CA2498404C - Apparatus and method for vitrification of contaminated soil or waste - Google Patents
Apparatus and method for vitrification of contaminated soil or waste Download PDFInfo
- Publication number
- CA2498404C CA2498404C CA2498404A CA2498404A CA2498404C CA 2498404 C CA2498404 C CA 2498404C CA 2498404 A CA2498404 A CA 2498404A CA 2498404 A CA2498404 A CA 2498404A CA 2498404 C CA2498404 C CA 2498404C
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- container
- treated
- waste
- materials
- hazardous
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims description 37
- 239000002689 soil Substances 0.000 title claims description 35
- 238000004017 vitrification Methods 0.000 title description 12
- 239000000463 material Substances 0.000 claims abstract description 113
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 239000011819 refractory material Substances 0.000 claims abstract description 18
- 238000009413 insulation Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000013056 hazardous product Substances 0.000 claims description 6
- 239000004567 concrete Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012857 radioactive material Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- -1 radionuclides Substances 0.000 claims description 2
- 239000000383 hazardous chemical Substances 0.000 claims 12
- 230000000996 additive effect Effects 0.000 claims 3
- 231100000357 carcinogen Toxicity 0.000 claims 1
- 239000003183 carcinogenic agent Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000011810 insulating material Substances 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000010309 melting process Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 6
- 229910052770 Uranium Inorganic materials 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 5
- 239000012768 molten material Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000011449 brick Substances 0.000 description 2
- 238000009933 burial Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/305—Glass or glass like matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
- B09B3/29—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix involving a melting or softening step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/067—Reclamation of contaminated soil thermally by vitrification
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/005—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture of glass-forming waste materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/425—Preventing corrosion or erosion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/10—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating electric
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/18—Door frames; Doors, lids, removable covers
- F27D1/1808—Removable covers
- F27D1/1816—Removable covers specially adapted for arc furnaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/20—Combustion to temperatures melting waste
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/18—Radioactive materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/20—Medical materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/24—Contaminated soil; foundry sand
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/10—Details, accessories, or equipment peculiar to hearth-type furnaces
- F27B3/12—Working chambers or casings; Supports therefor
- F27B2003/125—Hearths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
- F27B3/085—Arc furnaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0003—Linings or walls
- F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2001/00—Composition, conformation or state of the charge
- F27M2001/05—Waste materials, refuse
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Inorganic Chemistry (AREA)
- High Energy & Nuclear Physics (AREA)
- Processing Of Solid Wastes (AREA)
- Furnace Details (AREA)
- Furnace Charging Or Discharging (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
Abstract
A process for melting material to be treated includes placing material to be treated in a container that may include an insulating lining, heating the material to be treated and melting the material to be treated, preferably allowing the melted material to cool to form a vitrified and/or crystalline mass, and disposing of the mass. The mass is either disposed while contained in container or removed from container after cooling and disposed. Insulating lining may comprise one or more layers of a thermal insulating material, one or more layers of refractory material, or a combination thereof. The material to be treated may be heated by placing at least two electrodes in the material to be treated and passing a current between the electrodes, or alternatively, by placing at least one heating element in the material to be treated and passing heat into the material to be treated.
Description
APPARATUS AND METHOD FOR VITRIFICATION OF
CONTAMINATED SOIL OR WASTE
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[00011 The present invention relates to a method and apparatus for the melting of materials to be treated. More specifically, the invention relates to an apparatus that comprises a container in which melting is performed, thus enabling a one-step disposal method for the treated materials.
DESCRIPTION OF THE PRIOR ART
CONTAMINATED SOIL OR WASTE
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[00011 The present invention relates to a method and apparatus for the melting of materials to be treated. More specifically, the invention relates to an apparatus that comprises a container in which melting is performed, thus enabling a one-step disposal method for the treated materials.
DESCRIPTION OF THE PRIOR ART
[0002] The use of vitrification methods for safely disposing contaminated soil or waste materials (hereinafter referred to as material to be treated) is known in the art. Examples of such methods are provided in US patent numbers: 4,376,598; 5,024,556; 5,536,114;
5,443,618; and, RE 35,782.
5,443,618; and, RE 35,782.
[0003] Generally, the known vitrification methods involve placement of the materials to be treated into a vitrification chamber or vessel. Electrodes are then introduced into the material and high current is supplied there between. Application of the current is continued until the temperature of the material is raised to the point where the material begins to melt and is continued until the material is completely melted. If certain cases, other additives may be required to provide an initial electrically conductive resistance path through the material to be treated if such material is not capable of adequate current conduction. Once the resistance path is initiated and melting of the material begins, the molten material itself will continue current conduction.
[0004] In the course of melting the material, organic components are destroyed or vaporized and the gases are normally vented through a suitable scrubber, quencher, filter or other known device or method.
[0005] Once the material is sufficiently melted and all organic components are treated, the electricity supply is terminated and the molten material allowed to cool.
The cooling step then results in a vitrified and/or crystallized solid material. In this manner, inorganic contaminants are immobilized within a solid, vitrified mass thereby ensuring containment of the contaminants and facilitating disposal of same.
The cooling step then results in a vitrified and/or crystallized solid material. In this manner, inorganic contaminants are immobilized within a solid, vitrified mass thereby ensuring containment of the contaminants and facilitating disposal of same.
[0006] In the known methods, vitrification is accomplished within a complex refractory-lined melting apparatus or within a pit dug into the soil. In US patent 5,443,618, an example is provided of a vitrification apparatus comprising a chamber that is either permanently in place (as in a treatment facility) or one which can be dismantled and reassembled at desired locations. In each case, the molten mass is removed from the chamber and processed further separately. Such further processing may involve burial, or other type of disposal, of the vitrified and/or crystalline mass. The apparatus known in the art for conducting vitrification process are normally complex structures including various electrical supply systems, waste feed systems, molten glass discharge systems, cooling systems and venting systems. Such systems require the removal of the melted mass while in the molten state, hence requiring the above mentioned molten glass discharge systems. In these cases, the melt is either poured or flowed out as a molten liquid into a receiving container.
[0007] In US patents 4,376,598 and RE 35,782, vitrification processes within a pit are described. In this case, the material to be treated is dumped into a pit or trench in the ground and a soil or other type of cap is placed as a cover. Electrodes are then introduced to conduct the vitrification process as described above. Once the process is completed, the vitrified and/or crystalline mass is left buried in the ground. As will be appreciated, certain contaminants such as radioactive waste etc. cannot safely be disposed in this manner as they must be disposed of in regulated burial locations.
[0008] Generally, the known methods are expensive and are used in difficult situations to which there is no alternative. Therefore, there exists a need for a vitrification apparatus and method that overcomes various deficiencies in the prior art.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0009] Thus, in one embodiment, the present invention provides a process for melting materials to be treated, the process generally comprising the following exemplary steps:
-2- 501250-2007/032304/SEADOCS:174096. 5 - placing the material to be treated into a container;
- heating the material to be treated in the container until it melts to create melted material; and - allowing the melted material to cool in the container to create a solidified material.
-2- 501250-2007/032304/SEADOCS:174096. 5 - placing the material to be treated into a container;
- heating the material to be treated in the container until it melts to create melted material; and - allowing the melted material to cool in the container to create a solidified material.
[0010] The material to be treated can be (a) contaminated soil, such as soil containing radioactive or non-radioactive material, (b) hazardous material of any type, or (c) any waste.
The material to be treated is preferably heated by at least one heating element or at least two electrodes, depending on the method of heating, positioned in the material to be treated and passing a current between the electrodes (or passing heat from the heating element), and hence through the material to be treated. The current and/or heating element heats the material to be treated and causes it to melt sufficiently for the melted material to form a solidified vitreous and/or crystalline mass after it is allowed to cool. The solidified material may be disposed while it is within the container (i.e., the material and container are both disposed) or may be disposed after it cools by removing it from the container and disposing of it.
The material to be treated is preferably heated by at least one heating element or at least two electrodes, depending on the method of heating, positioned in the material to be treated and passing a current between the electrodes (or passing heat from the heating element), and hence through the material to be treated. The current and/or heating element heats the material to be treated and causes it to melt sufficiently for the melted material to form a solidified vitreous and/or crystalline mass after it is allowed to cool. The solidified material may be disposed while it is within the container (i.e., the material and container are both disposed) or may be disposed after it cools by removing it from the container and disposing of it.
[0011] In another embodiment, the present invention provides a container for treating material comprising a box, said box including an inner lining comprising one or more layers of a thermal insulating material, one or more layers of a refractory material, or a combination thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] These and other features of the preferred embodiments of the invention will become more apparent in the following detailed description in which reference is made to the appended drawings wherein:
Figure 1 is an end cross sectional elevation view of a container according to an embodiment of the present invention.
Figure 2 is an end cross sectional elevation view of an apparatus including the container of Figure 1 when in use according to an embodiment of the invention.
-3- 501250-2007/032304/SEADOCS:174096. 5 Figure 3 is an end cross sectional elevation view of an apparatus including the container of Figure 1 when in use according to another embodiment of the invention.
Figures 4a to 4d are end cross sectional elevation views of the apparatus of Figure 3 in various stages of the melting process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 is an end cross sectional elevation view of a container according to an embodiment of the present invention.
Figure 2 is an end cross sectional elevation view of an apparatus including the container of Figure 1 when in use according to an embodiment of the invention.
-3- 501250-2007/032304/SEADOCS:174096. 5 Figure 3 is an end cross sectional elevation view of an apparatus including the container of Figure 1 when in use according to another embodiment of the invention.
Figures 4a to 4d are end cross sectional elevation views of the apparatus of Figure 3 in various stages of the melting process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] As discussed above, traditional vitrification processes have been conducted in pits or in complex chambers. The present invention, however, provides a container into which the material to be treated is placed and in which the melting process is conducted. Moreover, the container is manufactured in such as a manner as to be low in cost and easily disposable once the melting process is completed. This avoids the need to remove and handle the vitrified and/or crystalline mass, thereby providing a safe and easy means of waste disposal.
[0014] The container of the present invention may be used in virtually all types of melting processes. The container of the present invention may be used with virtually any material that can be melted or treated by molten materials. For example, the container and process may be used for various contaminant types such as heavy metals, radionuclides, and organic and inorganic compounds. Concentrations of the contaminants can be of any range.
Further, the invention can be used with any material capable of being melted, such as silica or soil types such as, for example, sands, silts, clays, etc. The material types may be wet or comprise sludges, sediments, or ash.
Further, the invention can be used with any material capable of being melted, such as silica or soil types such as, for example, sands, silts, clays, etc. The material types may be wet or comprise sludges, sediments, or ash.
[0015] As indicated above, the general melting process involves electric melting of materials to be treated, such as contaminated soil or other earthen materials for purposes of destroying organic contaminants and immobilizing hazardous inorganic and radioactive materials within a high-integrity, vitrified and/or crystalline product.
Electric melting may occur using different types of heating processes such as joule-heating and plasma-heating. The process is initiated by placing at least two electrodes, or at least one heating element, within the material to be treated, followed, optionally, by placement of a conductive starter path material between the at least two electrodes. When electrical power is applied, current flows through the starter path, heating it up to the point that it melts the soil and waste adjacent to it. When the adjacent -4- 501250-2007/032304/SEADOCS:174096. 5 soil and waste becomes molten, they become electrically conductive, and from that point on, the molten material serves as the heating element for the process. Heat is conducted from the molten mass into adjacent un-melted materials, heating it also to the melting point, at which time it becomes part of the conductive heating element. The process continues by increasing the amount of material melted until the supply of electric power is terminated.
During the melting process, any off gases are captured and, where necessary, treated in a suitable, known manner.
The solidified mass resembles a vitrified and/or crystalline product and immobilizes non-gassified contaminants such as heavy metals and radionuclides etc. The melting process has a high tolerance for debris such as steel, wood, concrete, boulders, plastic, bitumen, tires etc.
Electric melting may occur using different types of heating processes such as joule-heating and plasma-heating. The process is initiated by placing at least two electrodes, or at least one heating element, within the material to be treated, followed, optionally, by placement of a conductive starter path material between the at least two electrodes. When electrical power is applied, current flows through the starter path, heating it up to the point that it melts the soil and waste adjacent to it. When the adjacent -4- 501250-2007/032304/SEADOCS:174096. 5 soil and waste becomes molten, they become electrically conductive, and from that point on, the molten material serves as the heating element for the process. Heat is conducted from the molten mass into adjacent un-melted materials, heating it also to the melting point, at which time it becomes part of the conductive heating element. The process continues by increasing the amount of material melted until the supply of electric power is terminated.
During the melting process, any off gases are captured and, where necessary, treated in a suitable, known manner.
The solidified mass resembles a vitrified and/or crystalline product and immobilizes non-gassified contaminants such as heavy metals and radionuclides etc. The melting process has a high tolerance for debris such as steel, wood, concrete, boulders, plastic, bitumen, tires etc.
[0016] For typical naturally occurring soil materials, the melting process may be performed in the temperature range of about 1400 to 2000 C, depending primarily on the composition of the materials being melted. Melts of various sizes and shapes can be produced.
It should also be understood that there is no set range of temperatures under which the melting process of the present invention may be performed. Instead, the temperature range may be raised or lowered depending on the additives used in connection with the present invention. The higher the temperature, the more costly the melting process.
It should also be understood that there is no set range of temperatures under which the melting process of the present invention may be performed. Instead, the temperature range may be raised or lowered depending on the additives used in connection with the present invention. The higher the temperature, the more costly the melting process.
[0017] During the melting process, volume reduction generally occurs due to the melting of the materials to be treated. Thus, in an optional embodiment, additional material may be added to the container, using active or passive feeding methods, thereby maximizing the amount of material treated in the container. Passive feeding occurs when additional material to be treated is stored on top of the container prior to the start of the melting process. During the melting process, the melting of the material to be treated results in the lowering of the additional material to be treated into the container, and subsequently, the treatment of the additional material to be treated. During active feeding, additional material to be treated is added to the container during the melting process.
[0018] In a preferred embodiment of the present invention, the melting process involves the use of a steel container such as a commercial "roll-off box", which is commonly available.
In accordance with the present invention, the container is insulated to inhibit transmission of heat, and is also provided with a refractory lining inside the box to protect the box during the -5- 501250-2007/032304/SEADOCS:174096. 5 melting step. The refractory lining and insulating material may be comprised of the same or different materials. The refractory lining may be comprised of pre-fabricated materials or naturally occurring refractory materials such as bricks, sand, or concrete, a mixture thereof, a thermal insulation board, or any other material having a high melting point.
The at least two electrodes or at least one heating element is placed within the box. The material to be treated is then placed within the box and the melting process is conducted as described above. Once melting is complete, the contents of the box are allowed to cool and solidify.
Subsequently, the box is then disposed of along with the vitrified and/or crystalline contents.
In an alternate embodiment, the vitrified and/or crystalline contents can be removed from the box and disposed of separately, thereby allowing the box to be re-used.
In accordance with the present invention, the container is insulated to inhibit transmission of heat, and is also provided with a refractory lining inside the box to protect the box during the -5- 501250-2007/032304/SEADOCS:174096. 5 melting step. The refractory lining and insulating material may be comprised of the same or different materials. The refractory lining may be comprised of pre-fabricated materials or naturally occurring refractory materials such as bricks, sand, or concrete, a mixture thereof, a thermal insulation board, or any other material having a high melting point.
The at least two electrodes or at least one heating element is placed within the box. The material to be treated is then placed within the box and the melting process is conducted as described above. Once melting is complete, the contents of the box are allowed to cool and solidify.
Subsequently, the box is then disposed of along with the vitrified and/or crystalline contents.
In an alternate embodiment, the vitrified and/or crystalline contents can be removed from the box and disposed of separately, thereby allowing the box to be re-used.
[0019] Figure 1 illustrates a treatment container according to one embodiment of the present invention. As illustrated, the container 10 comprises a box having sidewalls 12 and a base 14. The container 10 is provided with a layer of insulation 16 on each of the sidewalls 12 and the base 14. Insulation 16 may be comprised of materials such as bricks, sand, or concrete, a mixture thereof, a thermal insulation board, or any other material having a high melting point.
After placement of the insulation, the container is lined with a refractory material 18. The refractory material is provided so as to line the sides as well as base of the container. In this manner, a space 20 is left into which the material to be treated can be placed. In a preferred embodiment, when free liquids are used in connection with the invention, the refractory material may be further lined with a liquid impermeable liner 19, such as a plastic liner 19.
After placement of the insulation, the container is lined with a refractory material 18. The refractory material is provided so as to line the sides as well as base of the container. In this manner, a space 20 is left into which the material to be treated can be placed. In a preferred embodiment, when free liquids are used in connection with the invention, the refractory material may be further lined with a liquid impermeable liner 19, such as a plastic liner 19.
[0020] Figure 2 illustrates one embodiment of the present invention. As shown, the container of Figure 1 is provided with a lid or cover 22. The lid or cover 22 is positioned over the container 10 and seals the top thereof. The lid or cover is provided with openings 24 through which extend the at least two electrodes or the at least one heating element 26.
[0021] Between the lid or cover 22 and the container 10, may be placed a connector 28, which connects the lid or cover 22 to the container 10.
[0022] As indicated in the example shown in Figure 2, after the insulation 16 and refractory material 18 are placed in the container 10, the material to be treated 30 is then placed within the space 20. For example, if drums are used in connection with the present invention, the -6- 501250-2007/032304/SEADOCS:174096. 5 drums may comprise standard 55 or 30 gallon drums. It should be understood, however, that there is no limitation on the size of the drum or container used with the present invention. Void spaces between the drums 30 are filled with soil 32. Such soil, 32, is also provided to cover the drums. Further, a layer of cover soil 34 is placed over the covered drums and extends into the connector 28. An electrode or heating element placement tube 36 extends through the cover soil 34. The at least two electrodes or at least one heating element 26 for the treatment process extend through the placement tube 36.
[0023] Figure 3 illustrates another exemplary embodiment of the invention wherein compacted drums 30a or any other materials to be treated are provided in the container 10 instead of cylindrical drums as shown in Figure 2.
[0024] The present invention will now be described in terms of the steps followed. First, the containers are, as described above, lined with a thermal insulation board, followed by placement of a slip form to facilitate the installation of a layer of refractory material. A liquid impermeable liner is then placed in the container so that materials to be treated and soil can be staged within the liquid impermeable liner. The liquid impermeable liner may be used to contain liquids prior to treatment when the material to be treated contains appreciable liquids. The slip form may be removed once the material to be treated is emplaced.
[0025] As described below in the example, the material to be treated can be placed within the container in drums. Within the drums, the material to be treated can be compacted to maximize the amount of the material to be treated. Alternatively, in another embodiment, the material to be treated can be placed directly into the container without the need for drums. In another embodiment, the material to be treated can be placed within the container in bags or boxes. In still another embodiment, liquid wastes can be mixed with soil or other absorbents and placed in the container.
[0026] As will be understood by persons skilled in the art, various additives may be added to the material to be treated to improve or enhance the process or the invention. For example, such additives may increase the conductivity of the material to be treated (e.g. Na) or aid in oxidizing metals contained in the material to be treated (e.g. sucrose or KMnO4). Other additives may be used, such as additives to improve the durability of the vitrified and/or crystalline mass (i.e. the solidified material) or chemicals added to enhance the destruction of chlorinated organics such as PCBs. Additionally, additives may affect melt temperature by raising or lowering the melt temperature.
[0027] In one embodiment, the containers of the present invention can be standard "roll-off' boxes ranging in volume from 10 to 40 cubic yards. Such containers or boxes may have any variety of dimensions of length, width and height. As will be appreciated by persons skilled in the art, the dimensions of the box will be limited only by the requirements of any apparatus that must be attached thereto. In another embodiment, the container of the invention may comprise metal drums, such as standard 55 gallon steel drums. Such drums can be provided with the required insulation and/or refractory material layers as discussed herein. The wall thickness of the containers of the invention can also vary. Typically, standard boxes have wall thicknesses that are in the range of 10 to 12 gauge; however, as will be apparent to persons skilled in the art, other dimensions are possible.
[0028] In general terms, the pre-fabricated insulation and refractory materials form a liner or liner system in the interior of the container. Such liner serves to maintain heat within the container so as to increase the efficiency of the melting process. With this in mind, it will be appreciated that the refractory material can also serve as an insulating layer. In such case, the thickness of the refractory material in the container may be increased to provide the needed insulating value. Alternatively, the refractory material may be omitted and only an insulating layer provided in the container. In the case where both a refractory layer and separate insulating layer are used, the refractory material would also serve to slow down the transfer of heat to the insulating layer. In such case, it would be possible to extract the insulating layers from the container after the melting process and re-use them. In another embodiment, multiple layers of insulating and/or refractory liners may be used. As will be understood, the amount of insulating and/or refractory material would depend, amongst other criteria, on the nature of the soil and materials being treated. For example, if such soil and material to be treated has a high melting temperature, then extra insulating and/or refractory material would be required.
Example -8- 501250-2007/032304/SEADOCS 174096.5 [0029] The invention will now be described with reference to a specific example wherein radioactive substances, such as uranium chips in the presence of oil, are involved. It will be understood that the example is not intended to limit the scope of the invention in any way.
Example -8- 501250-2007/032304/SEADOCS 174096.5 [0029] The invention will now be described with reference to a specific example wherein radioactive substances, such as uranium chips in the presence of oil, are involved. It will be understood that the example is not intended to limit the scope of the invention in any way.
[0030] First, the material to be treated is placed within 30 gallon drums. The drums, containing the material to be treated, are then compressed or compacted and placed within 50 gallon drums and packed with soil and sealed. These latter drums arc then introduced into the treatment container 10. During the compression of the smaller drums, any oil in the material to be treated by need to be removed and treated separately, as described farther below.
[0031] The placement of the compacted drums of material to he treated (e.g.
uranium and oil) into the container 10 can be performed in two ways. The first method involves emptying of the 55-gal drums holding the compacted smaller drums and soil into the container 10. The compacted drums would be immediately covered with soil to prevent free exposure to air. In this method, the compacted drums may be staged more closely together for processing, and a higher loading of uranium can be achieved. In addition, by removing the compacted drums from the 55-gal drums, there would be no requirement to ensure that the 55-gal drums were violated or otherwise unsealed so as to release vapours during the melting phase.
uranium and oil) into the container 10 can be performed in two ways. The first method involves emptying of the 55-gal drums holding the compacted smaller drums and soil into the container 10. The compacted drums would be immediately covered with soil to prevent free exposure to air. In this method, the compacted drums may be staged more closely together for processing, and a higher loading of uranium can be achieved. In addition, by removing the compacted drums from the 55-gal drums, there would be no requirement to ensure that the 55-gal drums were violated or otherwise unsealed so as to release vapours during the melting phase.
[0032] Alternatively, the 55-gal drums containing the compacted drums could be placed directly into the waste treatment containers for treatment. In this case, vent holes will be installed into the drums to facilitate the release of vapours during processing.
[0033] Some of the contaminated oil removed during the compression phase of the smaller (30 gallon) drums can be added to the soil in the treatment volume in the container for processing with the drums of uranium. The liquid impermeable liner 19 will prevent the movement of free oil from the materials to be treated into the refractory sand materials 18. The slip form 21 will be raised as the level of waste, soil, and refractory sand are simultaneously raised, until the container is filled to the desired level. At that point the slip form 21 will be removed to a storage location.
[0034] A layer of clean soil is placed above the staged waste and refractory sand.
Electrodes are then installed into the soil layer. The installation of the electrodes may involve the use of pre-placed tubes to secure a void space for later placement of electrodes 26.
Alternatively, the pair of electrodes are installed in the staged waste and refractory sand prior to the layer of clean soil being placed above the staged waste and refractory sand. A starter path is then placed in the soil between the electrodes. Lastly, additional clean cover soil 34 is placed above the starter path 31. This will conclude the staging of the waste within the treatment container. The configuration of the waste treatment containers after waste staging is shown in Figures 2 and 3.
Electrodes are then installed into the soil layer. The installation of the electrodes may involve the use of pre-placed tubes to secure a void space for later placement of electrodes 26.
Alternatively, the pair of electrodes are installed in the staged waste and refractory sand prior to the layer of clean soil being placed above the staged waste and refractory sand. A starter path is then placed in the soil between the electrodes. Lastly, additional clean cover soil 34 is placed above the starter path 31. This will conclude the staging of the waste within the treatment container. The configuration of the waste treatment containers after waste staging is shown in Figures 2 and 3.
[0035] Once the waste treatment container 10 is staged with waste as described above, it is covered with an off-gas collection hood 22 that is connected to an off-gas treatment system.
Electrode feeder support frames 27, to support electrode feeders 29, are then positioned over the container-hood assembly 22 unless they are an integral part of the hood 22 design, in such case they will already be in position. At least two electrodes 26 are then placed through the feeder 29, into the hood 22 and into the tube 36 placed at the end of the starter path 31. Additional starter path material will be placed within the tube 36 to ensure a good connection with the starter path 31. Finally the remainder of the tube will be filled with clean cover soil 34.
This will complete the preparation of materials for melting. It will be appreciated that although the above discussion has been directed to at least two electrodes, it will be apparent to persons skilled in the art that at least one heating element may also be used with the system.
Electrode feeder support frames 27, to support electrode feeders 29, are then positioned over the container-hood assembly 22 unless they are an integral part of the hood 22 design, in such case they will already be in position. At least two electrodes 26 are then placed through the feeder 29, into the hood 22 and into the tube 36 placed at the end of the starter path 31. Additional starter path material will be placed within the tube 36 to ensure a good connection with the starter path 31. Finally the remainder of the tube will be filled with clean cover soil 34.
This will complete the preparation of materials for melting. It will be appreciated that although the above discussion has been directed to at least two electrodes, it will be apparent to persons skilled in the art that at least one heating element may also be used with the system.
[0036] Commencement of off-gas flow and readiness testing will be performed prior to initiation of the melting process. The melt processing will involve application of electrical power at an increasing rate (start-up ramp) over a period of time and at a given power output value. For example, electrical power may be applied for about 15 hours to a full power level of approximately 500 kW. It is anticipated that processing of waste containing uranium, drums and oil may take a total of two (2) to five (5) days cycle time to complete depending on the type of waste being treated, the power level being employed and the size of the container. Preferably, processing will be performed on a 24-hr/day basis until completed.
[0037] Figures 4a to 4d illustrate the progressive stages of melting of the material within the container 10.
_10- 501250-2007/032304/SEADOCS:174096. 5 [0038] Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention as outlined in the claims appended hereto.
-11- 501250-2007/032304/SEADOCS:174096. 5
_10- 501250-2007/032304/SEADOCS:174096. 5 [0038] Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention as outlined in the claims appended hereto.
-11- 501250-2007/032304/SEADOCS:174096. 5
Claims (29)
1. A process for melting materials to be treated, the process comprising:
providing a container that can withstand temperatures of up to 2000°C
without significant degradation of the container;
providing a first insulating layer comprising concrete in an interior portion of the container;
placing at least one of waste or hazardous materials to be treated into the container;
heating the at least one of waste or hazardous materials in the container until the materials melt to create at least one of melted waste or hazardous materials, wherein the container is positioned above ground; and allowing the at least one of melted waste or hazardous materials to cool in the container to create at least one of a vitrified waste or hazardous material.
providing a container that can withstand temperatures of up to 2000°C
without significant degradation of the container;
providing a first insulating layer comprising concrete in an interior portion of the container;
placing at least one of waste or hazardous materials to be treated into the container;
heating the at least one of waste or hazardous materials in the container until the materials melt to create at least one of melted waste or hazardous materials, wherein the container is positioned above ground; and allowing the at least one of melted waste or hazardous materials to cool in the container to create at least one of a vitrified waste or hazardous material.
2. The process of claim 1 further comprising disposing of the container with the at least one of waste or hazardous material therein.
3. The process of claim 2 wherein the at least one of waste or hazardous materials in the container are heated at a temperature of from about 1400 to about 2000 degrees C.
4. The process of claim 1 wherein the at least one of waste or hazardous materials are heated to form a molten state consisting essentially of. at least one of melted waste or hazardous materials.
5. The process of any one of claims 1 and 4 wherein the container has a structure to collect gases.
6. The process of claim 5 that further comprises:
removing the gas-collecting structure from the container after the melted material has been allowed to cool; and disposing of the container that includes the at least one of waste or hazardous material therein.
removing the gas-collecting structure from the container after the melted material has been allowed to cool; and disposing of the container that includes the at least one of waste or hazardous material therein.
7. The process of claim 1 wherein the at least one of waste or hazardous materials is heated by at least two removable electrodes located in the material and passing a current between the at least two removable electrodes.
8. The process of claim 7 wherein a starter path of material is placed between the at least two removable electrodes prior to the heating the material.
9. The process of claim 1 wherein the container further includes a hood and at least one heating device that extends through the hood and into the material.
10. The process of claim 1 wherein the at least one of waste or hazardous material contains contaminants chosen from the group consisting of hydrocarbons, radioactive materials, radionuclides, carcinogens, or any combination thereof.
11. The process of claim 1 wherein the container includes a second insulating layer.
12. The process of claim 11 wherein the second insulating layer comprises thermal insulation board.
13. The process of claim 12 wherein the container further includes a refractory material.
14. The process of claim 1 wherein an additive is added to the material before the material is heated.
15. The process of claim 14 wherein the additive increases the conductivity of the material to be treated.
16. The process of claim 14 wherein the additive aids in oxidizing metals contained in the material to be treated.
17. The process of claim 1 further comprising heating the material to a temperature of at least about 1400 degrees C.
18. The process of claim 1 wherein the container has a cavity and includes a slip form positioned in the cavity.
19. The process of claim 18 further including the step of placing sand in the container behind the slip form.
20. The process of claim 19 further including removing the slip form from the container and leaving the sand before heating the material to be treated.
21. The process of claim 1 that further includes the step of placing a liquid impermeable liner in the container, wherein the material to be treated is placed in the liner.
22. The process of claim 1 wherein the material to be treated is contained in one or more vessels that are placed in the container.
23. The process of claim 22 wherein there is a plurality of vessels in the container and soil is placed in voids between the vessels.
24. The process of claim 1 that further includes covering the material to be treated with soil prior to heating the material.
25. The process of claim 1 wherein the material to be treated is mixed with soil.
26. The process of claim 1 wherein the material to be treated is soil material.
27. The process of claim 1 that further includes the step of at least one of capturing or treating gases generated by heating the material.
28. A process for melting materials to be treated, the process comprising:
providing a container having an interior portion with a refractory material therein;
providing a first insulating layer comprising concrete;
providing a second insulating layer comprising thermal insulation board;
placing at least one of waste or hazardous materials to be treated into the container;
heating the at least one of waste or hazardous materials in the container until the materials melt to create at least one of melted waste or hazardous materials, wherein the container is positioned above ground; and allowing the at least one of melted waste or hazardous materials to cool in the container to create at least one of a vitrified waste or hazardous material.
providing a container having an interior portion with a refractory material therein;
providing a first insulating layer comprising concrete;
providing a second insulating layer comprising thermal insulation board;
placing at least one of waste or hazardous materials to be treated into the container;
heating the at least one of waste or hazardous materials in the container until the materials melt to create at least one of melted waste or hazardous materials, wherein the container is positioned above ground; and allowing the at least one of melted waste or hazardous materials to cool in the container to create at least one of a vitrified waste or hazardous material.
29. The process of claim 31 further including the step of placing sand in the container behind a slip form placed therein.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2001/042321 WO2003038361A1 (en) | 2001-09-25 | 2001-09-25 | Apparatus and method for vitrification of contaminated soil or waste |
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CA2498404A1 CA2498404A1 (en) | 2003-05-08 |
CA2498404C true CA2498404C (en) | 2011-03-22 |
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EP (1) | EP1451515A4 (en) |
JP (1) | JP2005507494A (en) |
CA (1) | CA2498404C (en) |
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US7211038B2 (en) | 2001-09-25 | 2007-05-01 | Geosafe Corporation | Methods for melting of materials to be treated |
DE102004052514B4 (en) * | 2004-10-21 | 2009-03-26 | Schott Ag | Method and mold for casting glass blocks |
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DE3204204C2 (en) * | 1982-02-08 | 1986-05-07 | Kraftwerk Union AG, 4330 Mülheim | Procedure for conditioning radioactive waste |
DE3247349C1 (en) * | 1982-12-22 | 1984-05-24 | Deutsche Gesellschaft für Wiederaufarbeitung von Kernbrennstoffen mbH, 3000 Hannover | Melting furnace for glazing highly radioactive waste |
JPH0778555B2 (en) * | 1989-05-20 | 1995-08-23 | 動力炉・核燃料開発事業団 | Electric melting furnace for solidification of waste |
US5443618A (en) * | 1991-12-09 | 1995-08-22 | Battelle Memorial Institute | Earth melter |
US5319669A (en) * | 1992-01-22 | 1994-06-07 | Stir-Melter, Inc. | Hazardous waste melter |
DE4217854C2 (en) * | 1992-05-29 | 1995-06-22 | Sorg Gmbh & Co Kg | Furnace for vitrifying waste, in particular dust from incinerators and asbestos |
US5536114A (en) * | 1994-05-20 | 1996-07-16 | Stir-Melter, Inc. | Apparatus for vitrifcation of hazardous waste |
US5673285A (en) * | 1994-06-27 | 1997-09-30 | Electro-Pyrolysis, Inc. | Concentric electrode DC arc systems and their use in processing waste materials |
DE19524215C2 (en) * | 1995-07-03 | 2003-04-17 | Alstom | Melting furnace for the thermal treatment of special waste containing heavy metals and / or dioxins |
GB9515299D0 (en) * | 1995-07-26 | 1995-09-27 | British Nuclear Fuels Plc | Waste processing method & apparatus |
US5678237A (en) * | 1996-06-24 | 1997-10-14 | Associated Universities, Inc. | In-situ vitrification of waste materials |
US6211424B1 (en) * | 1998-07-30 | 2001-04-03 | Radioactive Isolation Consortium, Llc | Advanced vitrification system |
US6283908B1 (en) * | 2000-05-04 | 2001-09-04 | Radioactive Isolation Consortium, Llc | Vitrification of waste with conitnuous filling and sequential melting |
US6558308B2 (en) * | 2001-05-07 | 2003-05-06 | Radioactive Isolation Consortium, Llc | AVS melting process |
US6485404B1 (en) * | 2002-04-04 | 2002-11-26 | Radioactive Isolation Consortium, Llc | Advanced vitrification system improvements |
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2001
- 2001-09-25 EP EP01975789A patent/EP1451515A4/en not_active Withdrawn
- 2001-09-25 CA CA2498404A patent/CA2498404C/en not_active Expired - Lifetime
- 2001-09-25 JP JP2003540588A patent/JP2005507494A/en active Pending
- 2001-09-25 WO PCT/US2001/042321 patent/WO2003038361A1/en active Application Filing
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EP1451515A4 (en) | 2011-08-10 |
WO2003038361A1 (en) | 2003-05-08 |
EP1451515A1 (en) | 2004-09-01 |
JP2005507494A (en) | 2005-03-17 |
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