METHODS, MATERIALS SYSTEMS, AND DEVICES FOR INHIBITING INFILTRATION AND PENETRATION OF MOLTEN SALTS INTO SOLID MATERIALS
20210047244 ยท 2021-02-18
Inventors
Cpc classification
C04B38/00
CHEMISTRY; METALLURGY
C04B41/4535
CHEMISTRY; METALLURGY
C23C14/046
CHEMISTRY; METALLURGY
C04B38/00
CHEMISTRY; METALLURGY
International classification
C04B41/45
CHEMISTRY; METALLURGY
Abstract
Methods, materials systems, and devices for inhibiting the infiltration and penetration of molten salts into solid materials, including porous materials at temperatures above the solidus temperature of the molten salt. The methods, materials systems, and devices utilize a non-wetted solid that is introduced into pores having entrances at an exterior surface of a porous solid material adapted to contact the molten salt.
Claims
1. A method for enhancing the resistance of a porous solid material to the infiltration and penetration of a molten salt, the method comprising: providing a porous solid material having an exterior surface adapted to contact the molten salt and pores having entrances at the exterior surface; and introducing into the pores of the porous solid material a non-wetted solid that is not infiltrated or penetrated by the molten salt.
2. The method of claim 1, wherein the non-wetted solid is a hydrophobic solid.
3. The method of claim 1, wherein the non-wetted solid is a carbon-bearing solid, or a hydrocarbon-bearing solid, or a mixture thereof.
4. The method of claim 3, wherein the non-wetted solid is introduced into the pores of the porous solid material by the infiltration of a fluid precursor material to the non-wetted solid into the pores of the porous solid material, followed by conversion of the fluid precursor material into the non-wetted solid within the pores of the porous solid material.
5. The method of claim 4, wherein the fluid precursor material to the non-wetted solid is a liquid precursor material to the non-wetted solid, a mixture of liquid and solid precursor materials to the non-wetted solid, or a vapor precursor material to the non-wetted solid.
6. The method of claim 4, wherein the fluid precursor material is pitch, tar, or a mixture thereof.
7. The method of claim 4, wherein the fluid precursor material is produced from a natural source or from a manufactured source, wherein the natural source or manufactured source is one of a plant, peat, coal, coal tar, pitch, charcoal, petroleum, or any combination of two or more thereof.
8. The method of claim 4, wherein the fluid precursor material to the non-wetted solid is a liquid precursor material to the non-wetted solid, or a mixture of liquid and solid precursor materials to the non-wetted solid, and the conversion of the liquid precursor material to the non-wetted solid, or the conversion of a mixture of liquid and solid precursor materials to the non-wetted solid, is conducted by a thermal treatment.
9. The method of claim 4, wherein the fluid precursor material to the non-wetted solid is a vapor precursor material and the conversion of the vapor precursor material to the non-wetted solid is conducted by one or more of condensation of the vapor precursor material onto the internal surfaces of the porous solid material and a thermal treatment to allow the vapor precursor material to undergo a chemical reaction.
10. The method of claim 1, wherein the non-wetted solid is present within the pores of the porous solid material and is not present solely as a continuous uninterrupted external layer on the exterior surface of the porous solid material.
11. The method of claim 10, wherein the non-wetted solid only penetrates a portion of a thickness of the porous solid material to completely close, or to partially close, the entrances of the pores at the exterior surface of the porous solid material, and a bulk of the porous solid material remains porous.
12. The method of claim 1, wherein the porous solid material comprises a porous metal, a porous metal alloy, a porous ceramic, a porous ceramic alloy, or a porous mixture of two or more of a porous metal alloy, a porous ceramic, or a porous ceramic alloy.
13. A materials system that is resistant to the infiltration and penetration of a molten salt, the materials system comprising: a porous solid material having an exterior surface adapted to contact the molten salt and pores having entrances at the exterior surface; and a non-wetted solid that is within the pores of the porous solid material and is not infiltrated or penetrated by the molten salt.
14. The materials system of claim 13, wherein the non-wetted solid is a hydrophobic solid.
15. The materials system of claim 13, wherein the non-wetted solid is a carbon-bearing solid, or a hydrocarbon-bearing solid, or a mixture thereof.
16. The materials system of claim 13, wherein the non-wetted solid is present within the pores of the porous solid material and is not present solely as a continuous uninterrupted external layer on the exterior surface of the porous solid material.
17. The materials system of claim 16, wherein the non-wetted solid only penetrates a portion of a thickness of the porous solid material to completely close, or to partially close, the entrances of the pores at the exterior surface of the porous solid material, and a bulk of the porous solid material remains porous.
18. The materials system of claim 13, wherein the porous solid material comprises a porous metal, a porous metal alloy, a porous ceramic, a porous ceramic alloy, or a porous mixture of two or more of a porous metal alloy, a porous ceramic, or a porous ceramic alloy.
19. The materials system of claim 13, wherein the porous solid material comprises a solid that is more resistant to abrasion and erosion than the non-wetted solid.
20. A device that is resistant to the infiltration and penetration of a molten salt, the device comprising: a porous solid material having an exterior surface in contact with the molten salt and pores having entrances at the exterior surface; and a non-wetted solid that is within the pores of the porous solid material and is not infiltrated or penetrated by the molten salt.
21. The device of claim 20, wherein the molten salt is one of a molten halide, a molten nitrate, a molten carbonate, a molten sulfate, a molten hydroxide, and a molten oxide, or any combination of two or more thereof.
22. The device of claim 21, wherein the molten halide is one of a molten fluoride, a molten chloride, a molten bromide, and a molten iodide, or any combination of two or more thereof.
23. The device of claim 20, wherein the non-wetted solid is a hydrophobic solid.
24. The device of claim 20, wherein the non-wetted solid is a carbon-bearing solid, or a hydrocarbon-bearing solid, or a mixture thereof.
25. The device of claim 20, wherein the non-wetted solid is present within the pores of the porous solid material and is not present solely as a continuous uninterrupted external layer on the exterior surface of the porous solid material.
26. The device of claim 25, wherein the non-wetted solid only penetrates a portion of a thickness of the porous solid material to completely close, or to p y close, the entrances of the pores at the exterior surface of the porous solid material, and a bulk of the porous solid material remains porous.
27. The device of claim 20, wherein the porous solid material comprises a porous metal, a porous metal alloy, a porous ceramic, a porous ceramic alloy, or a porous mixture of two or more of a porous metal alloy, a porous ceramic, or a porous ceramic alloy.
28. The device of claim 20, wherein the porous solid material comprises a solid that is more resistant to abrasion and erosion than the non-wetted solid.
29. The device of claim 20, wherein the device is a containment device that contains the molten salt, and the porous solid material is a thermally-insulating material.
30. The device of claim 20, wherein the device is a containment device chosen from the group consisting of pipes, receivers, valves, seals, and thermal energy storage tanks of a system operating at a temperature above the solidus temperature of the molten salt.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0024] Some of the figures shown herein include dimensions. Further, some of the figures shown herein have been created from photographs that are scalable. It is understood that such dimensions or the relative scaling within a figure are by way of example, and not to be construed as limiting. Further, in this disclosure, the figures are shown for illustrative purposes and those skilled in the art can readily recognize the relative dimensions of the different segments of the figures depending on how the principles of the disclosure are used in practical applications.
[0025]
[0026]
[0027]
[0028]
DETAILED DESCRIPTION OF THE INVENTION
[0029] For the purposes of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiments illustrated in the figures and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended, such alterations and further modifications in the principles of the disclosure, and such further applications of the principles of the disclosure as illustrated therein being contemplated as would normally occur to one skilled in the art to which the disclosure relates.
[0030] The present disclosure relates to methods, materials systems, and devices for inhibiting the infiltration and penetration of molten salts into solid materials, nonlimiting examples of which include containment materials comprised of metals, metallic alloys, metal-bearing composites, ceramics, and ceramic-bearing composites. The present disclosure also relates to methods, materials systems, and devices for inhibiting the infiltration and penetration of molten salts at high temperatures (e.g., above the solidus temperatures of the salts) into containment materials comprised of porous metals, porous metallic alloys, porous metal-bearing composites, porous ceramics, and porous ceramic-bearing composites. The present disclosure also relates to methods, materials systems, and devices for inhibiting the infiltration and penetration of molten salts at high temperatures into containment materials comprised of thermally-insulating materials comprised of porous metals, porous metallic alloys, porous metal-bearing composites, porous ceramics, and porous ceramic-bearing composites. It should be noted that the molten salts of interest to the present invention include, but are not limited to, any one of the following materials or any combinations of the following materials: chloride-bearing liquids, fluoride-bearing liquids, nitrate-bearing liquids, sulfate-bearing liquids, carbonate-bearing liquids, hydroxide-bearing liquids, and oxide-bearing liquids.
[0031] The present disclosure also provides methods and materials systems for achieving the infiltration resistance and penetration resistance to molten salts of solid metals, metallic alloys, metal-bearing composites, ceramics, and ceramic-bearing composites used in components in high-temperature systems. Examples of such high-temperature systems include, but are not limited to, systems for energy (e.g., electrical power) production, energy storage, waste heat recovery, and chemical processing. Examples of electrical power production systems in the context of this disclosure include, but are not limited to, systems for fossil fuel-derived power, solar energy-derived power, and nuclear energy-derived power. Solar energy-derived power production systems in the context of this disclosure include but not limited to concentrating solar power production systems. Components in the context of this disclosure suitable for use in such high temperature systems include, but are not limited to, pipes, valves, and thermal energy storage containers that may be required to continuously operate at temperatures above the solidus temperature of the molten salt used by the system.
[0032] The following description provides specific examples of the above general concepts of this disclosure with reference to several solid materials, alloys, solid products and liquids. These are merely exemplary embodiments and are not intended to limit the scope of this disclosure.
[0033] The infiltration and penetration of a solid material by a molten salt in a given environment can be inhibited by introducing, into such a solid material, a second solid phase that is not wetted or is poorly wetted by the molten salt. As a matter of convenience, such a second non-wetted or poorly-wetted solid phase is referred to herein as a non-wetted solid, and defined as a solid phase that is not wetted or is poorly wetted by a molten salt, as nonlimiting examples, molten halide salts including molten chloride salts and molten fluoride salts. To inhibit the infiltration and penetration of a molten salt into a porous solid material, the non-wetted solid need only be present within the pores of the porous solid material. Therefore the non-wetted solid is not present solely as a external layer on the exterior surface of the porous solid material that contacts the molten salt, and is not required to be present, and preferably is not present, as a continuous (uninterrupted) external layer on the exterior surface of the porous solid material. Furthermore, the non-wetted solid need only be introduced into interior surface portions of the pores that are contiguous with or immediately adjacent the exterior surface of the porous solid material, in other words the entrances of the pores, so that the non-wetted solid only penetrates a portion of the thickness of the porous solid material and the bulk of the porous solid material remains porous. The non-wetted solid may completely close the entrances of the pores at the exterior surface of the porous solid material, though in many cases the non-wetted solid is not required to completely close the entrances, but instead only partially closes the entrances, for example, by partially or completely coating the interior surface portions of the pores at the entrances of the pores to the extent that the non-wetted solid is present within the pore entrances in an amount sufficient to prevent the molten salt from contacting surfaces of the porous solid material located interiorly of the non-wetted solid.
[0034] Non-wetted solids of this invention include, but are not limited to, hydrophobic solids. Non-wetted solids of this invention also include, but are not limited to, carbon-bearing solids, hydrocarbon-bearing solids, mixtures of one or more carbon-bearing solids, mixtures of one or more hydrocarbon-bearing solids, and mixtures of one or more carbon-bearing solids and one or more hydrocarbon-bearing solids. The non-wetted solids may be a carbon-bearing solid produced from pitch, tar, or a mixture of pitch and tar, and/or a hydrocarbon-bearing solid produced from pitch, tar, charcoal, or a mixture of two or more of pitch, tar, and charcoal, and/or a carbon-bearing solid produced from a natural source or a manufactured source, as nonlimiting examples, plants, peat, coal, coal tar, and/or petroleum.
[0035] The non-wetted solid may be introduced into the solid containment material by infiltrating a fluid precursor material into the solid containment material, followed by conversion of the fluid precursor material into the non-wetted solid. Such a fluid precursor material may be a liquid precursor material or a vapor precursor material.
[0036] The conversion of a liquid precursor material into the non-wetted solid may be accomplished by a thermal treatment. Such a thermal treatment includes, but is not limited to, a thermal treatment to vaporize a volatile constituent of the liquid precursor material, a thermal treatment to crystallize a constituent of the liquid precursor material, and a thermal treatment to allow the liquid precursor material to undergo a chemical reaction.
[0037] The method used to convert a vapor precursor material into the non-wetted solid includes, but is not limited to, condensation of the vapor precursor material onto the internal surfaces of the solid containment material and a thermal treatment to allow the vapor precursor material to undergo a chemical reaction.
[0038]
[0039]
[0040] While the detailed description above described the resistance of pitch-infiltrated calcium-aluminate ceramic material to infiltration and penetration by a molten MgCl.sub.2KClNaCl salt at 750 C. in industrial-grade argon, the general principles of the disclosure are applicable to any molten salt that is likely to wet, infiltrate, and penetrate a solid containment material.
[0041] Based on the foregoing description, it is an objective of this disclosure to describe methods for enhancing the resistance of a solid containment material to infiltration and penetration by molten salts. The molten salts include, but are not limited to, molten halides, molten nitrates, molten carbonates, molten sulfates, molten hydroxides, and molten oxides. Molten halides include, but are not limited to, molten chlorides and molten fluorides. The method includes providing a porous solid containment material and introducing a non-wetted solid into pores of the porous solid containment material. The solid containment material in the method can be comprised of a porous metal, porous metal alloy, porous metal-bearing composite, porous ceramic, and porous ceramic-bearing composite. The non-wetted solid is introduced into the solid containment material by the infiltration of a fluid precursor material into the pores in the solid containment material, followed by conversion of the fluid precursor material, present in the pores of the solid containment material, into the non-wetted solid. Such a fluid precursor material may be a liquid precursor material or a vapor precursor material. The conversion of a liquid precursor material into the non-wetted solid may be accomplished by a thermal treatment. Such a thermal treatment includes, but is not limited to, thermal treatment to vaporize a volatile constituent of the liquid precursor material, thermal treatment to crystallize a constituent of the liquid precursor material, and thermal treatment to allow the liquid precursor material to undergo a chemical reaction. Methods capable of converting a vapor precursor material into the non-wetted solid include, but are not limited to, condensation of the vapor precursor material onto the internal pore surfaces of the solid containment material and thermal treatment to allow the vapor precursor material to undergo a chemical reaction.
[0042] It is another objective of this disclosure to describe materials systems for enhancing the resistance of a solid containment material to infiltration and penetration by a molten salt. The molten salts include, but are not limited to, molten halides, molten nitrates, molten carbonates, molten sulfates, molten hydroxides, and molten oxides. Molten halides include, but are not limited to, molten chlorides and molten fluorides. The materials system includes a solid containment material possessing pores, and a non-wetted solid that has been introduced into the pores of the solid containment material. Solid containment materials include, but are not limited to, porous metals, porous metal alloys, porous metal-bearing composites, porous ceramics, and porous ceramic-bearing composites. The non-wetted solids include, but are not limited to, hydrophobic solids. Examples of non-wetted solids include, but are not limited to, carbon-bearing solids, hydrocarbon-bearing solids, mixtures of one or more carbon-bearing solids, mixtures of one or more hydrocarbon-bearing solids, and mixtures of one or more carbon-bearing solids and one or more hydrocarbon-bearing solids. The non-wetted solids include, but are not limited to, carbon-bearing solids produced from pitch, tar, charcoal, or a mixture of two or more of pitch, tar, and charcoal. The non-wetted solids further include, but are not limited to, hydrocarbon-bearing solids produced from pitch, tar, charcoal, or mixtures of two or more of pitch, tar, and charcoal. The non-wetted solids also include, but are not limited to, carbon-bearing solids produced from a natural source or a manufactured source. The non-wetted solids also include, but are not limited to, hydrocarbon-bearing solids produced from natural sources or manufactured sources, including, but is not limited to, plants, peat, coal, coal tar, pitch, charcoal, petroleum, and mixtures of two or more of plants, peat, coal, coal tar, pitch, charcoal, petroleum.
[0043] It is another objective of this disclosure to describe materials systems for enhancing the resistance of a solid containment material to infiltration and penetration by a molten salt, while also being resistant to abrasion and erosion. The molten salts include, but are not limited to, molten halides, molten nitrates, molten carbonates, molten sulfates, molten hydroxides, and molten oxides. Molten halides include, but are not limited to, molten chlorides and molten fluorides. The materials system includes a solid containment material possessing pores, and a non-wetted solid that has been introduced into the pores of the solid containment material. Solid containment materials include, but are not limited to, porous metals, porous metal alloys, porous metal-bearing composites, porous ceramics, and porous ceramic-bearing composites. The non-wetted solids include, but are not limited to, hydrophobic solids. Examples of non-wetted solids include, but are not limited to, carbon-bearing solids, hydrocarbon-bearing solids, mixtures of one or more carbon-bearing solids, mixtures of one or more hydrocarbon-bearing solids, and mixtures of one or more carbon-bearing solids and one or more hydrocarbon-bearing solids. The non-wetted solids include, but are not limited to, carbon-bearing solids produced from pitch, tar, charcoal, or a mixture of two or more of pitch, tar, and charcoal. The non-wetted solids further include, but are not limited to, hydrocarbon-bearing solids produced from pitch, tar, charcoal, or mixtures of two or more of pitch, tar, and charcoal. The non-wetted solids also include, but are not limited to, carbon-bearing solids produced from a natural source or a manufactured source. The non-wetted solids also include, but are not limited to, hydrocarbon-bearing solids produced from natural sources or manufactured sources, including, but is not limited to, plants, peat, coal, coal tar, pitch, charcoal, petroleum, and mixtures of two or more of plants, peat, coal, coal tar, pitch, charcoal, petroleum. The porous solid material provides erosion resistance in contact with a flowing molten salt, whereas the non-wetted solid present within the pores of the porous solid material provides resistance to infiltration and penetration of the flowing molten salt.
[0044] It is yet another objective of this disclosure to describe devices in high-temperature systems that are resistant to the infiltration and penetration of a molten salt. Examples of such high-temperature systems include, but are not limited to, systems for energy (e.g., electrical power) production, energy storage, waste heat recovery, and chemical processing. Examples of electrical power production systems in the context of this disclosure include, but are not limited to, systems for fossil fuel-derived power, solar energy-derived power, and nuclear energy-derived power. Solar energy-derived power production systems in the context of this disclosure include but are not limited to concentrating solar power production systems. Devices in the context of this disclosure suitable for use in such high temperature systems include, but are not limited to, containment devices, nonlimiting examples of which include pipes, receivers, valves, seals, and thermal energy storage tanks, particularly those for use in high-temperature systems, including high-temperature systems for energy (e.g., electrical power) production, energy storage, waste heat recovery, and chemical processing.
[0045] It should be recognized that, in the methods, materials systems, and devices of this disclosure, the materials whose resistance to infiltration and penetration by molten salts is desired to be enhanced can be a thermally-insulating material.
[0046] While the present disclosure has been described with reference to certain embodiments, it will be apparent to those of ordinary skill in the art that other embodiments and implementations are possible that are within the scope of the present disclosure without departing from the spirit and scope of the present disclosure. For example, the solid containment materials could be formed of materials other than those noted, and could be used in high-temperature applications other than those described. The molten salts could be comprised of materials other than those noted. The non-wetted solid could be comprised of materials other than those noted. Accordingly, it should be understood that the disclosure is not limited to any embodiment described herein. It should also be understood that the phraseology and terminology employed above are for the purpose of describing the disclosed embodiments, and do not necessarily serve as limitations to the scope of the disclosure. Therefore, the scope of the invention is to be limited only by the following claims.