of the present invention to reduce the tendency to form secondary phases during vitrification by tailoring the glass former additives, thus increasing the amount of waste incorporated into unit amount of glass produced.
SUMMARY OF THE INVENTION
The above objectives are accomplished according to the present invention by providing a method for vitrification of high level waste to reduce the formation of persistent secondary phases comprising providing a high level waste for vitrification; providing a glass frit additive for mixing with the high level waste; providing at least one glass frit constituent selected from the group consisting of Al2O3, B2O3, and SiO2 separately from the glass frit additive for mixing with the high level waste; and, feeding the high level waste, the glass frit additive and the glass frit constituent to a melter to form a mixture for vitrification of the high level waste in which formation of secondary phases is suppressed.
In a further advantageous embodiment, the method includes the step of providing the glass frit additive in the form selected from the group consisting of glass beads, cylindrical glass fiber cartridges, glass powder, and glass flakes.
In a further advantageous embodiment, the method includes the step of redistributing selected components of the glass frit additive into individual glass frit constituents for mixing as raw chemicals with the high level waste separately from the glass frit additive.
In a further advantageous embodiment, the method includes the step of redistributing all components of the glass frit additive into individual glass frit constituents for mixing as raw chemicals with the high level waste.
In a further advantageous embodiment, the method includes the step of providing the glass frit additive having Al2O3, B2O3, and SiO2, and redistributing at least a portion of at least one of the Al2O3, B2O3 and SiO2 from the glass frit additive to provide at least one redistributed glass frit constituent for mixing separately as raw chemicals with the high level waste.
In a further advantageous embodiment, the method includes the step of redistributing all of the Al2O3 and a portion of the B2O3 from the glass frit additive to individual glass frit constituents for mixing separately with the high level waste so that the removed Al2O3 and B2O3 totals approximately at least 7 wt % by weight of the mixture.
In a further advantageous embodiment, the method includes the step of combining 15.81 wt % of the high level waste, 77.29 wt % of the glass frit additive, and 6.9 wt % of the Al2O3 and B2O3 for feeding to the melter.
In a further advantageous embodiment, the method includes the step of redistributing all of the Al2O3 and a portion of the B2O3 and the SiO2 from the glass frit additive to individual glass frit constituents for mixing separately with the high level waste so that the removed Al2O3 and B2O3 totals approximately 7 wt % and the SiO2 totals approximately 7 wt % of the mixture.
In a further advantageous embodiment, the method includes the step of combining 15.81 wt % of the high level waste, 70.56 wt % of the glass frit additive, 6.9 wt % of the redistributed Al2O3 and B2O3 and 6.73 wt % of the redistributed SiO2 for feeding to the melter.
In a further advantageous embodiment, the method includes the step of separately feeding the high level waste, the glass frit additive and the at least one glass frit constituent to the melter.
In a further advantageous embodiment, the method includes the step of mixing the high level waste, the glass frit additive and the at least one glass frit constituent together and feeding the resulting mixture to the melter.
In a further advantageous embodiment, the method includes the step of mixing the high level waste with the at least one glass frit constituent prior to feeding to the melter.
In a further advantageous embodiment, the method includes the step of providing the high level waste, the glass frit additive, and the at least one glass frit constituent in powder form for feeding to the melter.
In a further advantageous embodiment, a composition is made according to the method described above comprising about 15 wt % of the high level waste, about 70 wt %-78 wt % of the glass frit additive, and about 7 wt %-15 wt % of the glass frit constituent selected from the group consisting of Al2O3, B2O3, and SiO2 for feeding to a melter to form a borosilicate glass compound.



BRIEF DESCRIPTION OF THE DRAWINGS
The construction designed to carry out the invention will hereinafter be described, together with other features thereof. The invention will be more readily understood from a reading of the following specification and by reference to the accompanying drawings forming a part thereof, wherein an example of the invention is shown and wherein:
FIG. 1 shows a flow chart of the method for mitigation of secondary phase formation during waste vitrification according to the present invention.



DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
With reference to FIG. 1, the invention will now be described in more detail. In studies designed to develop and demonstrate the invention, oxide compositions were formed by combining 15.81 wt % of High Level Waste (HLW) simulant and 84.19 wt % of glass frit. The HLW simulant contained about 8.64 wt % of MoO3 for conducting the process discussed herein. The glass composition used in the studies had a waste loading of 15.81 wt %. The resulting glass had MoO3 concentration of 1.37 wt %.
Additives for mixing with the waste material were provided in the form of pre-melted glass frit beads. The 15.81 wt % of HLW simulant is provided in slurry form. Appropriate amounts of glass frit beads, totaling approximately 84.19%, were added so that the resulting glass melt formed the desired oxide composition having the characteristics noted above.
Heat treatment of the mixture in the range of 700 to 900° C. in gradient or isothermal furnaces resulted in the formation of the undesirable molybdate phases. Both alkali and alkaline earth molybdates were identified. Even though the nominal operating temperature of a typical glass melter is 1150° C., formation of molybdate phases at any temperature in the range of 100 to 1150° C. is of concern because the temperature in the cold-cap region ranges from about 100° C. at the top surface to about 1150° C. at the glass melt interface.
Next, a set of tests was designed to identify changes to the above formulation by manipulating the additives that would eliminate molybdate phase formation without any changes to the resulting product glass composition. As detailed herein below, this is accomplished by removing a portion of the additives from the glass frit prior to combination with the HLW slurry, reformulating the frit, and adding the components removed from the glass frit directly to the HLW slurry.
Crucible-scale tests were conducted to identify the most promising frit modifications to eliminate molybdate phase formation. It was found that removal of all Al2O3 and part of the B2O3 from the glass frit (initial glass frit), and the addition of the removed Al2O3 and B2O3 directly to the HLW slurry separately from the glass frit was an effective approach to the suppression of molybdate phase formation. To confirm this observation, a test was conducted in a continuously fed, Joule Heated Ceramic Melter (JHCM) during which about 20 kg of glass was produced over a period of about 64 hours. The combination added to the melter of the HLW simulant, the modified glass frit, the Al2O3 and B2O3 additives removed from the glass frit and added directly to the HLW simulant, resulted in a final glass composition that was unchanged but eliminated the problematic secondary phase formations.
About 10% by weight of the Al2O3 and B2O3 additives contained in the glass frit were removed and added directly to the HLW simulant. Preferably, this includes removing all of the Al2O3. Removal of B2O3 from the glass frit comprises the remainder of the 10% by weight being removed from the glass frit. In total, removal of all the Al2O3 and a portion of the B2O3 comprises 10% by weight of the total glass frit.
In a preferred embodiment, the target glass composition was obtained by combining 15.81 wt % of HLW simulant, 77.29 wt % of the modified glass frit, and 6.9 wt % of the removed Al2O3 and B2O3. The waste loading and the final glass composition were unchanged as desired. At the end of the test, examination showed the melter glass to be free of separate molybdate phases. The addition of all the Al2O3 and part of the B2O3 removed from the glass frit directly to the HLW simulant suppresses molybdate phase formation by being more effective at minimizing molybdate phase formation in the cold-cap area so that it does not accumulate. It also promotes the formation of desirable transient phases that incorporate molybdenum, thereby preventing the formation and segregation of a separate molybdate phase. Small molybdate droplets that may form in the cold-cap area are redissolved, thereby preventing the accumulation of molybdate phases in the melter. These tests were designed such that redistribution of the original frit constituents between the modified frit and the HLW simulant will result in minimal changes to the overall process.
Additional crucible tests were conducted to identify other promising frit modifications to eliminate molybdate phase formation. It was found that redistribution of all Al2O3 and part of the B2O3 and SiO2 from the glass frit, and the addition of the removed Al2O3, B2O3 and SiO2 directly to the HLW slurry separately from the glass frit was an even more effective approach to the suppression of molybdate phase formation than the redistribution of Al2O3 and B2O3 alone.
In a further advantageous embodiment, the target glass composition was obtained by combining 15.81 wt % of HLW simulant, 70.56 wt % of the modified glass fit, 6.9 wt % of the removed Al2O3 and B2O3 and 6.73 wt % of removed SiO2. The waste loading and the final glass composition were unchanged as desired. Examination of the heat treated crucible glass samples showed them to be free of separate molybdate phases.
The above tests conclusively demonstrated that redistribution of frit constituents is an effective method to suppress the formation and accumulation of separate molybdate phases during HLW simulant feed processing in JHCMs. In initial tests, only about 7%-10% by weight of the glass frit constituents were redistributed, which provided acceptable results. Further crucible tests showed that redistribution of about 15% by weight of selected amounts of glass frit constituents including Al2O3, B2O3 and SiO2 was even more effective in suppressing separate molybdate phase formation.
Accordingly, a method for vitrification of high level waste to reduce the formation of persistent secondary phases is disclosed that comprises the steps of providing about 15% of a high level waste for vitrification (16); providing about 85% of a glass frit additive for mixing with the high level waste (10); redistributing at least about 7%-15% by weight of the glass frit constituents (14) for mixing separately with the high level waste so that less than approximately 70%-78% of the total mixture comprises the glass frit (12); and, feeding the high level waste, the glass frit, and the redistributed glass fit constituents to a melter (18) for vitrification of the high level waste so that formation of secondary phases is suppressed.
Different variations of the invention that will also improve the suppression of secondary phase formations include: 1) redistribution of a higher percentage of the glass frit components to be added separately to the HLW slurry; 2) complete replacement of glass fit with raw chemicals that are added directly to the HLW slurry; 3) redistribution of glass frit components without change to the product glass composition; 4) redistribution of glass frit components and reformulation of the glass with change to the product glass composition; 5) redistribution of glass frit components in any of the ways described above to suppress secondary phase formation in an existing glass composition; 6) redistribution of glass frit components in any of the ways described above to suppress secondary phase formation so that waste loading in the glass can be increased; 7) Redistribution of glass frit components in any of the ways described above where the frit is in the form of glass beads (nominally 2 to 3 mm in diameter); 8) redistribution of glass frit components in any of the ways described above where the frit is in the form cylindrical glass fiber cartridges (nominally 70 mm diameter and 70 mm length); 9) redistribution of glass frit components in any of the ways described above where the frit is in the form of a powder (nominally less than 80 mesh); 10) redistribution of glass frit components in any of the ways described above where the frit is in the form of glass flakes.
The above innovations can be implemented in any and all of the following glass making processes: 1) JHCM in which the glass frit and HLW slurry with the redistributed glass frit components are fed separately to the melter; 2) JHCM in which the glass frit and HLW slurry with the redistributed glass frit components are mixed and fed together to the melter; 3) JHCM in which the glass frit, the redistributed glass frit components and calcined HLW are fed to the melter as solid powders; 4) Cold Crucible Melters (CCM) in which the glass frit and HLW slurry with the redistributed glass frit components are fed separately to the melter; 5) CCM in which the glass frit and HLW slurry with the redistributed glass frit components are mixed and fed together to the melter; 6) CCM in which the glass frit, the redistributed glass frit components, and calcined HLW are fed to the melter as solid powders; 7) Induction Melters (IM) in which the glass frit and HLW slurry with the redistributed glass frit components are fed separately to the melter; 8) IM in which the glass frit and HLW slurry with the redistributed glass fit components are mixed and fed together to the melter; 9) IM in which the glass frit, the redistributed glass frit components, and calcined HLW are fed to the melter as solid powders.
The invention has application in the suppression of secondary phases formed by molybdenum and sulfur and the same principles should be effective for mitigating other troublesome salt-forming species such as chlorine, fluorine, chromium (chromate), and phosphorous.
While a preferred embodiment of the invention has been described using specific terms, such description is for illustrative purposes only, and it is to be understood that changes and variations may be made without departing from the spirit or scope of the following claims.

## Claims

1. A method for vitrification of waste comprising:
mixing the waste, a glass frit additive, and at least one glass frit constituent including Al2O3, B2O3, and/or SiO2 to form a mixture, the glass frit additive and the at least one glass frit constituent being added as separate components to the mixture; and
vitrifying the mixture in a melter.

2. The method of claim 1 wherein the glass frit additive is in the form of glass beads, cylindrical glass fiber cartridges, glass powder, and/or glass flakes.

3. The method of claim 1 comprising separating at least a portion of Al2O3, B2O3, and/or SiO2 from an initial glass frit, wherein the at least one glass frit constituent includes the separated Al2O3, B2O3, and/or SiO2.

4. The method of claim 1 comprising separating at least a portion of Al2O3, B2O3, and/or SiO2 from an initial glass frit to form a modified glass frit, wherein the glass frit additive includes the modified glass frit and the at least one glass frit constituent includes the separated Al2O3, B2O3, and/or SiO2.

5. The method of claim 4 wherein the separated Al2O3, B2O3, and/or SiO2 includes at least approximately all of the Al2O3 and at least a portion of the B2O3 in the initial glass frit.

6. The method of claim 5 wherein the separated Al2O3, B2O3, and/or SiO2 includes at least a portion of the SiO2 in the initial glass frit.

7. The method of claim 4 wherein the separated Al2O3, B2O3, and/or SiO2 includes Al2O3 and B2O3 from the initial glass frit in an amount totaling at least approximately 7 wt % of the initial glass frit.

8. The method of claim 1 comprising mixing the waste, the glass frit additive, and the at least one glass frit constituent together in the melter.

9. The method of claim 1 comprising mixing the waste, the glass frit additive, and the at least one glass frit constituent together before entering the melter.

10. The method of claim 1 comprising mixing the waste and the at least one glass frit constituent together before entering the melter.

11. The method of claim 1 wherein the waste, the glass frit additive, and the at least one glass frit constituent are in powder form.

12. The method of claim 1 wherein the waste includes nuclear waste.

13. The method of claim 1 wherein the waste includes radioactive waste.

14. The method of claim 1 wherein the waste includes high level radioactive waste.

15. The method of claim 1 wherein the melter includes a joule heated ceramic melter.

16. The method of claim 1 wherein the melter includes a cold crucible melter and/or an induction melter.

17. The method of claim 1 wherein the mixture comprises:
approximately 70 wt % to 78 wt % of the glass frit additive; and
approximately 7 wt % to 15 wt % of the at least one glass frit constituent.

18. A method for vitrification of waste comprising:
separating at least one glass frit constituent from an initial glass frit to form a modified glass frit;
mixing the waste, the modified glass frit, and the at least one glass frit constituent to form a mixture, the modified glass frit and the at least one glass frit constituent being added as separate components to the mixture; and
vitrifying the mixture in a melter.

19. The method of claim 18 wherein the at least one glass frit constituent includes approximately 7 wt % to 15 wt % of the initial glass frit.

20. The method of claim 18 wherein the at least one glass frit constituent includes Al2O3, B2O3, and/or SiO2.

21. The method of claim 18 wherein the at least one glass frit constituent includes at least approximately all of the Al2O3 and at least a portion of the B2O3 in the initial glass frit.

22. The method of claim 21 wherein the at least one glass frit constituent includes at least a portion of the SiO2 in the initial glass frit.

23. The method of claim 18 wherein the at least one glass frit constituent includes Al2O3 and B2O3 from the initial glass frit in an amount totaling at least approximately 7 wt % of the initial glass frit.

24. The method of claim 18 wherein the waste, the modified glass frit, and the at least one glass frit constituent are in powder form.

25. The method of claim 18 wherein the waste includes nuclear waste.

26. The method of claim 18 wherein the waste includes radioactive waste.

27. The method of claim 18 wherein the waste includes high level radioactive waste.

28. The method of claim 18 wherein the melter includes a joule heated ceramic melter.

29. The method of claim 18 wherein the melter includes a cold crucible melter and/or an induction melter.

30. The method of claim 18 wherein the mixture comprises:
approximately 70 wt % to 78 wt % of the modified glass frit; and
approximately 7 wt % to 15 wt % of the at least one glass frit constituent.