WO2014074930A1 - Verre liquide à base de phosphore, à faible viscosité, à très faible coût pour le transfert thermique et le stockage d'énergie thermique - Google Patents

Verre liquide à base de phosphore, à faible viscosité, à très faible coût pour le transfert thermique et le stockage d'énergie thermique Download PDF

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WO2014074930A1
WO2014074930A1 PCT/US2013/069313 US2013069313W WO2014074930A1 WO 2014074930 A1 WO2014074930 A1 WO 2014074930A1 US 2013069313 W US2013069313 W US 2013069313W WO 2014074930 A1 WO2014074930 A1 WO 2014074930A1
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Prior art keywords
oxide
mol
amount
potassium
phosphorus
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PCT/US2013/069313
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English (en)
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Justin Raade
Benjamin ELKIN
Leo Finkelstein
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Halotechnics, Inc.
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Publication of WO2014074930A1 publication Critical patent/WO2014074930A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/006—Constructions of heat-exchange apparatus characterised by the selection of particular materials of glass
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F23/00—Features relating to the use of intermediate heat-exchange materials, e.g. selection of compositions
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the invention provides an oxide containing phosphorus oxide, in an amount of from about 25 to about 90 mol%.
  • the oxide also contains at least two oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the invention provides a method for storing or transporting thermal energy.
  • the method includes heating a composition with thermal energy, wherein the composition contains an oxide of the invention.
  • Figure 1 shows the PLK phase diagram, with the 340 °C eutectic highlighted in the shaded oval.
  • Figure 2 shows (L to R) Monofrax CS-3, CS-5, and M rods after a 200-hr corrosion test at 1100 °C.
  • Figure 3 shows viscosity data for glass 3i from three separate trials, measured at 400-1180 °C.
  • Figure 4 shows heat capacity data obtained for glass 3i.
  • Figure 5 shows a differential scanning calorimetry (DSC) trace obtained for glass 5a, containing phosphorus oxide, sodium oxide, calcium oxide, and boron oxide.
  • Figure 6a shows a DSC trace obtained for Green glass (6a), containing phosphorus oxide, sodium oxide, calcium oxide, boron oxide, and vanadium oxide.
  • Figure 6b shows thermogravimetric analysis (TGA) data for Green glass.
  • Figure 7 shows a DSC trace obtained for glass 7a, containing phosphorus oxide, sodium oxide, calcium oxide, boron oxide, vanadium oxide, and potassium oxide.
  • Figure 8 shows a DSC trace obtained for glass 8a, containing phosphorus oxide, sodium oxide, calcium oxide, boron oxide, vanadium oxide, potassium oxide, and zinc oxide.
  • Figure 9 shows a DSC trace obtained for glass 9, containing phosphorus oxide and sodium oxide.
  • Figure 10 shows a DSC trace obtained for glass 10, containing phosphorus oxide, sodium oxide, and calcium oxide.
  • the present invention provides higher order oxide compositions containing phosphorous oxide and at least two oxides selected from lithium oxide, sodium oxide, potassium oxide, and boron oxide.
  • the compositions can reduce the cost of concentrated solar power (CSP) electricity and thermal storage in two ways: 1) by enabling significantly higher operating temperatures in the plants and more effective sensible heat thermal storage, and 2) by enabling the use of a lower cost thermal storage material.
  • CSP concentrated solar power
  • the current state of the art thermal storage system is a two-tank sensible heat system using molten salt as the thermal storage media, a technology deployed in many commercial CSP plants. The high capital cost of this technology— over $100/kWht— represents a significant impediment to the construction and operation of plants with thermal storage.
  • the thermal storage medium This high cost is primarily due to the inefficient use of the most expensive component of the system, the thermal storage medium.
  • the thermal storage medium With sensible heat systems, the amount of thermal energy stored is directly proportional to the temperature difference of the storage material. Typical materials have a small temperature difference between the hot tank (at 400 °C) and the cold tank (at 300 °C).
  • the present invention provides storage materials with surprisingly large temperature differences. The materials of the present invention can store as much heat as conventional systems while using as little as 1/8 ⁇ , or less, of the storage material. This surprising reduction is further improved by reducing the cost of the storage material itself by 50% or more.
  • oxygen refers to a compound having a least one oxygen atom bound to a non-oxygen atom.
  • Alkali metal oxides refer to oxides of sodium, potassium, lithium, rubidium, and cesium.
  • Useful oxides in the present invention include, but are not limited to, phosphorus oxide (P 2 O 5 ), lithium oxide (Li 2 0), sodium oxide (Na 2 0), potassium oxide (K 2 0), boron oxide (B 2 0 3 ), calcium oxide (CaO), bismuth oxide (Bi 2 0 3 ), copper oxide (CuO), vanadium oxide (V 2 0 5 ), lead oxide (Pb 3 0 4 ), zinc oxide (ZnO), and magnesium oxide (MgO).
  • P 2 O 5 phosphorus oxide
  • Li 2 0 lithium oxide
  • Na 2 0 sodium oxide
  • K 2 0 potassium oxide
  • B 2 0 3 boron oxide
  • CaO calcium oxide
  • bismuth oxide Bi 2 0 3
  • CuO copper oxide
  • V 2 0 5 vanadium oxide
  • Pb 3 0 4 lead oxide
  • ZnO zinc oxide
  • MgO magnesium oxide
  • Other oxides can be used in the compositions of the invention.
  • Thermal energy refers to portion of energy in a system that gives rise to the temperature of the system.
  • a “thermal source” refers to a member of the system from which thermal energy is transferred to other members of the system.
  • Thermal energy can include, for example, radiation of varying wavelengths including, but not limited to, wavelengths in the infrared and visible portions of electromagnetic spectrum. Thermal energy can also include heat in fluids or solids which can be transferred by convection or conduction.
  • Thermal energy can also be generated by mechanical compression or electrical resistive elements. Thermal energy is transferred between members of the system as heat. "Heating" a composition of the invention refers to raising the temperature of the composition. Heating can be conducted by processes including, but not limited to, convection, conduction, mechanical compression, electrical resistive heating, and irradiation. Examples of thermal sources include, but are not limited to, natural sources such as sunlight and geothermal sources. Examples of thermal sources also include systems such as power plants and components thereof. III. Low-Order Alkali-Phosphate Glasses
  • phosphorus/lithium/potassium oxide system has but one data point (see, lk). Data is available for only one four-component system (see, phosphorous/ lithium/sodium/potassium oxide; entry 11), where the 652 °C reported liquidus temperature is unexpectedly high.
  • Phosphorus pentoxide molar compositions never exceed 50%, as P 2 0 5 is most often introduced as alkali-metaphosphate (X-PO3) batch component salts.
  • X-PO3 alkali-metaphosphate
  • Each mole of alkali-metaphosphate salt introduces equimolar quantities of P 2 0 5 and alkali oxide, no doubt responsible for P2O5 compositions hovering in the neighborhood of 50% molar (the PLNK system is lower at 33% due to the presence of three alkali oxides rather than two as in other cases).
  • the present invention provides higher-order compositions that include over 50% molar P2O5, leading to several useful alkali-phosphate glasses for heat transfer and storage.
  • the compositions were synthesized using batch components capable of adding P 2 0 5 independently of accompanying alkali oxides. Other oxides and thermally stable compounds were then added to the alkali-phosphate system so as to enhance stability and lower viscosity over very broad temperature ranges.
  • the invention provides glasses containing alkali metal oxides and phosphorus oxide.
  • the oxides of the invention contain phosphorus oxide and at least two oxides selected from lithium oxide, sodium oxide, potassium oxide, and boron oxide.
  • phosphorus oxide refers to P 2 0 5
  • lithium oxide refers to Li 2
  • sodium oxide refers to Na 2
  • potassium oxide refers to K 2 0
  • boron oxide refers to B 2 O 3 .
  • the present invention provides an oxide containing phosphorus oxide, in an amount of from about 25 to about 90 mol%, as well as at least two oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the present invention provides an oxide consisting essentially of phosphorus oxide and two or more oxides selected from lithium oxide, sodium oxide, potassium oxide, and boron oxide in any of the amounts described herein.
  • the oxide consists of phosphorus oxide and two or more oxides selected from lithium oxide, sodium oxide, potassium oxide, and boron oxide in any of the amounts described herein.
  • the oxides of the invention can contain any suitable amount of phosphorus oxide. In general, the oxides contain from about 25 mol% to about 90 mol% phosphorus oxide.
  • the oxides can contain from about 25 to about 75 mol% phosphorus oxide, or from about 50 to about 75 mol% phosphorus oxide, or from about 30 to about 70 mol% phosphorus oxide, or from about 30 to about 60 mol% phosphorus oxide, or from about 25 to about 50 mol% phosphorus oxide, or from about 40 to about 50 mol% phosphorus oxide.
  • the oxides can contain from about 50 to about 90 mol% phosphorus oxide, or about 65 to about 75 mol% phosphorus oxide.
  • the oxides can contain about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or about 80 mol% phosphorus oxide.
  • the oxides of the invention can contain any suitable amount of lithium oxide.
  • the oxides contain from about 0 mol% to about 50 mol% lithium oxide.
  • the oxides can contain, for example, from about 1 to about 50 mol% lithium oxide.
  • the oxides can contain from about 10 to about 50 mol% lithium oxide, or from about 20 to about 50 mol% lithium oxide, or from about 25 to about 50 mol% lithium oxide, or from about 30 to about 50 mol% lithium oxide, or from about 40 to about 50% lithium oxide, or from about 10 to about 40 mol% lithium oxide, or from about 20 to about 30 mol% lithium oxide, or from about 35 to about 45 mol% lithium oxide.
  • the oxides can contain from about 1 to about 25 mol% lithium oxide, or from about 5 to about 15 mol% lithium oxide.
  • the oxides can contain about
  • the oxides of the invention can contain any suitable amount of sodium oxide.
  • the oxides contain from about 0 mol% to about 75 mol% sodium oxide.
  • the oxides can include, for example, from about 1 to about 75 mol% sodium oxide.
  • the oxides can contain from about 5 to about 75 mol% sodium oxide, or from about 10 to about 75 mol% sodium oxide, or from about 25 to about 75 mol% sodium oxide, or from about 50 to about 75% sodium oxide, or from about 10 to about 60 mol%> sodium oxide, or from about 10 to about 55 mol%> sodium oxide, or from about 20 to about 50 mol%> sodium oxide, or from about 20 to about 45 mol%> sodium oxide, or from about 20 to about 40 mol%> sodium oxide, or from about 30 to about 40 mol% sodium oxide.
  • the oxides can contain from about 1 to about 25 mol%> sodium oxide, or from about 5 to about 15 mol%> sodium oxide.
  • the oxides can contain about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11,
  • the oxides of the invention can contain any suitable amount of potassium oxide.
  • the oxides contain from about 0%> to about 75%> potassium oxide.
  • the oxides can include, for example, from about 1 to about 75 mol%> potassium oxide.
  • the oxides can contain from about 1 to about 50 mol% potassium oxide, or from about 1 to about 40 mol% potassium oxide, or from about 1 to about 30 mol% potassium oxide, or from about 1 to about 25% potassium oxide, or from about 5 to about 60 mol% potassium oxide, or from about 10 to about 60 mol% potassium oxide, or from about 10 to about 50 mol% potassium oxide, or from about 10 to about 40 mol% potassium oxide, or from about 10 to about 30 mol% potassium oxide, or from about 10 to about 20 mol% potassium oxide, or from about 30 to about 40 mol% potassium oxide.
  • the oxides can contain about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or about 35 mol% potassium oxide.
  • the oxides of the invention can contain any suitable amount of boron oxide.
  • the oxides contain from about 0% to about 50 mol% boron oxide.
  • the oxides can include, for example, from about 1 to about 50 mol% boron oxide.
  • the oxides can contain from about 5 to about 45 mol% boron oxide, or from about 5 to about 30 mol% boron oxide, or from about 5 to about 20 mol% boron oxide, or from about 1 to about 25 mol% boron oxide, or from about 1 to about 20 mol% boron oxide, or from about 1 to about 10 mol% boron oxide, or from about 1 to about 5 mol% boron oxide.
  • the oxides can contain about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or about 10 mol% boron oxide.
  • the invention provides an oxide containing: phosphorus oxide, in an amount of from about 25 to about 90 mol%; and at least two oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the invention provides an oxide containing: phosphorus oxide, in an amount of from about 25 to about 75 mol%; lithium oxide, in an amount of from about 25 to about 50 mol%; and potassium oxide, in an amount of from about 1 to about 25 mol%.
  • the invention provides oxide containing phosphorus oxide, in an amount of from about 40 to about 50 mol%; lithium oxide, in an amount of from about 35 to about 45 mol%; and potassium oxide, in an amount of from about 10 to about 20 mol%.
  • the oxide contains phosphorus oxide, in an amount of about 45 mol%; lithium oxide, in an amount of about 39 mol%; and potassium oxide, in an amount of about 16 mol%.
  • the oxides contain phosphorus oxide, in an amount of from about 25 to about 75 mol%; sodium oxide, in an amount of from about 5 to about 75 mol%; and potassium oxide, in an amount of from about 5 to about 60 mol%.
  • the oxides contain phosphorus oxide, in an amount of from about 30 to about 70 mol%; sodium oxide, in an amount of from about 10 to about 55 mol%; and potassium oxide, in an amount of from about 10 to about 50 mol%.
  • the oxides of the invention can contain two, three, four, five, or more oxides in addition to phosphorus oxide.
  • the oxides can contain phosphorus oxide and at least three oxides selected from lithium oxide, sodium oxide, potassium oxide, and boron oxide.
  • the oxides can contain phosphorus oxide, lithium oxide, sodium oxide, potassium oxide, and boron oxide.
  • the oxides can contain phosphorus and boron oxide, as well as at least one oxide selected from lithium oxide, sodium oxide, and potassium oxide.
  • the oxides contain phosphorus and boron oxide, as well as at least one oxide selected from calcium oxide, bismuth oxide, and copper oxide.
  • the invention provides an oxide containing phosphorus oxide as described above, and further containing at least three oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the oxide contains lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the oxide contains phosphorus oxide, in an amount of from about 25 to about 90 mol%; and boron oxide, in an amount of from about 1 to about 10 mol%.
  • the oxide further contains at least one oxide selected from lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; and potassium oxide, in an amount of from about 1 to about 75 mol%.
  • the oxide further contains at least one oxide selected from calcium oxide (CaO), in an amount of from about 1 to about 25 mol%; bismuth oxide (Bi 2 0 3 ), in an amount of from about 1 to about 10 mol%; and copper oxide (CuO), in an amount of from about 1 to about 5 mol%.
  • CaO calcium oxide
  • Bi 2 0 3 bismuth oxide
  • CuO copper oxide
  • the oxides of the present invention can include one or more additional components including, but not limited to, potassium fluoride (KF), calcium fluoride (CaF 2 ), vanadium oxide (V 2 0 5 ), lead oxide ( ⁇ 3 ⁇ 40 4 ), zinc oxide (ZnO), and magnesium oxide (MgO).
  • the oxide contains phosphorus oxide, in an amount of from about 25 to about 90 mol%; boron oxide, in an amount of from about 1 to about 10 mol%; and at least one fluoride selected from calcium fluoride and potassium fluoride, in an amount of from about 1 to about 25 mol%, and calcium fluoride, in an amount of from about 1 to about 25 mol%.
  • the oxide contains: phosphorus oxide, in an amount of from about 50 to about 90 mol%; lithium oxide, in an amount of from about 1 to about 25 mol%; sodium oxide, in an amount of from about 1 to about 25 mol%; potassium oxide, in an amount of from about 1 to about 25 mol%; and boron oxide, in an amount of from about 1 to about 10 mol%.
  • the oxide contains: phosphorus oxide, in an amount of from about 65 to about 75 mol%; lithium oxide, in an amount of from about 5 to about 15 mol%; sodium oxide, in an amount of from about 5 to about 15 mol%; potassium oxide, in an amount of from about 5 to about 15 mol%; and boron oxide, in an amount of from about 1 to about 5 mol%.
  • the oxide contains: phosphorus oxide, in an amount of about 72 mol%; lithium oxide, in an amount of about 8.5 mol%; sodium oxide, in an amount of about 8.5 mol%; potassium oxide, in an amount of about 8.5 mol%; and boron oxide, in an amount of about 2.5 mol%.
  • an oxide of the invention can be prepared by weighing specific amounts of suitable starting materials and mechanically grinding or otherwise bringing the starting materials into uniform association with each other. The resulting mixture is then heated in an appropriate container, such as an alumina or porcelain crucible, in a furnace or similar apparatus. Synthesis temperatures can regulated to processes such as foaming, outgassing, and reaction of gaseous components in the batch.
  • Suitable starting materials include, but are not limited to, ammonium dihydrogen phosphate (NH 4 H 2 P0 4 ), boric acid (H 3 BO 3 ), sodium carbonate (Na 2 C0 3 ), sodium sulfate (Na 2 S0 4 ), potassium carbonate (K 2 C0 3 ), potassium sulfate (K 2 S0 4 ), potassium fluoride (KF), lithium carbonate (Li 2 C0 3 ), cuprous oxide (Cu 2 0), bismuth trioxide (Bi 2 0 3 ), calcium carbonate (CaC0 3 ), and calcium fluoride (CaF 2 ).
  • some embodiments of the invention provide methods for making an oxide as described herein.
  • the methods include forming a precursor mixture containing a phosphorus oxide precursor and at least two precursors selected from a lithium oxide precursor, a sodium oxide precursor, a potassium oxide precursor, and a boron oxide precursor.
  • the methods include heating the precursor mixture under conditions sufficient to form the oxide.
  • the phosphorus oxide precursor is ammonium dihydrogen phosphate.
  • the potassium oxide precursor is potassium carbonate.
  • the potassium oxide precursor is potassium sulfate.
  • an oxide prepared using potassium sulfate exhibits a glass melt that is more fluid than a corresponding oxide prepared using potassium carbonate.
  • the temperatures and heating rates used in the methods for preparing the oxides will depend in part on factors such as the particular precursor materials used and the relative quantities of the precursor materials.
  • the present invention provides a method for storing and transporting thermal energy.
  • the method includes heating a composition with thermal energy, wherein the composition includes and oxide containing: phosphorus oxide, in an amount of from about 25 to about 90 mol%, as well as at least two oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • Heating the composition with thermal energy causes the temperature of the composition to increase.
  • the composition includes an oxide containing: phosphorus oxide, in an amount of from about 25 to about 75 mol%; lithium oxide, in an amount of from about 25 to about 50 mol%; and potassium oxide, in an amount of from about 1 to about 25 mol%.
  • the composition includes an oxide containing phosphorus oxide, in an amount of from about 40 to about 50 mol%; lithium oxide, in an amount of from about 35 to about 45 mol%; and potassium oxide, in an amount of from about 10 to about 20 mol%.
  • the composition includes an oxide containing phosphorus oxide, in an amount of about 45 mol%; lithium oxide, in an amount of about 39 mol%; and potassium oxide, in an amount of about 16 mol%.
  • the compositions includes and oxide containing phosphorus oxide, in an amount of from about 25 to about 75 mol%; sodium oxide, in an amount of from about 5 to about 75 mol%; and potassium oxide, in an amount of from about 5 to about 60 mol%.
  • the compositions includes an oxide containing phosphorus oxide, in an amount of from about 30 to about 70 mol%; sodium oxide, in an amount of from about 10 to about 55 mol%; and potassium oxide, in an amount of from about 10 to about 50 mol%.
  • the composition includes an oxide containing phosphorus oxide as described above, and further containing at least three oxides selected from: lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the oxide contains lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; potassium oxide, in an amount of from about 1 to about 75 mol%; and boron oxide, in an amount of from about 1 to about 50 mol%.
  • the composition includes an oxide containing phosphorus oxide, in an amount of from about 25 to about 90 mol%, and boron oxide, in an amount of from about 1 to about 10 mol%.
  • the oxide in the composition further contains at least one oxide selected from lithium oxide, in an amount of from about 1 to about 50 mol%; sodium oxide, in an amount of from about 1 to about 75 mol%; and potassium oxide, in an amount of from about 1 to about 75 mol%.
  • the oxide in the composition further contains at least one oxide selected from calcium oxide, in an amount of from about 1 to about 25 mol%; bismuth oxide, in an amount of from about 1 to about 10 mol%; and copper oxide, in an amount of from about 1 to about 5 mol%.
  • the composition includes an oxide containing phosphorus oxide, in an amount of from about 25 to about 90 mol%; boron oxide, in an amount of from about 1 to about 10 mol%; and at least one fluoride selected from potassium fluoride, in an amount of from about 1 to about 25 mol%, and calcium fluoride, in an amount of from about 1 to about 25 mol%.
  • the composition includes and oxide containing: phosphorus oxide, in an amount of from about 50 to about 90 mol%; lithium oxide, in an amount of from about 1 to about 25 mol%; sodium oxide, in an amount of from about 1 to about 25 mol%; potassium oxide, in an amount of from about 1 to about 25 mol%; and boron oxide, in an amount of from about 1 to about 10 mol%.
  • the composition includes and oxide containing: phosphorus oxide, in an amount of from about 65 to about 75 mol%; lithium oxide, in an amount of from about 5 to about 15 mol%; sodium oxide, in an amount of from about 5 to about 15 mol%; potassium oxide, in an amount of from about 5 to about 15 mol%; and boron oxide, in an amount of from about 1 to about 5 mol%.
  • the composition includes and oxide containing: phosphorus oxide, in an amount of about 72 mol%; lithium oxide, in an amount of about 8.5 mol%;
  • sodium oxide in an amount of about 8.5 mol%
  • potassium oxide in an amount of about 8.5 mol%
  • boron oxide in an amount of about 2.5 mol%.
  • compositions consisting essentially of any of the oxides described above are used in the methods of the invention. In some embodiments,
  • compositions consisting of any of the oxides described above are used in the methods of the invention.
  • heating the composition with or otherwise exposing the composition to thermal energy causes the temperature of the composition to increase.
  • the temperature of the composition can increase, for example, by from about 1 °C to about 750 °C. In some embodiments, the temperature of the composition can increase by about 5 °C, 10, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, or by about 700 °C.
  • the temperature of the composition can increase to a temperature of about 30, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 °C, or greater.
  • thermo energy can be used in the methods of the invention.
  • Useful thermal sources include, but are not limited to, a concentrated solar power plant, a fossil fuel power plant, a nuclear power plant, sunlight, a geothermal source, fuel combustion, and a heat pump.
  • the thermal source can also be waste heat from an industrial process (e.g., metal production or glass production).
  • the invention provides a method for storing thermal energy as described above, wherein the thermal energy originates from a source selected from the group consisting of sunlight, a concentrated solar power plant, a fossil fuel power plant, fuel combustion, an industrial process, and a heat pump. V. Examples
  • Example 1 Phosphorus-lithium-potassium (PLK) reference composition
  • the alleged 340 °C eutectic composition can be synthesized from a variety of batch components.
  • the simplest route to synthesis was calculated as 29.4 mol% K 3 PO 4 and 70.6 mol% (LiP0 3 ) 3 .
  • a small, 10 g batch was synthesized and observed qualitatively during stages of melting.
  • the PLK glass was melted at 800 °C with little outgassing, forming a clear, vitreous, and fluid liquid.
  • vitreous glass character was maintained but with steeply increased viscosity. By 425-400 °C, the glass no longer flowed under the influence of gravity.
  • compositions of phosphorus pentoxide via ammonium di-hydrogen phosphate
  • sodium oxide via sodium carbonate
  • potassium oxide via potassium carbonate
  • Example 3 Alkali phosphate glasses
  • Weight percent conversions from starting batch materials to final oxide materials can be calculated as follows.
  • K 2 S0 4 (g) * (94.2 (g/mol) K 2 0)/(174.26 (g/mol) K 2 S0 4 ) K 2 0 (g)
  • Li 2 C0 3 (g) * (29.88 (g/mol) Li 2 0)/(73.89 (g/mol) Li 2 C0 3 ) Li 2 0 (g)
  • CaC0 3 (g) * (56.07 (g/mo) CaO)/(l 00.09 (g/mol) CaC0 3 ) CaO (g)
  • ADP adds half a mole of P 2 O 5 for every mole of batch component and exhibits low hygroscopic behavior. ADP also adds a considerable weight percentage of ammonia (NH 3 ) and water (H 2 0) to the melt. During heating, considerable outgassing occurs, such that the heating rate must be carefully controlled to prevent excessive foaming and subsequent furnace damage. This challenge aside, ADP's gas content is believed to be beneficial to the melt's overall fluidity. Without wishing to be bound by any particular theory, trapped gaseous molecules are believed to increase the concentration of non-bonding oxygen in the melt, leading to decreased viscosity as a result of less internal molecular resistance to flow.
  • K 2 SO 4 has greater thermal stability than K 2 CO 3 , resulting in a higher concentration of SO x gas in the melt. This is believed to contribute to a more fluid glass melt, where the gases create non-bonding oxygen connections that reduce the liquid's resistance to flow.
  • Another benefit of K 2 SO 4 is that it is available at a third of the cost of K 2 CO 3 .
  • composition in Table 3 was weighed using an analytical balance, mechanically ground via mortar and pestle, and synthesized in alumina or porcelain crucibles in time-and- temperature programmable furnaces capable of reaching 1200 °C. While no DSC thermal analysis (liquidus, glass transition, heat capacity, heat of fusion) was initially conducted with these samples, viscosity and crystallization dynamics were qualitatively observed over all temperatures (400 - 1200 °C) through numerous thermal cycles to assess repeatability.
  • Example 4 Physical characterization of a novel alkali-phosphate glass.
  • glass 3i The chemical composition of glass 3i resulted in an unexpected combination of favorable physical properties. Of the 62 glass samples surveyed, glass 3i exhibited superior fluid properties, thermal properties, materials compatibility. The glass itself is completely clear, which can be advantageous in a solar receiver designed to utilize infrared radiation.
  • a significant weight percent of glass batch components will be outgassed during melting, where a majority of the gas released will be NH 3 . There will also be smaller quantities of C0 2 , H 2 0, and SO x released during batch component melting. As a result, slow, controlled heating to 500 °C should be conducted with foaming and outgassing occurring below this temperature. Careful control can prevent violent reaction of the gaseous elements incorporated into the batch. After holding at 500 °C for several hours, the melt can be ramped to 1100 °C for final outgassing.
  • Graphite crucible/liner materials, including an inert N 2 gas purge should be used, because phosphate glasses are particularly sensitive to corrosion and pollution from alumina-based refractory ceramics.
  • Viscosity was subsequently measured using a molten glass viscometer (Orton 1600V) at 400 - 1180 °C, with results summarized in Table 4 and shown in Figure 3. The viscosity of the glass over these temperatures is well within the range necessary for use with molten glass pump apparatuses. [0077] The heat capacity of the glass was measured using a Netzsch Fl Pegasus 404 autosampler DSC. Heat capacity data is displayed below in Figure 4.
  • the liquidus temperature (410 °C) for glass 5a was measured via differential scanning calorimetry (DSC), with the data trace depicted in Figure 5. Based upon high temperature furnace tests with glasses of similar composition, the glass is expected to be stable to 1200 °C with minimal weight loss or thermal decomposition for heat transfer and thermal storage applications.
  • Example 6 Na?Q-CaO-P?0_s-B?C -V?Cs glass (Green glass)
  • This is a molten glass oxide composition comprised of sodium (I), phosphorus (V), calcium (II), boron (III), and vanadium (V) oxides.
  • the original Na 2 0-CaO-P 2 0 5 -B 2 0 3 components were kept in the same ratio relative to one another, while the levels of vanadium pentoxide were varied over six compositions.
  • the best overall composition tested included approximately 8% by weight of vanadium pentoxide. See, Table 7.
  • the glass is referred to here as Green glass because of the emerald green color it assumes upon quench cooling. Table 7.
  • Composition of glass 6a Green glass
  • the liquidus temperature (422 °C) for the Green glass was measured via differential scanning calorimetry (DSC), with the data trace depicted in Figure 6a. Additionally, the DSC measured a heat capacity of 1.44 J/g-K. Green glass is stable to 1200 °C, as measured by negligible weight loss in a muffle furnace at this upper temperature limit for several hours. Green glass was also subjected to thermo gravimetric analysis (TGA) to show that there was minimal weight loss at temperatures up to 1000 °C (the maximum operating range of that instrument). See, Figure 6b.
  • TGA thermo gravimetric analysis
  • Example 7 Green glass + K?0 [0083] This is a molten glass oxide composition comprised of sodium (I), phosphorus (V), calcium (II), boron (III), vanadium (V), and potassium (I) oxides.
  • the original Green glass components were kept in the same ratio relative to one another, while the levels of potassium oxide were varied to replace sodium oxide over five compositions.
  • the best overall composition tested, glass 7a included approximately 16% by weight of potassium oxide. See, Table 8:
  • This is a molten glass oxide composition comprised of sodium (I), phosphorus (V), calcium (II), boron (III), vanadium (V), potassium (I), and zinc (II) oxides.
  • the original glass 7a components were kept in the same ratio relative to one another, while the levels of zinc oxide were varied to replace some calcium oxide over three compositions.
  • the best overall composition tested, glass 8a included approximately 2% by weight of zinc oxide. See, Table 9:
  • liquidus temperature (380 °C) for glass 8a was measured via differential scanning calorimetry (DSC), with the data trace depicted in Figure 8. Earlier melting onset and liquidus temperatures were observed, along with much lower viscosity, than the other glasses. Based upon high temperature furnace tests with glasses of similar composition, glass 8a is expected to be stable to 1200 °C with minimal weight loss or thermal decomposition for heat transfer and thermal storage applications.
  • E490 is a glass composition of sodium (I) and phosphorus (V) oxides derived from the extensive literature of binary and ternary oxide phase diagrams and eutectics.
  • E490 was synthesized at the eutectic region, with mol% 55.9 Na 2 0 - 44.1 P 2 0 5 .
  • This composition's glass transition (386 °C) and liquidus temperatures (580 °C) were measured via differential scanning calorimetry (DSC), with the data trace depicted in Figure 9.
  • DSC differential scanning calorimetry
  • E490 is expected to be stable to 1200 °C with minimal weight loss or thermal decomposition for heat transfer and thermal storage applications.
  • Example 10 E410 (glass 10)
  • E410 is a glass composition of sodium (I), phosphorus (V), and calcium (II) oxides derived from the extensive literature of binary and ternary oxide phase diagrams and eutectics [4]. This was the last composition screened before moving to higher-order oxide
  • E410 was synthesized at the eutectic region, with mol% 49.1 Na 2 0 - 44.2 P 2 0 5 - 6.7 CaO. E410's glass transition (283 °C) and liquidus temperatures (495 °C) were measured via differential scanning calorimetry (DSC), with the data trace depicted in Figure 10. The addition of calcium oxide to E490 results in E410, with an 85 °C liquidus melting point reduction. Based upon high temperature furnace tests with glasses of similar composition, E410 is expected to be stable to 1200 °C with minimal weight loss or thermal decomposition for heat transfer and thermal storage applications. [0091] Molten glasses were visually observed in a molten state by manual agitation in a crucible.

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Abstract

La présente invention concerne un système de mélanges d'oxydes. Ces compositions peuvent avoir des températures de liquidus inférieure à 400 °C et des limites de stabilité thermique supérieures à 1200 °C. De telles compositions d'oxydes présentent une faible viscosité sur toute leur plage de stabilité, ce qui permet de les pomper en tant que fluide de transfert thermique et milieu de stockage thermique avec de faibles pertes d'énergie parasites.
PCT/US2013/069313 2012-11-08 2013-11-08 Verre liquide à base de phosphore, à faible viscosité, à très faible coût pour le transfert thermique et le stockage d'énergie thermique WO2014074930A1 (fr)

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US9728288B2 (en) 2010-02-18 2017-08-08 Terrapower, Llc Method, system, and apparatus for the thermal storage of energy generated by multiple nuclear reactor systems
US9748007B2 (en) 2010-02-18 2017-08-29 Terrapower, Llc Method, system, and apparatus for the thermal storage of energy generated by multiple nuclear reactor systems
US9761337B2 (en) 2010-02-18 2017-09-12 Terrapower, Llc Method, system, and apparatus for the thermal storage of nuclear reactor generated energy
US10438705B2 (en) 2014-12-29 2019-10-08 Terrapower, Llc Fission reaction control in a molten salt reactor
US10535437B2 (en) 2010-02-18 2020-01-14 Terrapower, Llc Method, system, and apparatus for the thermal storage of nuclear reactor generated energy
US10665356B2 (en) 2015-09-30 2020-05-26 Terrapower, Llc Molten fuel nuclear reactor with neutron reflecting coolant
US10734122B2 (en) 2015-09-30 2020-08-04 Terrapower, Llc Neutron reflector assembly for dynamic spectrum shifting
US10741293B2 (en) 2016-05-02 2020-08-11 Terrapower, Llc Molten fuel reactor cooling and pump configurations
US10867710B2 (en) 2015-09-30 2020-12-15 Terrapower, Llc Molten fuel nuclear reactor with neutron reflecting coolant
US10914293B2 (en) 2018-06-20 2021-02-09 David Alan McBay Method, system and apparatus for extracting heat energy from geothermal briny fluid
US10923238B2 (en) 2016-11-15 2021-02-16 Terrapower, Llc Direct reactor auxiliary cooling system for a molten salt nuclear reactor
US11075015B2 (en) 2018-03-12 2021-07-27 Terrapower, Llc Reflectors for molten chloride fast reactors
US11075013B2 (en) 2016-07-15 2021-07-27 Terrapower, Llc Removing heat from a nuclear reactor by having molten fuel pass through plural heat exchangers before returning to core
US11145424B2 (en) 2018-01-31 2021-10-12 Terrapower, Llc Direct heat exchanger for molten chloride fast reactor
US11276503B2 (en) 2014-12-29 2022-03-15 Terrapower, Llc Anti-proliferation safeguards for nuclear fuel salts
US11373765B2 (en) 2016-08-10 2022-06-28 Terrapower, Llc Electro-synthesis of uranium chloride fuel salts
US11728052B2 (en) 2020-08-17 2023-08-15 Terra Power, Llc Fast spectrum molten chloride test reactors
US11881320B2 (en) 2019-12-23 2024-01-23 Terrapower, Llc Molten fuel reactors and orifice ring plates for molten fuel reactors

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US9748007B2 (en) 2010-02-18 2017-08-29 Terrapower, Llc Method, system, and apparatus for the thermal storage of energy generated by multiple nuclear reactor systems
US9761337B2 (en) 2010-02-18 2017-09-12 Terrapower, Llc Method, system, and apparatus for the thermal storage of nuclear reactor generated energy
US10535437B2 (en) 2010-02-18 2020-01-14 Terrapower, Llc Method, system, and apparatus for the thermal storage of nuclear reactor generated energy
US9728288B2 (en) 2010-02-18 2017-08-08 Terrapower, Llc Method, system, and apparatus for the thermal storage of energy generated by multiple nuclear reactor systems
US11205523B2 (en) 2010-02-18 2021-12-21 Terrapower, Llc Method, system, and apparatus for the thermal storage of nuclear reactor generated energy
US11170901B2 (en) 2014-12-29 2021-11-09 Terrapower, Llc Fission reaction control in a molten salt reactor
US10438705B2 (en) 2014-12-29 2019-10-08 Terrapower, Llc Fission reaction control in a molten salt reactor
US11276503B2 (en) 2014-12-29 2022-03-15 Terrapower, Llc Anti-proliferation safeguards for nuclear fuel salts
US10665356B2 (en) 2015-09-30 2020-05-26 Terrapower, Llc Molten fuel nuclear reactor with neutron reflecting coolant
US10734122B2 (en) 2015-09-30 2020-08-04 Terrapower, Llc Neutron reflector assembly for dynamic spectrum shifting
US11798694B2 (en) 2015-09-30 2023-10-24 Terrapower, Llc Molten fuel nuclear reactor
US10867710B2 (en) 2015-09-30 2020-12-15 Terrapower, Llc Molten fuel nuclear reactor with neutron reflecting coolant
US11367536B2 (en) 2016-05-02 2022-06-21 Terrapower, Llc Molten fuel reactor thermal management configurations
US10741293B2 (en) 2016-05-02 2020-08-11 Terrapower, Llc Molten fuel reactor cooling and pump configurations
US11075013B2 (en) 2016-07-15 2021-07-27 Terrapower, Llc Removing heat from a nuclear reactor by having molten fuel pass through plural heat exchangers before returning to core
US11373765B2 (en) 2016-08-10 2022-06-28 Terrapower, Llc Electro-synthesis of uranium chloride fuel salts
US10923238B2 (en) 2016-11-15 2021-02-16 Terrapower, Llc Direct reactor auxiliary cooling system for a molten salt nuclear reactor
US11488731B2 (en) 2016-11-15 2022-11-01 Terrapower, Llc Direct reactor auxiliary cooling system for a molten salt nuclear reactor
US11145424B2 (en) 2018-01-31 2021-10-12 Terrapower, Llc Direct heat exchanger for molten chloride fast reactor
US11791057B2 (en) 2018-03-12 2023-10-17 Terrapower, Llc Reflectors for molten chloride fast reactors
US11075015B2 (en) 2018-03-12 2021-07-27 Terrapower, Llc Reflectors for molten chloride fast reactors
US11225951B2 (en) 2018-06-20 2022-01-18 David Alan McBay Method, system and apparatus for extracting heat energy from geothermal briny fluid
US11692530B2 (en) 2018-06-20 2023-07-04 David Alan McBay Method, system and apparatus for extracting heat energy from geothermal briny fluid
US10914293B2 (en) 2018-06-20 2021-02-09 David Alan McBay Method, system and apparatus for extracting heat energy from geothermal briny fluid
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US11728052B2 (en) 2020-08-17 2023-08-15 Terra Power, Llc Fast spectrum molten chloride test reactors

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